WO2022182082A1 - Photosensitive laminate, preparation method of photosensitive laminate, and preparation method of circuit board - Google Patents

Abstract

The present invention relates to a photosensitive laminate and a preparation method of the photosensitive laminate, the photosensitive laminate comprising: a support substrate; and a photosensitive resin layer comprising an alkali developable binder resin and a photopolymerizable compound which comprises an ester-based monomer or oligomer, wherein at most 5/mm2 bubbles having a diameter of less than 1 µm are present in the photosensitive resin layer.

Description

Photosensitive laminate, photosensitive laminate manufacturing method, and circuit board manufacturing method

Cross-Citation with Related Application(s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2021-0026802 dated February 26, 2021, and all contents disclosed in the literature of the Korean patent application are incorporated as a part of this specification.

The present invention relates to a photosensitive laminate, a method for manufacturing a photosensitive laminate, and a method for manufacturing a circuit board.

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. .

Recently, high-density circuit boards are required in accordance with the trend toward light, thin, compact, and multi-stage packaging of semiconductor devices. A manufacturing process of a circuit board using

Accordingly, there is a continuous demand for the development of a method and process that realizes high density and sensitivity while securing higher reliability, and enables the formation of finer wiring.

Prior art literature

Patent Literature

(Patent Document 1) Japanese Patent Application Laid-Open No. 2006-106287 (published on: April 20, 2006)

An object of the present invention is to provide a photosensitive laminate capable of reducing defects in the formation of fine wiring, and ensuring high reliability during development, and capable of forming high-density circuits.

Moreover, this invention is for providing the manufacturing method of the said photosensitive laminated body.

Moreover, this invention relates to the manufacturing method of the circuit board using the said photosensitive laminated body.

In the present specification, a supporting substrate; and a photosensitive resin layer comprising a photopolymerizable compound comprising an ester-based monomer or oligomer and an alkali developable binder resin, wherein the number of bubbles having a diameter of less than 1 μm in the photosensitive resin layer is 5/mm ² or less. Existing photosensitive laminates can be provided.

Also, in the present specification, a method for manufacturing a circuit board using the photosensitive laminate may be provided.

Also, in the present specification, a method for manufacturing the photosensitive laminate may be provided.

Hereinafter, the photosensitive laminate, the photosensitive laminate manufacturing method, and the circuit board manufacturing method according to specific embodiments of the present invention will be described in more detail.

In this specification, in this specification, a weight average molecular weight means the weight average molecular weight of polystyrene conversion 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 Ⅱ System, RI Detector was used as a detector for measurement at 40°C.

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

In this specification, "(photo)cured product" or "(photo)cured" means not only when all of the components having an unsaturated group that can be cured or crosslinked in the chemical structure are cured, crosslinked or polymerized, but also a part of it is cured , cross-linked or polymerized.

In this specification, (meth)acrylate means acrylate or methacrylate.

According to one embodiment of the invention, a supporting substrate; and a photosensitive resin layer comprising a photopolymerizable compound comprising an ester-based monomer or oligomer and an alkali developable binder resin, wherein 5 bubbles/mm2 or less exist in the photosensitive resin layer having a diameter of less than 1 μm A photosensitive laminate may be provided.

The present inventors have newly developed a photosensitive laminate including a photosensitive resin layer having 5 cells/mm ² or less of cells having a diameter of less than 1 μm. Through experimentation, it was confirmed through experiments that high sensitivity and high reliability can be realized during development, and high density and sensitivity can be realized while securing high reliability, and the formation of finer wiring is possible.

The present inventors have continued research and development to remove traces of fine bubbles or fine by-products that may occur for various reasons in the manufacturing process, and have a boiling point of 115° C. or higher as described in the method for manufacturing a photosensitive laminate to be described later. By forming the photosensitive resin layer by using a resin composition comprising an alkali developable binder resin, a photopolymerizable compound and a photoinitiator together with a mixed solvent including a high boiling point solvent and a low boiling point solvent having a boiling point of 100° C. or less, in the photosensitive resin layer Bubbles having a diameter of less than 1 μm were allowed to exist at 5/mm ² or less, or 3/mm ² or less.

Further, in the method for producing the photosensitive laminate, in addition to using a mixed solvent including a high boiling point solvent having a boiling point of 115° C. or higher and a low boiling point solvent having a boiling point of 100° C. or lower, a drying rate and/or a drying temperature The amount of microbubbles formed in the photosensitive resin layer can be greatly reduced or substantially absent through adjustment of the .

On the other hand, the number of bubbles having a diameter of less than 1 μm in the photosensitive resin layer may be 5 / mm ² or less, or 3 / mm ² or less, in particular the opposite surface of the interface between the support substrate and the photosensitive resin layer, or Bubbles having a diameter of less than 1 μm toward the outer surface of the photosensitive resin layer may be present in a trace amount or substantially absent.

More specifically, within 50% of the total thickness of the photosensitive resin layer from the opposite surface of the interface between the support substrate and the photosensitive resin layer, 3 bubbles/mm ² or less having a diameter of less than 1 μm may be present.

As a small amount or substantially no air bubbles having a diameter of less than 1 μm are present on the opposite surface of the interface between the supporting substrate and the photosensitive resin layer, or toward the outer surface of the photosensitive resin layer, It is possible to form high-density circuits due to increased reliability during development and to reduce defects in the formation of fine wiring. Accordingly, when using the photosensitive laminate, high sensitivity to exposure can be realized, and high-density printed circuit boards can be manufactured. yield can be improved.

In addition, the photosensitive laminate may not only contain a very small amount or substantially not contain the above-mentioned bubbles having a diameter of less than 1 μm, but also may not include bubbles having a diameter of 1 μm to 5 μm.

As described above, using the photosensitive laminate in which bubbles having a diameter of less than 1 μm are present in a trace amount in the photosensitive resin layer, high reliability and high density and sensitivity are achieved while manufacturing circuit boards, and finer wiring is formed. can do.

More specifically, even if the photosensitive resin layer is exposed to ultraviolet light and developed with an alkaline solution, defects do not occur over the entire area or may occur in a very small amount, especially on the upper surface of the photosensitive resin layer. This is not substantially present, and micro-sized defects may exist in a very small amount on the lower surface or inside of the photosensitive resin layer after development.

