WO2021137444A1 - Photosensitive laminate, method for manufacturing photosensitive laminate, and method for manufacturing circuit board - Google Patents

Abstract

The present invention relates to: a photosensitive laminate comprising a support substrate and a photosensitive resin layer formed on the support substrate, wherein the number of bubbles having a diameter of less than 1 μm present in the photosensitive resin layer is at most 5/mm2; and a method for manufacturing the photosensitive laminate.

Description

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

Cross-Citation with Related Application(s)

This application is based on Korean Patent Application No. 10-2019-0179860 on December 31, 2019, Korean Patent Application No. 10-2020-0099130 on August 07, 2020, and Korean Patent Application No. 10-2020 on September 25, 2020 Claims the benefit of priority based on No. -0125243, and all contents disclosed in the literature of the corresponding Korean patent applications 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. Processes to which ultra-high pressure mercury lamps or laser direct exposure are applied, or a photosensitive laminate including a support film and a photosensitive resin layer A manufacturing process of a circuit board using the same is also widely used.

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 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, securing high reliability during development, and 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 formed on the paper substrate, wherein 5 cells/mm ² or less of bubbles having a diameter of less than 1 μm are present in the photosensitive resin layer.

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, the weight average molecular weight means the weight average molecular weight in terms of polystyrene measured by the GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a commonly known analyzer and a detector such as a differential refraction detector and a column for analysis may be used, and the temperature generally 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 to measure at 40°C.

For this, the polystyrene standard sample (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 was 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 obtained 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 the present 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 supporting substrate; and a photosensitive resin layer comprising a photopolymerizable compound comprising a trifunctional or higher polyfunctional (meth)acrylate compound and an alkali developable binder resin, wherein the cells having a diameter of less than 1 μm in the photosensitive resin layer are 5 A photosensitive laminate may be provided, present at up to pcs/mm ^{2 .}

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 experiments, it was confirmed through experiments that it is possible to realize high sensitivity to high sensitivity and to increase reliability during development, to realize high density and sensitivity while securing high reliability, and to form finer wiring, and completed the invention.

The present inventors continued research and development to remove traces of micro-bubbles or micro-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 containing a mixed solvent including a high boiling point solvent and a low boiling point solvent having a boiling point of 100° C. or less together with an alkali developable binder resin, a photopolymerizable compound and a photoinitiator, Cells 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 less, 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 by adjusting 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 supporting 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, Reliability during development is increased, so that high-density circuits can be formed and defects can be reduced in the formation of fine wiring. Accordingly, when the photosensitive laminate is used, 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 include a very small amount or substantially no air bubbles having a diameter of less than 1 μm, and 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 microscopic defects may be present 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 alkali solution, there are 3 defects/mm ² or less having a cross-sectional diameter of 0.3 μm to 4 μm, or 0.5 μm or more and 3 μm 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 can be carried out by a method such as a 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 higher sensitivity can be realized while using lower energy. More specifically, the amount of energy at which the remaining number of steps becomes 15 when the wavelength of the light irradiated to the photosensitive laminate is in the range of 340 nm to 420 nm, measured using a 41-step step tablet manufactured by Stouffer Graphic Arts Equipment, 300 mJ/cm2 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.

In the photosensitive laminate, the thickness of the supporting substrate and the photosensitive resin layer is not particularly limited, but as a specific example, the thickness of the supporting substrate may be 1 μm to 100 μm, or 5 μm to 50 μm, and the thickness of the photosensitive resin layer. The thickness may be from 1 μm to 100 μm, or from 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 exist 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 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, 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 3-1, _{the contents of R 4} and R ₅ are the same as those 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 contents of Ar are the same as those 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, or 30,000 g/mol to 150,000 g/mol. It may have a weight average molecular weight of g/mol.

In addition, the alkali developable binder resin should have heat resistance of at least a certain level, and thus may have a glass transition temperature of 20° C. or more and 150° C. or less.

