WO2022211453A1 - Photosensitive laminate, method for manufacturing photosensitive laminate, and method for manufacturing circuit board - Google Patents

Abstract

The present invention relates to a photosensitive laminate and a method for manufacturing the photosensitive laminate, the photosensitive laminate comprising: a barrier layer having a haze of 2% or less; and a photosensitive resin layer which includes a binder resin and a photopolymerizable compound including a bifunctional to deca-functional (meth)acrylate monomer or oligomer that has an aromatic functional group in the molecule, wherein the number of bubbles having a diameter of less than 1 µm present in the photosensitive resin layer is 5 bubbles/mm2 or less.

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. 10-2021-0042138 dated March 31, 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 barrier layer having a haze of 2% or less; and a photosensitive resin layer including a photopolymerizable compound and a binder resin including a 2 to 10-functional (meth)acrylate monomer or oligomer containing an aromatic functional group in the molecule, and a diameter of less than 1 μm in the photosensitive resin layer A photosensitive laminate can be provided, in which the number of cells having the present invention is 5/mm ² or less.

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

Also, in the present specification, a method for manufacturing a circuit board using 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, 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 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.

According to one embodiment of the invention, a barrier layer having a haze of 2% or less; and a photosensitive resin layer including a photopolymerizable compound and a binder resin including a 2 to 10-functional (meth)acrylate monomer or oligomer containing an aromatic functional group in the molecule, and a diameter of less than 1 μm in the photosensitive resin layer A photosensitive laminate can be provided, in which the number of cells having the present invention is 5/mm ² or less.

The present inventors have newly developed a photosensitive laminate comprising a barrier layer having a haze of 2% or less and a photosensitive resin layer having 5 cells/mm ² or less of bubbles having a diameter of less than 1 μm, or 0.001 μm or more and less than 1 μm. By using this photosensitive laminate, it is possible to realize high sensitivity to exposure during the manufacturing process of circuit boards, and the reliability during development is increased, so that high density and sensitivity are realized while ensuring high reliability, and the formation of finer wiring is achieved. Possible points were confirmed through experiments and the invention was completed.

The present inventors have confirmed that excellent circuit pattern resolution can be realized in a dry film photoresist manufacturing process using a photosensitive laminate by including a barrier layer having excellent optical properties having a haze of 2% or less. Specifically, as a barrier layer having a haze of 2% or less is included, the barrier layer acts as an oxygen barrier film that blocks oxygen radical reactions, minimizing the formation of foreign substances or bubbles in the photosensitive resin layer. It was confirmed that the resolution and reliability of the resist could be improved, and the present invention was completed.

Specifically, in the photosensitive laminate of the embodiment, the barrier layer may have a haze of 2% or less, 0.001% or more and 2% or less, and 0.1% or more and 2% or less.

The haze measurement method is not particularly limited, but may be measured according to the measurement method of ASTM D1003 using, for example, a HAZE METER (model name: NDH7000, Nippon Denshoku Corporation).

The thickness of the barrier layer to be measured for the haze may be 0.1 μm to 10 μm, or 1 μm to 3 μm. When the thickness of the barrier layer increases or decreases by a specific value, physical properties measured in the barrier layer may also change by a predetermined value.

When the haze of the barrier layer exceeds 2%, there may be a problem in that the resolution of circuit properties is impaired.

In the photosensitive laminate of the embodiment, the barrier layer is 10cc/m ² /day or less, 5cc/m ² /day or less, 4cc/m ² /day or less, 0.01 cc/m ² /day or more 10cc/m ² /day It may have an oxygen permeability of 0.01 cc/m ² /day or more and 5 cc/m ² /day or less, or 0.01 cc/m ² /day or more and 4 cc/m ² /day or less. The method for measuring the oxygen permeability is not particularly limited, but, for example, it may be measured according to the measurement method of ASTM F1927 using OX-Tran (Model 2/61, Mocon Corporation).

The thickness of the barrier layer to be measured for the oxygen permeability may be 0.1 μm to 10 μm, or 1 μm to 3 μm. When the thickness of the barrier layer increases or decreases by a specific value, physical properties measured in the barrier layer may also change by a predetermined value.

As the barrier layer has an oxygen permeability of 10 cc/m ² /day or less, the barrier layer may act as an oxygen barrier film that blocks oxygen radical reaction, and thus formation of foreign substances or bubbles in the photosensitive resin layer is prevented. By minimizing it, the resolution and reliability of the final manufactured dry film photoresist can be improved.