Specifically, after exposing the photosensitive resin layer to ultraviolet light and developing with an alkaline solution, a defect having a cross-sectional diameter of 0.3 μm or more to 4 μm or less, 0.5 μm or more and 4 μm or less, or 0.5 μm or more and 3 μm or less These 3 pieces/mm ² or less, 2 pieces/mm ² or less, or 1 piece/mm ² or less may be observed, and may be substantially absent. The cross-sectional diameter of the defect may be defined as the largest diameter among diameters of the bond defined in a cross-section in one direction on the photosensitive resin layer.

The conditions of the exposure and development are not particularly limited. For example, in the exposure, the wavelength of the light irradiated to the photosensitive laminate is in the range of 340 nm to 420 nm, and the remaining number of steps measured using a 41-step step tablet manufactured by Stouffer Graphic Arts Equipment is 15 steps. It may proceed from 1 minute to 60 minutes. In addition, the development may be carried out by a method such as a spray spray method with an aqueous alkali solution such as Na ₂ CO ₃ having a concentration of 0.1 to 3.0 wt%.

In addition, when the photosensitive laminate is used, higher density and sensitivity can be realized while using lower energy. More specifically, the amount of energy at which the remaining number of steps is 15 steps measured using a 41-step step tablet manufactured by Stouffer Graphic Arts Equipment in a wavelength range of 340 nm to 420 nm of the light irradiated to the photosensitive laminate is 300 mJ/cm 2 It may be less than or equal to 100 mJ/cm 2 , and the resolution after development may be realized to be less than or equal to 15 μm or less than or equal to 10 μm.

In the photosensitive laminate, the thickness of the supporting substrate and the photosensitive resin layer is not particularly limited, but in a specific example, the thickness of the supporting substrate is 1 μm to 100 μm, 5 μm to 100 μm, 5 μm to 80 μm, or 5 μm. to 50 μm, and the thickness of the photosensitive resin layer may be 1 μm to 100 μm, 5 μm to 100 μm, 5 μm to 80 μm, or 5 μm to 50 μm.

On the other hand, the characteristics of the photosensitive laminate or the constitutional characteristics in which 5 cells/mm ² or less of bubbles having a diameter of less than 1 μm are present in the photosensitive resin layer may be attributed to the above-described manufacturing method, and the photosensitive number It may be due to the characteristics of the strata.

Specifically, the photosensitive resin layer may include an alkali developable binder resin. The alkali developable binder may include at least one carboxyl group in a molecule to react with alkali during the development process.

Specific examples of the alkali developable binder are not limited, but at least one repeating unit selected from the group consisting 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 It may be a polymer or a copolymer comprising

[Formula 4]

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

[Formula 5]

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

[Formula 6]

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

In Formulas 4 to 6, 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

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

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 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, R ₃ is hydrogen or alkyl having 1 to 10 carbon atoms. In Formula 4-1, the contents of R ₃ are the same as those described above in Formula 4 above. Specific examples of the monomer represented by Formula 4-1 include acrylic acid (AA) and methacrylic acid (MAA).

The repeating unit represented by the formula (5) may be a repeating unit derived from a monomer represented by the following formula (5-1).

[Formula 5-1]

In Formula 5-1, 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 5-1, R ₄ and R ₅ are the same as described above in Formula 5. Specific examples of the monomer represented by Formula 5-1 include methyl (meth)acrylate (MMA) and butyl acrylate (BA).

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

[Formula 6-1]

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

On the other hand, the alkali developable binder resin may serve as a base material for the photosensitive resin layer, and thus should have a minimum molecular weight, for example, 20,000 g/mol to 300,000 g/mol, 20,000 g/mol to 200,000 g It may have a weight average molecular weight of /mol, 30,000 g/mol to 200,000 g/mol, or 30,000 g/mol to 150,000 g/mol.

In addition, the alkali developable binder resin should have heat resistance of at least a certain level, and accordingly, 20 ℃ or more and 150 ℃ or less, 30 ℃ or more and 150 ℃ or less, 50 ℃ or more and 150 ℃ or less, 50 ℃ or more and 130 ℃ or less, 70 ℃ or more It may have a glass transition temperature of 130 °C or less, or 70 °C or more and 120 °C or less.

In addition, the alkali developable binder resin is 100 mgKOH/g or more and 300 mgKOH/g or less, 120 mgKOH/g or more and 300 mgKOH/g or less, 120 mgKOH/g or more and 250 mgKOH in consideration of the developability of the photosensitive resin layer. It may have an acid value of /g or less, 120 mgKOH/g or more and 200 mgKOH/g or less, or 140 mgKOH/g or more and 160 mgKOH/g or less.

Meanwhile, the alkali developable binder resin may include two or more alkali developable binders having different types or different properties. Specifically, the alkali developable binder resin may include a first alkali developable binder resin and a second alkali developable binder resin.

The first alkali developable binder resin and the second alkali developable binder resin have a weight average molecular weight of 30000 g/mol or more and 150000 g/mol or less, 20,000 g/mol to 200,000 g/mol, 30,000 g/mol to 200,000 g/mol mol, or 30,000 g/mol to 150,000 g/mol, and the glass transition temperature is 20 ℃ or more and 150 ℃ or less, 30 ℃ or more and 150 ℃ or less, 50 ℃ or more and 150 ℃ or less, 50 ℃ or more and 130 ℃ or less, 70 ℃ or more 130 ℃ or less, or 70 ℃ or more and 120 ℃ or less, respectively, may have different weight average molecular weight, glass transition temperature, or acid value.

For example, the first alkali developable binder resin has an acid value of 100 mgKOH/g or more, 300 mgKOH/g, 120 mgKOH/g or more, 300 mgKOH/g, 120 mgKOH/g or more, 250 mgKOH/g, 120 mgKOH/g or more 200 mgKOH/g, or 140 mgKOH/g or more and 160 mgKOH/g or less. In addition, the second alkali developable binder resin has an acid value of 100 mgKOH/g or more 300 mgKOH/g, 120 mgKOH/g or more 300 mgKOH/g, 120 mgKOH/g or more 250 mgKOH/g, 120 mgKOH/g or more 200 mgKOH/g g, or 160 mgKOH/g or more and 200 mgKOH/g or less.

In addition, 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 1:75 or less, or 1:1.6 or more and 1:7 or less.

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

Meanwhile, as described above, the photosensitive resin layer may include a photopolymerizable compound including an ester-based monomer or oligomer and an alkali developable binder resin. More specifically, the photosensitive resin layer may include a crosslinked copolymer between an alkali developable binder resin and a photopolymerizable compound including a (meth)acrylate monomer or oligomer.