In addition, the alkali developable binder resin may have an acid value of 100 mgKOH/g or more and 300 mgKOH/g in consideration of the developability of the photosensitive resin layer.

On the other hand, the alkali developable binder resin may include two or more alkali-forming 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, and a glass transition temperature may be 20° C. or more and 150° C. or less, and each different weight average It may have a molecular weight, a glass transition temperature, or an acid value.

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

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, 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 (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 (meth)acrylate monomer or oligomer can be adjusted, for example, relative to 100 parts by weight of the alkali developable binder resin (meth) It may contain 1 to 80 parts by weight of the photopolymerizable compound including the acrylate monomer or oligomer.

The photopolymerizable compound may be 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, but in order for the photosensitive resin layer to satisfy the above-described properties, the photopolymerizable compound is trifunctional or more polyfunctional. It may include a (meth)acrylate compound.

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 depending on the selection of the photopolymerizable compound to be used, microbubbles are formed inside the photosensitive resin layer. It may be present in trace amounts or substantially absent.

Specifically, the trifunctional or more polyfunctional (meth)acrylate compound has a structure in which three or more alkylene oxide groups and (meth)acrylate functional groups each having 1 to 10 carbon atoms are bonded to a central group having 1 to 20 carbon atoms. can have

Due to the structure of the trifunctional or higher polyfunctional (meth)acrylate compound, it is possible to cause a small amount of bubbles having a diameter of 1 μm or less to exist in the photosensitive resin layer, thereby reducing defects in the formation of fine wiring. In addition, a photosensitive laminate capable of forming high-density circuits by securing high reliability during development may be provided.

More specifically, the trifunctional or higher polyfunctional (meth)acrylate compound may include a compound of Formula 1 below.

[Formula 1]

In Formula 1,

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

R ₅ is alkylene having 1 to 10 carbon atoms,

R ₆ is a p-valent functional group including a central group having 1 to 20 carbon atoms,

n2 is an integer from 1 to 20,

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

A more specific example of the compound of Formula 1 may include a compound of Formula 1-1 below.

[Formula 1-1]

In Formula 1-1,

R ₆ ' is a trivalent functional group having 1 to 10 carbon atoms,

R ₇ to R ₉ are each independently alkylene having 1 to 10 carbon atoms,

R ₁₀ to R ₁₂ are each independently hydrogen, or alkyl having 1 to 10 carbon atoms,

n3 to n5 are each independently an integer of 1 to 3.

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

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

Specifically, the monofunctional (meth)acrylate compound may include a monofunctional (meth)acrylate compound represented by Formula 2 below.

[Formula 2]

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

The photopolymerizable compound may include the monofunctional (meth)acrylate compound and the trifunctional or more polyfunctional (meth)acrylate compound together. Specifically, the photopolymerizable compound may include a monofunctional (meth)acrylate compound including a (meth)acrylate including an alkylene oxide group having 1 to 10 carbon atoms; and a trifunctional or more polyfunctional (meth)acrylate compound having a structure in which three or more alkylene oxide groups and (meth)acrylate functional groups having 1 to 10 carbon atoms are bonded to a central group having 1 to 20 carbon atoms; can

In consideration of the characteristics of the photosensitive resin layer and the photosensitive laminate, the content of the monofunctional (meth) acrylate compound and the trifunctional or more polyfunctional (meth) acrylate compound included in the photopolymerizable compound may be adjusted.

For example, the photopolymerizable compound may include 110 parts by weight or more and 500 parts by weight or less of the trifunctional or more polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound.

In addition, the photopolymerizable compound may be included in an amount of 500 parts by weight or more and 1000 parts by weight or less of the bifunctional (meth)acrylate compound based on 100 parts by weight of the trifunctional or higher polyfunctional (meth)acrylate compound.