The barrier layer may be formed from a composition for forming a barrier layer, and the composition for forming the barrier layer may include a polyvinyl alcohol resin.

That is, the barrier layer is 5,000 g/mol to 1,000,000 g/mol, 7,000 g/mol to 750,000 g/mol, 7,000 g/mol to 700,000 g/mol, 7,000 g/mol to 50,000 g/mol, 7,000 g/mol to 30,000 g/mol, or a polyvinyl alcohol resin having a weight average molecular weight of 10,000 g/mol to 30,000 g/mol. As the barrier layer includes a polyvinyl alcohol resin having a weight average molecular weight of 10,000 g/mol to 1,000,000 g/mol, a haze of the barrier layer may satisfy 2% or less.

More specifically, the polyvinyl alcohol resin may have a viscosity of 1.0 cP to 10.0 cP, 3.0 cP to 10.0 cP, 3.0 cP to 5.0 cP. As the viscosity of the polyvinyl alcohol resin satisfies 1.0 cP to 10.0 cP, the haze of the barrier layer may satisfy 2% or less.

In addition, the composition for forming a barrier layer may include a high boiling point solvent having a boiling point of 115° C. or higher.

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.

Specifically, the composition for forming the barrier layer contains 60 parts by weight or more, 60 parts by weight or more and 200 parts by weight or less, 70 parts by weight or more and 200 parts by weight of the high boiling point solvent having a boiling point of 115° C. or more with respect to 100 parts by weight of the polyvinyl alcohol resin. It may be included in an amount of 80 parts by weight or more and 200 parts by weight or less, 80 parts by weight or more and 100 parts by weight or less, or 90 parts by weight or more and 100 parts by weight or less.

As the composition for forming the barrier layer contains 60 parts by weight or more of the high boiling point solvent having a boiling point of 115° C. or higher based on 100 parts by weight of the polyvinyl alcohol resin, the haze of the barrier layer may satisfy 2% or less, , When the composition for forming the barrier layer contains less than 60 parts by weight of the high boiling point solvent having a boiling point of 115° C. or higher with respect to 100 parts by weight of the polyvinyl alcohol resin, the haze of the barrier layer rapidly increases. can occur

The thickness of the barrier layer and the photosensitive resin layer in the photosensitive laminate is not particularly limited, but as a specific example, the thickness of the barrier layer may be 0.1 μm to 10 μm, or 1 μm to 3 μm, and the thickness of the photosensitive resin layer may be 1 μm to 100 μm, or 5 μm to 50 μm.

The photosensitive laminate of the embodiment may further include a support substrate formed on the barrier layer and having a thickness of 1 μm to 100 μm. As a specific example, the thickness of the supporting substrate may be 1 μm to 100 μm, or 5 μm to 50 μm. That is, the photosensitive laminate of the embodiment may have a laminate structure in which a supporting substrate, a barrier layer, and a photosensitive resin layer are sequentially laminated. The supporting substrate may serve as a kind of carrier in the manufacturing process of the photosensitive laminate. In addition, the supporting substrate may or may not be selectively included in the photosensitive laminate according to a semiconductor manufacturing process to which the photosensitive laminate is applied or a final manufactured product.

In addition, the photosensitive laminate of the embodiment may further include a release layer formed on the photosensitive resin layer and having a thickness of 0.01 μm to 1 m. As a specific example, the thickness of the release layer may be 0.01 μm to 1 m, 1 μm to 100 μm, or 5 μm to 50 μm. That is, the photosensitive laminate of the embodiment may have a laminate structure in which a support substrate, a barrier layer, a photosensitive resin layer, and a release layer are sequentially stacked.

As described above, in the dry film photoresist manufacturing process using the photosensitive laminate, the supporting substrate and the release layer may be removed. As the photosensitive laminate includes a barrier layer having a haze of 2% or less, even if the supporting substrate is removed, the finally manufactured dry film photoresist may implement excellent reliability and resolution.

Specifically, in the photosensitive laminate of one embodiment, the number of bubbles having a diameter of less than 1 μm in the photosensitive resin layer is 5/mm ² or less, or as substantially no bubbles exist, haze of 2% or less It can be applied to the semiconductor manufacturing process in a state in which only the barrier layer having a barrier layer is formed, and thus, even with a thinner thickness, reliability and sensitivity equal to or higher than that of the conventionally known photosensitive laminate can be realized.