The photopolymerizable compound including the ester-based monomer or oligomer may serve as a crosslinking agent to increase mechanical strength of the photosensitive resin layer, etc. or to increase resistance to a developer and to provide flexibility of the cured film.

In addition, by using the photopolymerizable compound including the ester-based monomer or oligomer, the photosensitive resin layer can have a higher adhesion to the supporting base, and the development time or peeling time of the photosensitive laminate can be greatly shortened. have.

Specific examples of the ester-based monomer or oligomer include (meth)acrylate in which one or more hydroxyl groups, epoxy groups, or amine groups are bonded.

In the (meth)acrylate to which one or more hydroxyl groups, epoxy groups, or amine groups are bonded, the (meth)acrylate functional group is located at one end, and at least one of a hydroxyl group, an epoxy group, or an amine group is located at the other end. and a divalent organic functional group may be bonded as a medium between the (meth)acrylate functional group and the functional group of a hydroxyl group, an epoxy group, or an amine group.

In addition, a more specific example of the ester-based monomer or oligomer may include a compound of Formula 1 below.

[Formula 1]

CH ₂ =CR ¹ -COO-R ² -OH

In Formula 1, R ¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ² is a divalent saturated aliphatic hydrocarbon group having 1 to 100, or 2 to 50 carbon atoms, and the saturated aliphatic hydrocarbon group is optionally a halogen atom, ether It may contain a bond (-O-), an ester bond (-COO- or O-CO-), an amide bond (-NHCO- or CONH-) or an aryl group.

More specifically, the ester-based monomer or oligomer is glycerol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol monoacrylate, hydroxypropyl (meth) ) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol mono acrylate, poly (ethylene glycol propylene glycol) - mono (meth) acrylate, polyethylene glycol polypropylene glycol - mono (meth) acrylate, poly (Ethylene glycol tetramethylene glycol)-mono(meth)acrylate (trade name: Blemmer 55 PET-800, etc.), poly(propylene glycol tetramethylene glycol)-mono(meth)acrylate, propylene glycol polybutylene glycol-mono( meth)acrylate, 2-hydroxyethylacrylate, 2-hydroxypropylacrylate, 4-hydroxybutylacrylate, 1,4-cyclohexanedimethanol monoacrylate, or a mixture of two or more thereof. can do.

Although the weight average molecular weight of the ester-based monomer or oligomer is not particularly limited, for example, 50 g/mol to 10,000 g/mol, or 70 g/mol to 5,000 g/mol, or 80 g/mol to 1,200 g/mol mol, or may have a weight average molecular weight of 100 g/mol to 1,000 g/mol.

According to the specific use or characteristics of the photosensitive resin layer, the content of the photopolymerizable compound including the ester-based monomer or oligomer can be adjusted, for example, an ester-based monomer or oligomer relative to 100 parts by weight of the alkali developable binder resin. 1 to 80 parts by weight, 5 to 80 parts by weight, 5 to 70 parts by weight, 10 to 70 parts by weight, 10 to 60 parts by weight, 10 to 50 parts by weight, 25 to 50 parts by weight, or 30 to 50 parts by weight of the photopolymerizable compound comprising It may contain parts by weight.

That is, the photosensitive laminate of the embodiment is used by mixing two or more solvents having different boiling points as described in the manufacturing method to be described later, and by selecting a photopolymerizable compound including an ester-based monomer or oligomer, the number of photosensitivities Microbubbles may or may not be present in trace amounts within the formation.

Specifically, due to the structure and characteristics of the photopolymerizable compound including the ester-based monomer or oligomer, it is possible to cause a small amount of air bubbles having a diameter of 1 μm or less to exist in the photosensitive resin layer, thereby forming fine wiring. A photosensitive laminate can be provided that can reduce defects in , and can form high-density circuits by ensuring high reliability during development.

Meanwhile, the photopolymerizable compound may further include a monofunctional or polyfunctional (meth)acrylate monomer or oligomer. As the photopolymerizable compound, a commonly known monofunctional or polyfunctional (meth)acrylate monomer or oligomer may be used.

Examples of the additionally usable photopolymerizable compound are not particularly limited, but ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth) Acrylate (tetraethylene glycol dimethacrylate), propylene glycol di (meth) acrylate (propylene glycol dimethacrylate), polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate (polypropylene glycol dimethacrylate), butylene glycol di (meth) acrylate (butylene glycol dimethacrylate), neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate (1,6-hexane glycol dimethacrylate), trimethylol Propane tri(meth)acrylate, trimethylolpropane triacrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol dimethacrylate Erythritol tri (meth) acrylate (pentaerythritol trimethacrylate), dipentaerythritol penta (meth) acrylate (dipentaerythritol pentamethacrylate), 2,2-bis (4-methacryloxy diethoxyphenyl) propane (2,2-bis (4-methacryloxydiethoxyphenyl) propane), 2,2-bis (4-methacryloxy polyethoxyphenyl) propane (2,2-bis (4-methacryloxypolyethoxyphenyl) propane), 2-hydroxy-3-methacryloyl Oxypropyl (meth)acrylate t(2-hydroxy-3-methacryloyloxypropyl methacrylate), ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate (diethylene glycol) diglycidyl ether dimethacrylate), phthalic acid diglycidyl ester dimethacrylate, glycerin polyglycidyl ether polymethacrylate, and polyfunctional urethane groups (meth)acrylate etc. are mentioned.

According to the specific use or characteristics of the photosensitive resin layer, the content of the monofunctional (meth) acrylate compound or the polyfunctional (meth) acrylate compound can be adjusted, for example, the photopolymerizable compound is the ester-based monomer or The monofunctional (meth)acrylate compound or the polyfunctional (meth)acrylate compound may be included in an amount of 50 to 500 parts by weight based on 100 parts by weight of the oligomer.

On the other hand, the supporting substrate may serve as a support for the photosensitive laminate, and may facilitate handling of the photosensitive resin layer having adhesive force during exposure.

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.

Meanwhile, the photosensitive laminate may further include a protective film formed to face the supporting substrate with the photosensitive resin layer as a center. 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 may be 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 adhesion so that it does not release 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 100 μm.