On the other hand, the photopolymerizable compound further includes a monofunctional or polyfunctional (meth) acrylate compound that does not overlap with these other than a monofunctional (meth) acrylate compound and a trifunctional or more polyfunctional (meth) acrylate compound. can do. In this case, as a usable monofunctional or polyfunctional (meth)acrylate compound, the trifunctional or more polyfunctional (meth)acrylate compound of Formula 1 and the monofunctional (meth)acrylate compound of Formula 2 are excluded.

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.

Meanwhile, 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 suitable releasability and adhesiveness so as not to be released during storage and distribution.

Various plastic films can be used as the protective film, for example, an acrylic film, a polyethylene (PE) film, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a polynorbornene (PNB) film, a cyclo It may include at least one plastic film selected from the group consisting of an olefin polymer (COP) film, and a polycarbonate (PC) film. The thickness of the protective film is not particularly limited, but can be freely adjusted within, for example, 0.01 μm to 100 μm.

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 comprising a trifunctional or more polyfunctional (meth)acrylate compound; alkali developable binder resin; and a photoinitiator; applying and drying a resin composition containing a resin composition 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 manufacturing a photosensitive laminate, including in a weight ratio of 1:18, 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 includes a supporting substrate; and a photosensitive resin layer comprising a photopolymerizable compound comprising a trifunctional or higher polyfunctional (meth)acrylate compound and an alkali developable binder resin. The number of bubbles having a diameter of less than 1 μm in the photosensitive resin layer ^{may be 5/mm 2} or less.

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 may be present in ^{the photosensitive resin layer at 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 supporting substrate and the photosensitive resin layer or the photosensitive resin layer toward the outer surface are present in a trace amount or substantially absent, the 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 a certain amount or more, 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 1:18, or a weight ratio of 1:3 to 1:15 can be included as The high boiling point solvent having a boiling point of 115° C. or more: 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 Cypionate, dipropylene glycol dimethyl ether, cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), and one or more mixed solvents thereof are mentioned.

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 include a solid content in consideration of specific uses or fields of application, 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 particularly 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 less, the drying rate and/or drying temperature are adjusted. Through this, the amount of microbubbles formed in the photosensitive resin layer may be greatly reduced or may be substantially absent.

More specifically, the drying of the coated resin composition may be performed by a 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. of 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 of 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 may have a weight average molecular weight of 20,000 g/mol to 300,000 g/mol, or 30,000 g/mol to 150,000 g/mol, and a glass transition temperature of 20°C or more and 150°C or less.

The alkali developable binder resin may have an acid value of 100 mgKOH/g or more and 300 mgKOH/g.

The resin composition may further include a photopolymerizable compound including a (meth)acrylate monomer or oligomer together with an alkali developable binder resin.

The resin composition may include 1 to 80 parts by weight of a photopolymerizable compound including a (meth)acrylate monomer or oligomer based on 100 parts by weight of the alkali developable binder resin.

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

The photopolymerizable compound may be 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, but in order for the photosensitive resin layer to satisfy the above-described properties, the photopolymerizable compound is trifunctional or more polyfunctional. It may include a (meth)acrylate compound.

In the method of 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, the trifunctional or more polyfunctional (meth)acrylate compound has a structure in which three or more alkylene oxide groups and (meth)acrylate functional groups each having 1 to 10 carbon atoms are bonded to a central group having 1 to 20 carbon atoms. can have

Due to the structure of the trifunctional or higher polyfunctional (meth)acrylate compound, it is possible to cause a small amount of bubbles having a diameter of 1 μm or less to exist in the photosensitive resin layer, thereby reducing defects in the formation of fine wiring. In addition, a photosensitive laminate capable of forming high-density circuits by securing high reliability during development may be provided.

More specifically, the trifunctional or higher polyfunctional (meth)acrylate compound may include a compound of Formula 1 below.

[Formula 1]

In Formula 1,

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

R ₅ is alkylene having 1 to 10 carbon atoms,

R ₆ is a p-valent functional group including a central group having 1 to 20 carbon atoms,

n2 is an integer from 1 to 20,

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

A more specific example of the compound of Formula 1 may include a compound of Formula 1-1 below.