In addition, since the photosensitive laminate of the embodiment can be applied to a semiconductor manufacturing process in a state in which a supporting substrate such as a polyethylene terephthalate (PET) film is peeled off, separately performing the peeling process of the supporting substrate in the semiconductor manufacturing process It can be omitted, and it is possible to improve the limitations in optical properties, exposure, development, and sensitivity implementation due to the support substrate in a structure in which a supporting substrate such as a polyethylene terephthalate (PET) film is laminated or laminated.

On the other hand, the present inventors 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 detail in the method for manufacturing a photosensitive laminate to be described later. a mixed solvent including a high boiling point solvent having a and a low boiling point solvent having a boiling point of 100°C or less; binder resin; a photopolymerizable compound including a 2 to 10 functional (meth)acrylate monomer or oligomer containing an aromatic functional group in the molecule; and a photoinitiator; using a resin composition including, 5/mm ² or less, or 3/mm ² or less of bubbles having a diameter of less than 1 μm in the photosensitive resin layer.

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 or may not be present in a trace amount, more specifically, from the opposite surface of the interface between the barrier layer and the photosensitive resin layer of the photosensitive resin layer. Within 50% of the total thickness, 3 cells/mm ² or less of cells 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 barrier layer 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, and may not include bubbles having a diameter of 1 μm or more and 5 μm or less.

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 when the photosensitive resin layer is exposed to ultraviolet light and developed with an alkali solution, defects do not occur or occur over the entire area, and a very small amount may occur. It is not substantially present, and after development, micro-sized defects may be present in a very small amount on the lower surface or inside of the photosensitive resin layer.

Specifically, after exposing the photosensitive resin layer to ultraviolet light and developing with an alkali solution, 3 defects/mm ² or less, or 1/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 15 μm, or less than 10 μm, or less than 7 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 including a carboxyl group. 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 a repeating unit represented by the following Chemical Formula 3, a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by the following Chemical Formula 5, and a repeating unit represented by the following Chemical Formula 6 It may be a polymer or a copolymer including one or more repeating units selected from the group consisting of.

[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

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 methyl can be heard

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 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 include methyl methacrylate (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 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, 30,000 g/mol to 300,000 g/mol, It may have a weight average molecular weight of 30,000 g/mol to 250,000 g/mol, 30,000 g/mol to 200,000 g/mol, or 30,000 g/mol to 150,000 g/mol.

In addition, the binder resin should have heat resistance of at least a certain level, and accordingly, 20 ℃ or more and 150 ℃ or less, 50 ℃ or more and 150 ℃ or less, 70 ℃ or more and 150 ℃ or less, 70 ℃ or more 120 ℃ or less, 80 ℃ or more and 120 ℃ or less , or may have a glass transition temperature of 100 °C or more and 120 °C or less.

In addition, the 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 in consideration of the developability of the photosensitive resin layer. , 120 mgKOH/g or more and 200 mgKOH/g or less, or 150 mgKOH/g or more and 200 mgKOH/g or less.

On the other hand, the photosensitive resin layer includes a cross-linked copolymer between an alkali developable binder resin including a carboxyl group and a photopolymerizable compound including a 2 to 10 functional (meth)acrylate monomer or oligomer containing an aromatic functional group in the molecule. may be

The photopolymerizable compound including the (meth)acrylate monomer or oligomer may serve as a crosslinking agent to increase mechanical strength of the photosensitive resin layer, or to increase resistance to a developer and to provide flexibility of the cured film.

According to the specific use or characteristics of the photosensitive resin layer, the content of the photopolymerizable compound including the 2 to 10 functional (meth)acrylate monomer or oligomer containing the aromatic functional group in the molecule may be adjusted, for example, Based on 100 parts by weight of the binder resin, 1 to 80 parts by weight of a photopolymerizable compound including 2 to 10 functional (meth)acrylate monomers or oligomers containing an aromatic functional group in a molecule may be included.

Specifically, the photopolymerizable compound including the 2 to 10 functional (meth)acrylate monomer or oligomer containing the aromatic functional group in the molecule may include a bifunctional (meth)acrylate compound represented by the following Chemical Formula 1 .