Meanwhile, according to another embodiment of the present invention, a mixed solvent comprising a high boiling point solvent having a boiling point of 115° C. or higher and a low boiling point solvent having a boiling point of 100° C. or less; a photopolymerizable compound including an ester-based monomer or oligomer; alkali developable binder resin; and a photoinitiator; applying and drying a resin composition comprising a supporting substrate on a supporting substrate, wherein the mixed solvent is a high boiling point having a boiling point of 115° C. or higher: a low boiling point solvent having a boiling point of 100° C. or less is 1:2 to A method for producing a photosensitive laminate may be provided, including in a weight ratio of 1:18, or 1:3 to 1:15, or 1:5 to 1:10, or 1:6 to 1:8.

According to the manufacturing method, the photosensitive laminate described above in the embodiment may be provided. As described above, the photosensitive laminate includes a supporting substrate; and a photosensitive resin layer comprising a photopolymerizable compound comprising an ester-based monomer or oligomer and an alkali developable binder resin, wherein the number of bubbles having a diameter of less than 1 μm in the photosensitive resin layer is 5/mm ² or less. may exist.

In the process of forming the photosensitive resin layer, a diameter of less than 1 μm may be formed in the photosensitive resin layer for reasons such as bubbles generated during the solution preparation process of the photosensitive resin composition or the solution drying process of the composition. In the manufacturing method, by using a mixed solvent including a high boiling point solvent having a boiling point of 115° C. or higher and a low boiling point solvent having a boiling point of 100° C. or less, the evaporation time of the solution of the photosensitive resin composition is delayed so that bubbles are not trapped in the numerical layer Accordingly, the number of bubbles having a diameter of less than 1 μm in the photosensitive resin layer may be 5/mm ² or less.

More specifically, the number of bubbles having a diameter of less than 1 μm in the photosensitive resin layer may be 5/mm ² or less, or 3/mm ² or less.

In addition, within 50% of the total thickness of the photosensitive resin layer from the opposite surface of the interface between the supporting substrate and the photosensitive resin layer, 3 bubbles/mm ² or less having a diameter of less than 1 μm may exist.

As bubbles having a diameter of less than 1 μm on the opposite surface of the interface between the support substrate and the photosensitive resin layer or the photosensitive resin layer toward the outer surface are present in a trace amount or are substantially absent, reliability during development is increased, resulting in a high-density circuit It is possible to form and reduce defects in the formation of fine wiring. Accordingly, when the photosensitive laminate is used, high sensitivity to exposure can be realized, and the manufacturing yield of a high-density printed circuit board can be improved.

As described above, the high boiling point solvent having a boiling point of 115° C. or higher may serve to slow the evaporation time of the liquid component of the photosensitive resin composition, thereby preventing air bubbles from being trapped in the numerical layer. Accordingly, 5 bubbles/mm 2 or less may exist in the photosensitive resin layer having a diameter of less than 1 μm.

The mixed solvent may include the high boiling point solvent having a boiling point of 115° C. or higher in an amount of at least a certain amount, for example, the content of the high boiling point solvent having a boiling point of 115° C. or higher relative to 100 parts by weight of the mixed solvent is 3 parts by weight or more. , or 5 parts by weight or more, 50 parts by weight or less, 40 parts by weight or less, or 3 to 50 parts by weight, 3 to 40 parts by weight, 5 to 50 parts by weight, or 5 to 40 parts by weight.

By using the low boiling point solvent having a boiling point of 100° C. or less together with the high boiling point solvent having a boiling point of 115° C. or higher, the dissolving power of the photosensitive resin composition can be increased.

The mixed solvent may contain a higher content of the low boiling point solvent having a boiling point of 100° C. or less than the high boiling point solvent having a boiling point of 115° C. or higher.

More specifically, the mixed solvent is a high boiling point solvent having a boiling point of 115°C or higher: 1:2 to 1:18, or 1:3 to 1:15, or 1: It may be included in a weight ratio of 5 to 1:10, or 1:6 to 1:8. The high boiling point solvent having a boiling point of 115° C. or higher: By including the low boiling point solvent having a boiling point of 100° C. or less in the above content, the dissolving power of the photosensitive resin composition can be increased.

Examples of the high boiling point solvent having a boiling point of 115° C. or higher include butanol, dimethylformamide, N-methyl-2-pyrrolidone, gamma butyrolactone, butyl capitol, butyl cellosolve, methyl cellosolve, butyl acetate , Diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, methyl 3-methoxy propionate, ethyl 3-ethoxy propionate, propylene glycol methyl ether pro cionate, dipropylene glycol dimethyl ether, cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), and one or more mixed solvents thereof.

Examples of the low boiling point solvent having a boiling point of 100° C. or less include methyl ethyl ketone, methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, isopropyl alcohol, and one or more mixed solvents thereof.

a mixed solvent including the high boiling point solvent having a boiling point of 115° C. or higher and a low boiling point solvent having a boiling point of 100° C. or less; alkali developable binder resin; and a photoinitiator; the resin composition may control the solid content in consideration of specific uses or fields of application, and for example, the resin composition may include 10 to 99% by weight of the mixed solvent.

On the other hand, the method or apparatus that can be used in the step of applying and drying the resin composition on the supporting substrate is not greatly limited, For example, the resin composition may be coated on a conventional base film such as polyethylene terephthalate using a conventional coating method, and then dried to prepare a dry film.

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

In the method for producing the photosensitive laminate, in addition to using a mixed solvent containing a high boiling point solvent having a boiling point of 115° C. or higher and a low boiling point solvent having a boiling point of 100° C. or lower, the drying rate and/or drying temperature are adjusted. Through this, the amount of microbubbles formed in the photosensitive resin layer can be greatly reduced or substantially absent.

More specifically, the drying of the coated resin composition may be carried out by heating means such as a hot air oven, a hot plate, a hot air circulation furnace, an infrared furnace, and a temperature of 50 ° C. to 100 ° C., or 60 ° C. to 90 ° C. temperature, it can be carried out at a temperature of 70 ℃ to 85 ℃.

The time for which the drying is performed may vary depending on the drying temperature, for example, may be 30 seconds to 20 minutes, and more specifically, may be 1 minute to 10 minutes, or 3 minutes to 7 minutes.

The content regarding the alkali developable binder resin included in the resin composition includes the content described above in the photosensitive laminate of the embodiment.