[Formula 1]

In Formula 1, R ₁ and R ₂ are the same as or different from each other, and are H or CH ₃ , and j and k are each an integer of 1 to 20.

More specifically, the bifunctional (meth)acrylate compound of Formula 1 may include a bifunctional (meth)acrylate compound of Formula 11 below and a bifunctional (meth)acrylate compound of Formula 12 below.

[Formula 11]

In Formula 11, R ₁₁ and R ₁₂ are the same as or different from each other, and are H or CH ₃ , and J1 and K1 are each an integer of 1 to 8.

[Formula 12]

In Formula 12, R ₂₁ and R ₂₂ are the same as or different from each other, and are H or CH ₃ , and J2 and K2 are each an integer of 10 to 20.

More specifically, the bifunctional (meth) acrylate compound of Formula 1 is the bifunctional (meth) acrylate compound of Formula 11: the difunctional (meth) acrylate compound of Formula 12 is 1:1 to 1:30, 1:1.1 to 1:30, 1:1.1 to 1:20, 1:1.1 to 1:10, 1:1.1 to 1:5, 1:2 to 1:30, 1:2 to 1:20, 1: It may be included in a weight ratio of 2 to 1:10, 1:2 to 1:5.

By using the bifunctional (meth)acrylate compound of Formula 12 in an equivalent weight or more than the bifunctional (meth)acrylate compound of Formula 11, adhesion to the substrate is increased and resistance to developer is improved As a result, excellent fine wire adhesion and resolution can be secured.

Meanwhile, the photopolymerizable compound may further include a monofunctional or polyfunctional (meth)acrylate compound in addition to the bifunctional (meth)acrylate compound of Formula 1 above. In this case, the usable monofunctional or polyfunctional (meth)acrylate compound excludes the compound included in the bifunctional (meth)acrylate compound of Formula 1 above.

Examples of additionally usable photopolymerizable compounds are not particularly limited, but ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate ), propylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol Dimethacrylate (neopentyl glycol dimethacrylate), 1,6-hexane glycol dimethacrylate (1,6-hexane glycol dimethacrylate), trimethylolpropane trimethacrylate, trimethylolpropane triacrylate (trimethyolpropane) triacrylate), glycerin dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentamethacrylate, 2,2-bis(4-methacryloxydiethoxyphenyl)propane (2,2-bis(4-methacryloxydiethoxyphenyl)propane), 2,2-bis(4-methacryloxypolyethoxyphenyl)propane (2, 2-bis(4-methacryloxypolyethoxyphenyl)propane), 2-hydroxy-3-methacryloyloxypropyl methacryl ate), ethylene glycol diglycidyl ether dimethacrylate, diethylene glycol diglycidyl ether dimethacrylate, phthalic acid diglycidyl ether dimethacrylate and acrylate (phthalic acid diglycidyl ester dimethacrylate), glycerin polyglycidyl ether polymethacrylate, and polyfunctional (meth)acrylate containing a urethane group.

On the other hand, various plastic films can be used as the supporting substrate, for example, an acrylic film, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a polynorbornene (PNB) film, a cycloolefin polymer (COP) ) film, and at least one plastic film selected from the group consisting of a polycarbonate (PC) film.

Meanwhile, the release layer may include a protective film.

That is, 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 the range of, for example, 0.01 μm to 1 m.

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; binder resin; a photopolymerizable compound including a 2 to 10 functional (meth)acrylate monomer or oligomer containing an aromatic functional group in the molecule; And a photoinitiator; and coating and drying the resin composition containing the barrier layer on the barrier layer, a method of manufacturing a photosensitive laminate may be provided.

According to the manufacturing method, the photosensitive laminate described above in the embodiment may be provided.

As described above, the photosensitive laminate may include a barrier layer having a haze of 2% or less; and a photosensitive resin layer including a photopolymerizable compound and a binder resin including a 2 to 10-functional (meth)acrylate monomer or oligomer containing an aromatic functional group in the molecule, and a diameter of less than 1 μm in the photosensitive resin layer 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 barrier layer 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 barrier layer and the photosensitive resin layer or on the outer surface of the photosensitive resin layer are present in a trace amount or substantially absent, reliability during development is increased, so that high-density It is possible to form a circuit 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, or 3 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 includes the high boiling point solvent 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 1:20, or 1:3 to 1:15 can do. 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; binder resin; a photopolymerizable compound including a 2 to 10 functional (meth)acrylate monomer or oligomer containing an aromatic functional group in the molecule; 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 barrier layer is not greatly limited, For example, the resin composition may be coated on the barrier layer 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 drying time may vary depending on the drying temperature, for example, may be 30 seconds to 20 minutes, more specifically 1 minute to 10 minutes, or 3 minutes to 7 minutes.