The alkali developable binder resin is a weight average of 20,000 g/mol to 300,000 g/mol, 20,000 g/mol to 200,000 g/mol, 30,000 g/mol to 200,000 g/mol, or 30,000 g/mol to 150,000 g/mol have a molecular weight and a glass transition temperature of 20 °C or more and 150 °C or less, 30 °C or more 150 °C or less, 50 °C or more 150 °C or less, 50 °C or more 130 °C or less, 70 °C or more 130 °C or less, or 70 °C or more and 120 °C or less can

The alkali developable binder resin is 100 mgKOH/g or more and 300 mgKOH/g or less, 120 mgKOH/g or more and 300 mgKOH/g or less, 120 mgKOH/g or more and 250 mgKOH/g or less, 120 mgKOH/g or more and 200 mgKOH/g or less , or may have an acid value of 140 mgKOH/g or more and 160 mgKOH/g or less.

The resin composition may include a photopolymerizable compound including an ester-based monomer or oligomer together with an alkali developable binder resin.

The resin composition is 1 to 80 parts by weight, 5 to 80 parts by weight, 5 to 70 parts by weight, 10 to 70 parts by weight, 10 to 60 parts by weight, 10 to 50 parts by weight, 25 to 50 parts by weight, or 30 to 50 parts by weight may be included.

The content of the photopolymerizable compound includes the content described above in the photosensitive laminate of the embodiment.

In the method for manufacturing the photosensitive laminate of the embodiment, two or more solvents having different boiling points are mixed and used, and, depending on the selection of the photopolymerizable compound to be used, the photosensitive resin layer in which microbubbles are present in a trace amount or not substantially present. can form.

Specifically, specific examples of the ester-based monomer or oligomer may include the compound of Formula 1 above.

The photopolymerizable compound including the ester-based monomer or oligomer may serve as a crosslinking agent to increase mechanical strength of the photosensitive resin layer, etc. or to increase resistance to a developer and to provide flexibility of the cured film. In addition, by using the photopolymerizable compound including the ester-based monomer or oligomer, the photosensitive resin layer can have a higher adhesion to the supporting base, and the development time or peeling time of the photosensitive laminate can be greatly shortened. have.

Due to the structure and characteristics of these ester-based monomers or oligomers, bubbles having a diameter of 1 μm or less can be present in a trace amount in the photosensitive resin layer, thereby reducing defects in the formation of fine wiring. A photosensitive laminate capable of forming high-density circuits by securing high reliability during operation may be provided.

Meanwhile, the photopolymerizable compound may further include a monofunctional (meth)acrylate compound or a bifunctional (meth)acrylate compound.

According to the specific use or characteristics of the photosensitive resin layer, the content of the monofunctional (meth) acrylate compound or the polyfunctional (meth) acrylate compound can be adjusted, for example, the photopolymerizable compound is the ester-based monomer or The monofunctional (meth)acrylate compound or the polyfunctional (meth)acrylate compound may be included in an amount of 50 to 500 parts by weight based on 100 parts by weight of the oligomer.

The photoinitiator is a material that initiates a chain reaction of photopolymerizable monomers by UV and other radiation, and plays an important role in curing the photosensitive resin layer of the resin composition and the photosensitive laminate.

Examples of the compound that can be used as the photoinitiator 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 a photoinitiator, but is limited thereto not.

The content of the photoinitiator is included in an amount of 0.1 to 20% by weight or 1% by weight or more and 10% by weight or less, based on the solid content, based on the total weight of the resin composition. When the content of the photoinitiator is within the above range, sufficient sensitivity can be obtained.

When the content of the photoinitiator is too low, the production efficiency may be extremely reduced because the light efficiency is low and a large amount of exposure is required. If the content of the photoinitiator is too high, the film may be brittle, and the contamination of the developer may be increased, which may lead to defects such as short circuit.

In addition, the resin composition may further include other additives as necessary. Other additives include dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, 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 order to improve the handleability of the said resin composition, you may put a leuco dye or 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 0.1% by weight or more and 10% by weight or less in the photosensitive resin composition. From a viewpoint of expression of contrast, 0.1 weight% or more is preferable, and 10 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.

Meanwhile, according to another embodiment of the present invention, a method of manufacturing a circuit board using the photosensitive laminate of the embodiment may be provided.

The photosensitive laminate of the embodiment may be used for lamination on copper clad laminates.

As an example of a manufacturing process of a circuit board or a printed circuit board (PCB), a pretreatment process is first performed in order to laminate a copper-clad laminate, which is a raw 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 processes are mainly used, and soft etching and sulfuric acid pickling can be used for pickling.

In order to form a circuit on a copper-clad laminate that has undergone a pre-treatment process, in general, the photosensitive laminate or dry film photoresist (hereinafter referred to as DFR) may be 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 rate may be 0.5 to 3.5 m/min, a temperature of 100 to 130° C., and a roller pressure heating roll pressure of 10 to 90 psi.

The printed circuit board that has undergone the lamination process may be left for at least 15 minutes for stabilization of the substrate and then exposed to the photoresist of the DFR using a photomask having a desired circuit pattern formed thereon. In this process, when the photomask is irradiated with ultraviolet rays, polymerization of the photoresist irradiated with ultraviolet rays may be initiated by the photoinitiator contained in the irradiated area. First, oxygen in the photoresist is consumed, and then the activated monomer is polymerized to cause a crosslinking reaction. After that, a large amount of monomer is consumed and the polymerization reaction can proceed. may exist.

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 may be 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 may remain on the copper surface.

A circuit may be formed through different processes according to the next inner layer and outer layer processes. In the inner layer process, a circuit may be formed on the substrate through corrosion and peeling processes, and in the outer layer process, after plating and tenting processes, etching and solder peeling may be performed to form a predetermined circuit.

For the exposure, a commonly known light source, more specifically, an ultra-high pressure mercury lamp or laser direct exposure equipment, may be used.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive laminated body which can reduce defects in the formation of fine wiring, and can form high-density circuits with increased reliability during development, a manufacturing method of the photosensitive laminate, and a circuit board using the photosensitive laminate A manufacturing method may be provided.

1 is a photograph confirming the surface and cross-section of the photosensitive resin layer of Example 1 with a field emission scanning electron microscope (FE-SEM, 10,000 times) using a polarizing microscope.

2 is a photograph obtained by confirming the surface and cross-section of the photosensitive resin layer of Comparative Example 2 with a field emission scanning electron microscope (FE-SEM, 12,000 times) using a polarizing microscope.

3 is a photograph of the photosensitive resin layer of Comparative Example 2 exposed to ultraviolet light and alkali-developed, and the formed defects were confirmed with a field emission scanning electron microscope (FE-SEM, 3000x).

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.

<Production Example: Preparation of alkali developable binder resin>

Preparation Example 1

A mechanical stirrer and a reflux device were installed in a four-necked round-bottom flask, and then the inside of the flask was purged with nitrogen. In the flask purged with nitrogen, 170 g of methyl ethyl ketone (Methyl Ethyl Ketone, MEK) and 12.5 g of methanol (Methanol, MeOH) were added, and then 2.25 g of azobisisobutyronitrile (AIBN) was added and completely dissolved. did it Here, as a monomer, 60 g of methacrylic acid (MAA), 100 g of benzyl methacylrate (BzMA), 15 g of methyl methacrylate (MMA), and 75 g of styrene (Styrene, SM) The monomer mixture was added, and the temperature was raised to 80 ° C., and then polymerized for 6 hours. Alkali developable binder resin 2 (weight average molecular weight 40,000 g/mol, glass transition temperature 102 ° C., solid content 50 wt%, acid value 156 mgKOH/g) was prepared.

Measurement of weight average molecular weight (Mw) of alkali developable binder resin

The alkali developable binder resin prepared in Preparation Examples 1 and 2 was 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) to 0.45㎛ Pore Size After filtration using a Syringe Filter, 20 μl was injected into GPC. As the mobile phase of GPC, tetrahydrofuran (THF) was used, and it was introduced at a flow rate of 1.0 mL/min, and the analysis was performed at 40°C. For the column, one Agilent PLgel 5㎛ Guard (7.5 x 50 mm) and two Agilent PLgel 5㎛ Mixed D (7.5 x 300 mm) were connected in series. As a detector, the Agilent 1260 Infinity Ⅱ System, RI Detector was used for measurement at 40°C.

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

<Examples 1 to 3 and Comparative Example 1: Preparation of photosensitive resin composition and dry film photoresist>

According to the composition shown in Table 1 below, the photoinitiator was dissolved in an organic solvent, a photopolymerizable compound and an alkali developable binder resin were added, and mixed using a mechanical stirrer for about 1 hour to prepare a photosensitive resin composition.

The obtained photosensitive resin composition was coated on a 16 μm PET film using a coating bar. The coated photosensitive resin composition layer was dried using a hot air oven, wherein the drying temperature was 80° C., the drying time was 5 minutes, and the thickness of the photosensitive resin composition layer after drying was 25 μm.

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

ingredient	product name (or ingredient name)	Content (wt%)
		Example 1	Example 2	Example 3	Comparative Example 1
Alkali developable binder resin	Preparation Example 1	55	55	55	55
photopolymerizable compound	Blemmer 55 PET-800	2	3	3
	M-2101	12	11	13	14
	M-241	3	3	3	3
	T063	2	2
	A040	One	One	One	3
photopolymerization initiator	BCIM	3.5	3.5	3.5	3.5
	9,10-dibutoxyanthracene	0.5	0.5	0.5	0.5
additive	N,N-Diethylbutylamine	0.2	0.2	0.2	0.2
	Ruiko Crystal Violet (Japan Hodogaya Co.)	0.5	0.5	0.5	0.5
	Diamond Green GH (Japan Hodogaya Co.)	0.3	0.3	0.3	0.3
solvent	MEK (Methyl Ethyl Ketone, boiling point about 80 ℃)	15	15	15	18
	Methanol (about 64.7 ℃)	2	2	2	2
	Propylene glycol monomethyl ether acetate (PGMEA, boiling point about 146.4°C)	3	3	3
* Blemmer 55 PET-800: poly(ethylene glycol tetramethylene glycol)-mono(meth)acrylate (1) M2101: Bisphenol A (EO) 10 dimethacrylate (Miwon Specialty Chemical) (2) M241: bisphenol A (ethoxylate) 4 di (meth) acrylate (Miwon Specialty Chemical) (3) T063: Trimethylolpropane [EO] 6 triacrylate (4) A040: Methoxy propylene glycol [400] acrylate (n=9) (5) BCIM: 2,2'-Bis-(2-chlorophenyl-4,5,4',5'-tetraphenylbisimidazole, Aldrich Chemical

[Comparative Example 2: Photosensitive resin composition and dry film photoresist production] Examples of Patent Document 1 based on the specification identification numbers [0088] and [0093] of Patent Document 1 (Japanese Patent Application Laid-Open No. 2006-106287) An experiment to reproduce 4 was conducted.

1. Preparation of photosensitive resin composition

Based on the description of Example 4 of Patent Document 1, based on 300 parts by weight of the "alkali developable binder resin" obtained in Preparation Example 1 of the present specification, the following components were mixed using a mechanical stirrer for about 1 hour to achieve photosensitivity A resin composition was prepared.

<Component of the photosensitive resin composition>

(1) 2,2-bis(4-(methacryloxy pentaethoxy)phenyl)propane 100 parts by weight

(2) EO, PO modified urethane di (meth) acrylate 50 parts by weight

(3) polypropylene glycol diacrylate (the number of propylene glycol chains: 7) 50 parts by mass

(4) photoinitiator: 25 parts by mass of benzophenone, 1.0 parts by mass of 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer, and 1.0 part by mass of diethylaminobenzophenone

(5) 5.0 parts by mass of photochromic agent

(6) 0.15 parts by mass of dye

(7) Mixed solvents:

477 parts by mass of acetone (boiling point 56° C.), 26.5 parts by mass of toluene (boiling point 110° C.) and 26.5 parts by mass of propylene glycol monomethyl ether (boiling point 146.4° C.) [low boiling point solvent having a boiling point of 100° C. or less: having a boiling point of 115° C. or higher Weight ratio of high boiling point solvent = 19: 1]

2. Dry Film Photoresist Manufacturing

The obtained photosensitive resin composition was coated on a 25 μm PET film using a coating bar. The coated photosensitive resin composition layer was dried using a hot air oven, wherein the drying temperature was 80° C., the drying time was 5 minutes, and the thickness of the photosensitive 20 resin layer after drying was 25 μm.

<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 3.

1. Measurement of exposure dose (unit: mJ/cm ² )

The dry film photoresist prepared in Examples and Comparative Examples was laminated on a 1.6 mm thick copper-clad laminate that had been brush-polished. At this time, the lamination was performed using a HAKUTO MACH 610i, at a substrate preheating roll temperature of 120 °C, a laminator roll temperature of 115 °C, and a roll pressure of 4.0 kgf/cm2. and a roll speed of 2.0 min/m was applied.