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

The binder resin is 20,000 g/mol to 300,000 g/mol, 30,000 g/mol to 300,000 g/mol, 30,000 g/mol to 250,000 g/mol, 30,000 g/mol to 200,000 g/mol, or 30,000 g/mol to A weight average molecular weight of 150,000 g/mol and 20 °C or more and 150 °C or less, 50 °C or more and 150 °C or less, 70 °C or more and 150 °C or less, 70 °C or more and 120 °C or less, 80 °C or more and 120 °C or less, or 100 °C or more and 120 °C It may have the following glass transition temperature.

The 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 150 It may have an acid value of mgKOH/g or more and 200 mgKOH/g or less.

The resin composition may further include a photopolymerizable compound including a 2 to 10 functional (meth)acrylate monomer or oligomer including an aromatic functional group in the molecule together with the binder resin.

The resin composition may include 1 to 80 parts by weight of a photopolymerizable compound including a 2 to 10 functional (meth)acrylate monomer or oligomer containing an aromatic functional group in a molecule relative to 100 parts by weight of the binder resin.

Specifically, the photopolymerizable compound may be a bifunctional (meth) acrylate compound represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ and R ₂ are the same as or different from each other, and are H or CH ₃ , and j and k are each an integer of 1 to 20.

More specifically, the bifunctional (meth)acrylate compound of Formula 1 may include a bifunctional (meth)acrylate compound of Formula 11 below and a bifunctional (meth)acrylate compound of Formula 12 below.

[Formula 11]

In Formula 11, R ₁₁ and R ₁₂ are the same as or different from each other, and are H or CH ₃ , and J1 and K1 are each an integer of 1 to 8.

[Formula 12]

In Formula 12, R ₂₁ and R ₂₂ are the same as or different from each other, and are H or CH ₃ , and J2 and K2 are each an integer of 10 to 20.

More specifically, the bifunctional (meth) acrylate compound of Formula 1 is the bifunctional (meth) acrylate compound of Formula 11: the difunctional (meth) acrylate compound of Formula 12 is 1:1 to 1:30, 1:1.1 to 1:30, 1:1.1 to 1:20, 1:1.1 to 1:10, 1:1.1 to 1:5, 1:2 to 1:30, 1:2 to 1:20, 1: It may be included in a weight ratio of 2 to 1:10, 1:2 to 1:5.

By using the bifunctional (meth)acrylate compound of Formula 12 in an equivalent weight or more than the bifunctional (meth)acrylate compound of Formula 11, adhesion to the substrate is increased and resistance to developer is improved As a result, excellent fine wire adhesion and resolution can be secured.

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, it can proceed at a lamination speed of 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 method of manufacturing 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, 800×) using a polarizing microscope.

2 is a photograph obtained by confirming the surface and cross-section of the photosensitive resin layer of Comparative Example 1 with a field emission scanning electron microscope (FE-SEM, 800×) using a polarizing microscope.

3 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, 800×) using a polarizing microscope.

4 is a photograph obtained by confirming the surface and cross-section of the photosensitive resin layer of Comparative Example 3 with a field emission scanning electron microscope (FE-SEM, 800×) using a polarizing microscope.

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 Example 1: Preparation of alkali developable binder resin

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, a monomer mixture of 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) as a monomer was added, and the temperature was raised to 80 ° C. and then polymerized for 6 hours to prepare an alkali developable binder resin (weight average molecular weight 40,000 g/mol, glass transition temperature 102 ° C., solid content 50 wt%, acid value 156 mgKOH/g). .

The alkali developable binder resin prepared in Preparation Example 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), and a Syringe Filter of 0.45㎛ Pore Size After filtration, 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

Preparation Example 2: Preparation of a composition for forming a barrier layer

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, 200 g of distilled water and 20 g of butyl cellosolve (BC) were added and completely dissolved. Here, 20 g of PVA-205 (KURARAY, polyvinyl alcohol, viscosity: 3.5 cP, weight average molecular weight: 22,000 g/mol) and 1.5 g of BYK-349 (BYK) were added to prepare a composition for forming a barrier layer. .

Preparation Example 3: Preparation of a composition for forming a barrier layer

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. Into the flask purged with nitrogen, 200 g of distilled water and 10 g of butyl cellosolve (BC) were added and completely dissolved. Here, 20 g of PVA-205 (KURARAY, polyvinyl alcohol, viscosity: 3.5 cP, weight average molecular weight: 22,000 g/mol) and 1.5 g of BYK-349 (BYK) were added to prepare a composition for forming a barrier layer. .

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

Examples 1-6

The composition for forming a barrier layer obtained in Preparation Example 2 was coated on a 25 μm PET film using a coating bar. The coated barrier layer is dried using a hot air oven, where the drying temperature is 80 ℃, the drying time is 10 minutes, the thickness of the barrier layer after drying is 2-3 μm, the haze value of the barrier layer is 1%, and oxygen The transmittance was 3.5 cc/m ² /day.

Then, according to the composition shown in Table 1, after dissolving the photoinitiator in an organic solvent, the photopolymerizable compound and the 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 the barrier layer 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 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.

The haze of the barrier layer is a value measured according to the measurement method of ASTM D1003 by peeling the PET film and using a HAZE METER (model name: NDH7000, Nippon Denshoku Co.).

The oxygen permeability of the barrier layer was 3.5 cc/m ² /day, and was measured according to ASTM F1927 using an OX-Tran (Model 2/61, Mocon) instrument.

Comparative Example 1

According to the composition described in Example 1 of Table 1 below, a 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 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 resin 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.

Comparative Example 2

A photosensitive laminate (dry film photoresist) was prepared in the same manner as in Example 1, except that the composition for forming a barrier layer obtained in Preparation Example 3 was used instead of the composition for forming a barrier layer obtained in Preparation Example 2 .

The haze of the prepared barrier layer was 5%, and the haze of the barrier layer was peeled off the PET film before the photosensitive resin composition was applied, and according to the measurement method of ASTM D1003 using a HAZE METER (model name: NDH7000, Nippon denshoku Corporation). is the measured value.

The oxygen permeability of the prepared barrier layer was 4.0 cc/m ² /day, and was measured according to the measurement method of ASTM F1927 using an OX-Tran (Model 2/61, Mocon Company) instrument.

Comparative Example 3-4

According to the composition shown in Table 2, a photosensitive laminate (dry film photoresist) was prepared in the same manner as in the above Example, except that the photosensitive resin composition was prepared.

ingredient (weight%)	product name (or ingredient name)	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
Alkali developable binder resin	Preparation Example 1	55	55	55	55	55	55
photopolymerizable compound	M-2101	15	10	15	15	15	15
	M-241	3	8	3	3	3	3
	M-281	2	2	2	2	2	2
photoinitiator	BCIM	3.5	3.5	3.5	3.5	3.5	3.5
	9,10-dibutoxyanthracene	0.5	0.5	0.5	0.5	0.5	0.5
additive	N,N-Diethylbutylamine	0.2	0.2	0.2	0.2	0.2	0.2
	Ruiko Crystal Violet (Japan Hodogaya Co.)	0.5	0.5	0.5	0.5	0.5	0.5
	Diamond Green GH (Japan Hodogaya Co.)	0.3	0.3	0.3	0.3	0.3	0.3
solvent	MEK (Methyl Ethyl Ketone, boiling point about 80 ℃)	15	15	15	10	15	15
	Methanol (Methanol, about 64.7 ° C)	2	2		4	4
	n-butanol (boiling point 117.7 ° C)			2			5
	Propylene glycol monomethyl ether acetate (PGMEA, boiling point 146.4° C.)	3	3	3	6	One

(1) M2101: Bisphenol A (EO) ₁₀ dimethacrylate (Miwon Specialty Chemical) (2) M281: Polyethylene glycol dimethacrylate (Miwon Specialty Chemical)

(3) M241: bisphenol A (ethoxylate) ₄ dimethacrylate (Miwon Specialty Chemical)