Dry film photoresist laminated on a copper clad laminate was irradiated with UV rays at a wavelength of 405 nm using ORC's FDi-3, using a 41-layer step tablet from Stouffer Graphic Arts Equipment, and the remaining number of steps was 15. did. After that, Na ₂ CO ₃ 1.0wt% aqueous solution was developed under the development conditions of the spray injection method. At this time, the amount of energy at which the determined number of remaining step steps becomes 15 steps was measured.

2. Measurement of 1:1 resolution (unit: μm)

The dry film photoresist prepared in Examples and Comparative Examples was laminated on a 1.6 mm thick copper-clad laminate that had been brush-polished. At this time, the lamination was performed using a HAKUTO MACH 610i, at a substrate preheating roll temperature of 120 °C, a laminator roll temperature of 115 °C, and a roll pressure of 4.0 kgf/cm2. and a roll speed of 2.0 min/m was applied.

ORC's data was formed at an interval of 0.5 μm from 4 to 20 μm so that the space interval between the circuit line width and the circuit line after development in the laminate is 1:1. Through FDi-3, using a 41-step step tablet of Stouffer Graphic Arts Equipment, the remaining number of steps was 15 steps. After that, development was carried out under the conditions of spray spraying with a 1.0 wt% aqueous solution of Na2CO3.

Thereafter, the resolution was determined with the measured value using the ZEISS AXIOPHOT Microscope with the space between the circuit line and the non-circuit line being 1:1.

3. Check the air bubbles (unit: number/mm ² )

For the dry film photoresists prepared in Examples and Comparative Examples, after removing the PET film and the PE film, using a polarizing microscope, 1 μm present in the photosensitive resin layer (unit area (1 mm * 1 mm)) The number of bubbles having a diameter of less than (number/mm ² ) was confirmed.

4. After exposure/development, check for defects (unit: number/mm ² )

The dry film photoresist prepared in Examples and Comparative Examples was laminated on a 1.6 mm thick copper-clad laminate that had been brush-polished. At this time, the lamination was performed using a HAKUTO MACH 610i, at a substrate preheating roll temperature of 120 °C, a laminator roll temperature of 115 °C, and a roll pressure of 4.0 kgf/cm2. and a roll speed of 2.0 min/m was applied.

After development in the laminate, a 41-step tablet from Stouffer Graphic Arts Equipment was used through ORC's FDi-3 so that the distance between the circuit line width and the circuit line could be 14㎛: 14㎛. Thus, after irradiating ultraviolet rays with a wavelength of 405 nm at an exposure amount such that the number of remaining step stages becomes 15 stages, it was allowed to stand for 15 minutes. After that, Na ₂ CO ₃ 1.0wt% aqueous solution was developed under the development conditions of the spray injection method.

For each of the developed dry film photoresists prepared in Examples and Comparative Examples, the upper and lower surfaces of the resist were observed within a unit area (1 mm * 1 mm) using an electron microscope, and defects of 0.5 μm or more and 3 μm or less (Defect) ) was confirmed, and the surface and cross-section of the photosensitive resin layer obtained in each of Examples and Comparative Examples were examined using a field emission scanning electron microscope (FE-SEM, manufactured by Hitachi, magnification 3000 times). was observed using

division	exposure [mJ/cm 2 ]	1:1 resolution [μm]	less than 1 μm Bubbles in diameter [Number/㎟]	Defect of lower limb after exposure/development [number/㎟]
Example 1	50	7	One	0
Example 2	50	7	0	0
Example 3	50	6	0	0
Comparative Example 1	50	12	28	14
Comparative Example 2	350	15	17	8

As can be seen in Table 2 and FIG. 1, in the photosensitive resin layer of the photosensitive laminates of the Examples, there is 1 bubble/mm ² or less having a diameter of less than 1 μm, and also 1 μm to 5 μm It was confirmed that there was also no macrobubbles having a diameter. In addition, the photosensitive resin layer of the above examples showed substantially no defects having a diameter of 0.5 μm or more and 3 μm or less even after exposure to ultraviolet light and development with an alkaline solution. It was confirmed that it does not occur, or occurs at 1/mm ² or less.

Since there is a small amount of bubbles having a diameter of less than 1 μm in the photosensitive resin layer of the above embodiments, defects in the formation of fine wiring can be reduced when manufacturing a circuit board using the photosensitive laminate, and high reliability is ensured It was also observed that high density and sensitivity could be realized, and finer wiring could be formed.

On the other hand, in the photosensitive resin laminate of Comparative Example 1, it was confirmed that it was difficult to implement the resolution of the Example level even using an energy equivalent to that of the Example, and in particular, in the photosensitive resin laminate of Comparative Example 2, 350 mJ/cm 2 It was confirmed that it was difficult to implement the resolution at the level of the embodiment even using the energy reached.

Furthermore, in the dry film photoresists of Comparative Examples 1 and 2, 15 or more "bubbles with a diameter of less than 1 μm" were generated, and as shown in FIG. 3 , after the photosensitive resin layer was exposed and developed with an alkaline solution, It was confirmed that a large number of defects (8 pieces/mm2 or more) with a diameter of 0.5 μm or more and 3 μm or less appeared in the

Claims (23)

1. support substrate; and

   A photosensitive resin layer comprising a photopolymerizable compound comprising an ester-based monomer or oligomer and an alkali developable binder resin;

   In the photosensitive resin layer, the number of bubbles having a diameter of less than 1 μm is 5/mm ² or less,

   photosensitive laminate.
2. The method of claim 1,

   The photosensitive resin layer does not contain bubbles having a diameter of 1 μm to 5 μm,

   photosensitive laminate.
3. According to claim 1,

   Within 50% of the total thickness of the photosensitive resin layer from the opposite surface of the interface between the support substrate and the photosensitive resin layer, 3 cells/mm ² or less of cells having a diameter of less than 1 μm exist.
4. According to claim 1,

   The thickness of the support substrate is 1 μm to 100 μm,

   The thickness of the photosensitive resin layer is 1 μm to 100 μm, the photosensitive laminate.
5. According to claim 1,

   In the photosensitive resin layer, after UV exposure and alkali development, defects having a cross-sectional diameter of 0.3 μm to 4 μm are present in 3/mm ² or less.
6. According to claim 1,