(4) BCIM: 2,2'-Bis-(2-chlorophenyl-4,5,4',5'-tetraphenylbisimidazole, Aldrich Chemical

ingredient (weight%)	product name (or ingredient name)	Comparative Example 3	Comparative Example 4
Alkali developable binder resin	Preparation Example 1	55	55
photopolymerizable compound	M-2101	15	15
	M-241	3	3
	M-280	2	2
photoinitiator	BCIM	3.5	3.5
	9,10-dibutoxyanthracene	0.5	0.5
additive	N,N-Diethylbutylamine	0.2	0.2
	Ruiko Crystal Violet (Japan Hodogaya Co.)	0.5	0.5
	Diamond Green GH (Japan Hodogaya Co.)	0.3	0.3
solvent	MEK (Methyl Ethyl Ketone, boiling point about 80 ℃)	15	20
	Methanol (about 64.7 ℃)	5
	n-butanol (boiling point 117.7 ° C)
	Propylene glycol monomethyl ether acetate (PGMEA, boiling point 146.4 ℃)

Comparative Example 5 Based on the description of Example 4 of Patent Document 1, 300 parts by weight of the “alkali developable binder resin” obtained in Preparation Example 1 of the present specification, the following components were mixed with a mechanical stirrer for about 1 hour A photosensitive laminate (dry film photoresist) was prepared in the same manner as in the above Example, except that the photosensitive resin composition was prepared by mixing.

<Component of the photosensitive resin composition>

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

(2) EO, PO modified urethane dimethacrylate 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]

<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.

Remove the PET film of the dry film photoresist laminated on the copper clad laminate and use ORC's FDi-3 on the barrier layer using the Stouffer Graphic Arts Equipment's 41-step step tablet. After irradiating with UV light, it was left for 15 minutes. 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.

Comparative Example 1 uses a 41-layer step tablet from Stouffer Graphic Arts Equipment using ORC's FDi-3 on a PET film of dry film photoresist laminated on a copper clad laminate, and has a 405 nm wavelength with an exposure amount such that the remaining number of steps is 15. After irradiation with ultraviolet light, it was left for 15 minutes. 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.

After removing the PET film of the laminate and developing on the barrier layer, it is formed with an interval of 0.5 μm from 4 to 20 μm so that the spacing between the circuit line width and the circuit line can be 1:1. Using the existing data, using the 41-step step tablet of Stouffer Graphic Arts Equipment through ORC's FDi-3, the remaining step number was 15 steps, irradiated with ultraviolet light of a wavelength of 405 nm, and left for 15 minutes. After that, Na ₂ CO ₃ 1.0wt% aqueous solution was developed under the development conditions of the spray injection method.

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.

Comparative Example 1 uses a 41-layer step tablet from Stouffer Graphic Arts Equipment using ORC's FDi-3 on a PET film of dry film photoresist laminated on a copper clad laminate, and has a 405 nm wavelength with an exposure amount such that the remaining number of steps is 15. After irradiation with ultraviolet light, it was left for 15 minutes. 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.

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 removing the PET film of the laminate and developing on the barrier layer, Stouffer Graphic Arts through ORC's FDi-3 so that the distance between the circuit line width and the circuit line becomes 14㎛: 14㎛ Using a 41-step step tablet of Equipment Co., Ltd., irradiated with ultraviolet light of a wavelength of 405 nm at an exposure dose at which the number of remaining step steps became 15 steps, and left 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

Comparative Example 1 uses a 41-layer step tablet from Stouffer Graphic Arts Equipment using ORC's FDi-3 on a PET film of dry film photoresist laminated on a copper clad laminate, and has a 405 nm wavelength with an exposure amount such that the remaining number of steps is 15. After irradiation with ultraviolet light, it was left for 15 minutes. 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.

division	exposure [mJ/cm 2 ]	1:1 resolution [μm]	less than 1 μm diameter bubble [Number/㎟]	Defect after exposure/development [Number/㎟]
Example 1	50	6	0	0
Example 2	60	6	0	0
Example 3	50	6	0	0
Example 4	50	6	0	0
Example 5	50	6	One	One
Example 6	50	6	0	0
Comparative Example 1	50	8	0	0
Comparative Example 2	50	9	11	7
Comparative Example 3	50	9	36	13
Comparative Example 4	50	8	18	7
Comparative Example 5	350	14	17	7

As can be seen in Table 3 and FIG. 1, it was confirmed that the number of bubbles having a diameter of less than 1 μm was present in the photosensitive resin layer of the photosensitive laminates of Examples 1/mm ² or less. In addition, the photosensitive resin layer of the above embodiments does not substantially generate defects having a diameter of 0.5 μm or more and 3 μm or less, or 1 piece/mm ² or less after exposure to ultraviolet light and development with an alkaline solution. has been confirmed to occur. That is, in the photosensitive resin layer of the above embodiments, bubbles having a diameter of less than 1 μm are present in a trace amount and include a barrier layer having a haze of 2% or less. It was also observed that it was possible to realize high density and sensitivity and to form finer wiring while securing it.