   The ester-based monomer or oligomer is a photosensitive laminate comprising a (meth)acrylate bonded to one or more hydroxyl groups, epoxy groups, or amine groups:
7. 7. The method of claim 1 or 6,

   The ester-based monomer or oligomer is a photosensitive laminate comprising a compound of Formula 1:

   [Formula 1]

   CH ₂ =CR ¹ -COO-R ² -OH

   In Formula 1,

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

   R ² is a divalent saturated aliphatic hydrocarbon group having 1 to 100 carbon atoms, or 2 to 50 carbon atoms,

   The saturated aliphatic hydrocarbon group may optionally include a halogen atom, an ether bond (-O-), an ester bond (-COO- or O-CO-), an amide bond (-NHCO- or CONH-) or an aryl group.
8. 7. The method of claim 1 or 6,

   The ester-based monomer or oligomer is glycerol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol monoacrylate, hydroxypropyl (meth) acrylate, Polypropylene glycol mono (meth) acrylate, polypropylene glycol mono acrylate, poly (ethylene glycol propylene glycol) - mono (meth) acrylate, polyethylene glycol polypropylene glycol - mono (meth) acrylate, poly (ethylene glycol tetra) Methylene glycol)-mono(meth)acrylate, poly(propylene glycol tetramethylene glycol)-mono(meth)acrylate, propylene glycol polybutylene glycol-mono(meth)acrylate, 2-hydroxyethyl acrylate, 2 -Hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, or a photosensitive laminate comprising a mixture of two or more thereof.
9. According to claim 1,

   The photopolymerizable compound further comprises a monofunctional (meth) acrylate compound or a polyfunctional (meth) acrylate compound, the photosensitive laminate.
10. 10. The method of claim 9,

    The photopolymerizable compound comprises 50 parts by weight to 500 parts by weight of the monofunctional (meth) acrylate compound or the polyfunctional (meth) acrylate compound based on 100 parts by weight of the ester-based monomer or oligomer, the photosensitive laminate.
11. According to claim 1,

    The alkali developable binder resin has a weight average molecular weight of 20,000 g / mol to 300,000 g / mol and a glass transition temperature of 20 ℃ or more and 150 ℃ or less,

    photosensitive laminate.
12. According to claim 1,

    The alkali developable binder resin has an acid value of 100 mgKOH/g or more and 300 mgKOH/g, the photosensitive laminate.
13. The manufacturing method of a circuit board using the photosensitive laminated body of Claim 1.
14. a mixed solvent including a high boiling point solvent having a boiling point of 115°C or higher and a low boiling point solvent having a boiling point of 100°C or lower; a photopolymerizable compound including an ester-based monomer or oligomer; alkali developable binder resin; And a photoinitiator; including the step of applying and drying the resin composition comprising a support substrate,

    The mixed solvent contains the high boiling point having a boiling point of 115° C. or higher: the low boiling point solvent having a boiling point of 100° C. or less in a weight ratio of 1:2 to 1:18,

    The method for manufacturing the photosensitive laminate of claim 1 .
15. 15. The method of claim 14,

    The mixed solvent includes the high boiling point having a boiling point of 115° C. or higher: the low boiling point solvent having a boiling point of 100° C. or less in a weight ratio of 1:3 to 1:15.
16. 15. The method of claim 14,

    The high boiling point solvent having a boiling point of 115° C. or higher is butanol, dimethylformamide, N-methyl-2-pyrrolidone, gamma butyrolactone, butyl capitol, butyl cellosolve, methyl cellosolve, butyl acetate, di Ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, methyl 3-methoxy propionate, ethyl 3-ethoxy propionate, propylene glycol methyl ether propionate Containing at least one organic solvent selected from the group consisting of , dipropylene glycol dimethyl ether, cyclohexanone and propylene glycol monomethyl ether acetate (PGMEA),

    A method for producing a photosensitive laminate.
17. 15. The method of claim 14,

    The low boiling point solvent having a boiling point of 100° C. or less includes at least one organic solvent selected from the group consisting of methyl ethyl ketone, methanol, ethanol, acetone, tetrahydrofuran and isopropyl alcohol,

    A method for producing a photosensitive laminate.
18. 16. The method of claim 15,

    The ester-based monomer or oligomer is a method for producing a photosensitive laminate comprising a compound of Formula 1:

    [Formula 1]

    CH ₂ =CR ¹ -COO-R ² -OH

    In Formula 1,

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

    R ² is a divalent saturated aliphatic hydrocarbon group having 1 to 100 carbon atoms, or 2 to 50 carbon atoms,

    The saturated aliphatic hydrocarbon group may optionally include a halogen atom, an ether bond (-O-), an ester bond (-COO- or O-CO-), an amide bond (-NHCO- or CONH-) or an aryl group.
19. 15. The method of claim 14,

    The ester-based monomer or oligomer is glycerol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol monoacrylate, hydroxypropyl (meth) acrylate, Polypropylene glycol mono (meth) acrylate, polypropylene glycol mono acrylate, poly (ethylene glycol propylene glycol) - mono (meth) acrylate, polyethylene glycol polypropylene glycol - mono (meth) acrylate, poly (ethylene glycol tetra) Methylene glycol)-mono(meth)acrylate (trade name: Blemmer 55 PET-800, etc.), poly(propylene glycol tetramethylene glycol)-mono(meth)acrylate, propylene glycol polybutylene glycol-mono(meth)acrylate , 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, or a mixture of two or more thereof. A method of manufacturing a sieve.
20. 15. The method of claim 14,

    The photopolymerizable compound further comprises a monofunctional (meth) acrylate compound or a polyfunctional (meth) acrylate compound, the method for producing a photosensitive laminate.
21. 21. The method of claim 20,

    The photopolymerizable compound comprises 50 parts by weight to 500 parts by weight of the monofunctional (meth) acrylate compound or the polyfunctional (meth) acrylate compound based on 100 parts by weight of the ester-based monomer or oligomer, the photosensitive laminate.
22. 15. The method of claim 14,

    The alkali developable binder resin has a weight average molecular weight of 20,000 g / mol to 300,000 g / mol and a glass transition temperature of 20 ℃ or more and 150 ℃ or less,

    A method for producing a photosensitive laminate.
23. 15. The method of claim 14,

    The alkali developable binder resin has an acid value of 100 mgKOH/g or more and 300 mgKOH/g, a method for producing a photosensitive laminate.

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