On the other hand, in the photosensitive resin laminate of Comparative Examples, it is difficult to realize the resolution of the Example level even using the same level of energy as the Example, and in the photosensitive resin layer, 10 cells/ mm ² or more.

In addition, as confirmed in FIGS. 2 to 4, after the photosensitive resin layer obtained in Comparative Example was exposed and developed with an alkali solution, a large number of defects having a diameter of 0.5 μm or more and 3 μm or less appeared. Confirmed.

Claims (16)

1. a barrier layer having a haze of 2% or less; and

   A photosensitive resin layer including a photopolymerizable compound and a binder resin including 2 to 10 functional (meth)acrylate monomers or oligomers containing an aromatic functional group in the molecule;

   The photosensitive laminate, wherein the number of bubbles having a diameter of less than 1 μm is present in the photosensitive resin layer at 5/mm ² or less.
2. According to claim 1,

   The barrier layer has an oxygen permeability of 10 cc/m ² /day or less, the photosensitive laminate.
3. According to claim 1,

   The barrier layer comprises a polyvinyl alcohol resin having a weight average molecular weight of 5,000 g / mol to 1,000,000 g / mol, the photosensitive laminate.
4. 4. The method of claim 3,

   The polyvinyl alcohol resin has a viscosity of 1.0 cP to 10.0 cP, the photosensitive laminate.
5. According to claim 1,

   The barrier layer has a thickness of 0.1 μm to 10 μm,

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

   The photosensitive laminate further comprising a supporting substrate formed on the barrier layer and having a thickness of 1 μm to 100 μm.
7. The method of claim 1,

   The photosensitive laminate further comprising a release layer formed on the photosensitive resin layer and having a thickness of 0.01 μm to 1 m.
8. The method of claim 1,

   Within 50% of the total thickness of the photosensitive resin layer from the opposite surface of the interface between the barrier layer and the photosensitive resin layer, 3 cells/mm ² or less of bubbles having a diameter of less than 1 μm are present.
9. According to claim 1,

   wherein the photosensitive resin layer does not contain bubbles having a diameter of 1 μm or more and 5 μm or less.
10. 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.
11. The method of claim 1,

    The binder resin is a photosensitive laminate comprising an alkali developable binder resin containing a carboxyl group.
12. According to claim 1,

    The photosensitive resin layer comprises a crosslinked copolymer between an alkali developable binder resin including a carboxyl group and a photopolymerizable compound including a 2 to 10 functional (meth)acrylate monomer or oligomer containing an aromatic functional group in the molecule, photosensitive laminate.
13. According to claim 1,

    The photopolymerizable compound including a 2 to 10 functional (meth)acrylate monomer or oligomer containing the aromatic functional group in the molecule is a photosensitive laminate comprising a bifunctional (meth)acrylate compound of Formula 1 below:

    [Formula 1]

    

    In Formula 1,

    R ₁ and R ₂ are the same as or different from each other, and H or CH ₃ ,

    j and k are each an integer from 1 to 20;
14. 14. The method of claim 13,

    The bifunctional (meth)acrylate compound of Formula 1 includes the bifunctional (meth)acrylate compound of Formula 11: the bifunctional (meth)acrylate compound of Formula 12 below in a weight ratio of 1:1 to 1:30 which is a photosensitive laminate:

    [Formula 11]

    

    In the above formula (11),

    R ₁₁ and R ₁₂ are the same as or different from each other, and H or CH ₃ ,

    J1 and K1 are each an integer from 1 to 8;

    [Formula 12]

    

    In the above formula (12),

    R ₂₁ and R ₂₂ are the same as or different from each other and are H or CH ₃ ,

    J2 and K2 are each an integer from 10 to 20.
15. According to claim 1,

    The 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, the photosensitive laminate.
16. The manufacturing method of a circuit board using the photosensitive laminated body of Claim 1.

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