[Formula 1-1]

In Formula 1-1,

R ₆ ' is a trivalent functional group having 1 to 10 carbon atoms,

R ₇ to R ₉ are each independently alkylene having 1 to 10 carbon atoms,

R ₁₀ to R ₁₂ are each independently hydrogen, or alkyl having 1 to 10 carbon atoms,

n3 to n5 are each independently an integer of 1 to 3.

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

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

Specifically, the monofunctional (meth)acrylate compound may include a monofunctional (meth)acrylate compound represented by Formula 2 below.

[Formula 2]

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

The photopolymerizable compound may include the monofunctional (meth)acrylate compound and the trifunctional or more polyfunctional (meth)acrylate compound together. Specifically, the photopolymerizable compound may include a monofunctional (meth)acrylate compound including (meth)acrylate including an alkylene oxide group having 1 to 10 carbon atoms; and a trifunctional or more polyfunctional (meth)acrylate compound having a structure in which three or more alkylene oxide groups and (meth)acrylate functional groups having 1 to 10 carbon atoms are bonded to a central group having 1 to 20 carbon atoms; can

In consideration of the characteristics of the photosensitive resin layer and the photosensitive laminate, the content of the monofunctional (meth) acrylate compound and the trifunctional or more polyfunctional (meth) acrylate compound included in the photopolymerizable compound may be adjusted.

For example, the photopolymerizable compound may include 110 parts by weight or more and 500 parts by weight or less of the trifunctional or more polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound.

In addition, the photopolymerizable compound may be included in an amount of 500 parts by weight or more and 1000 parts by weight or less of the bifunctional (meth)acrylate compound based on 100 parts by weight of the trifunctional or higher polyfunctional (meth)acrylate compound.

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-diethyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethyl thioxanthone, 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, benzyl ketone 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 the present invention is limited thereto. no.

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 with respect to the total weight of the resin composition based on the solid content. 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 developer contamination may be increased, which may lead to defects such as short circuit.

In addition, the resin composition may further include other additives as necessary. Examples of the other additives include dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, and diallyl phthalate in the form of phthalic acid esters as plasticizers; triethylene glycol diacetate, tetraethylene glycol diacetate in the form of glycol esters; 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 wt% or more and 10 wt% 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, fucine, 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.

In addition, 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 for 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.

After the printed circuit board that has undergone the lamination process is left for at least 15 minutes to stabilize the substrate, the photoresist of the DFR may be exposed 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, and the unexposed area is left in a state where the crosslinking reaction has not proceeded. may exist.

Next, a developing process of removing the unexposed portion of the photoresist is performed. In the case of alkaline 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 improved 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, 10,000 times) using a polarizing microscope.

FIG. 2 is a photograph 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×) 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, 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 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) did.

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 have a pore size of 0.45㎛. 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. As a 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, the polystyrene standard sample (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 was 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 obtained 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 and Comparative Examples: Preparation of photosensitive resin composition and dry film photoresist>

According to the composition shown in Table 1 below, 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 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	M-2101	14	13	12	14
	M-241	3	3	3	3
	T063	2	3	3
	A040	One	One	2	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.)	0.3C	0.3C	0.3C	0.3C
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
(1) M2101: Bisphenol A (EO) 10 dimethacrylate (Miwon Specialty Chemical) (2) M241: bisphenol A (ethoxylate) 4 dimethacrylate (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: Preparation of photosensitive resin composition and dry film photoresist]

An experiment was performed to reproduce Example 4 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).

1. Preparation of photosensitive resin composition

Based on the description of Example 4 of the cited invention 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 for about 1 hour using a mechanical stirrer to obtain photosensitivity A resin composition was prepared.

<Components 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 part 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 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 of 405 nm wavelength using ORC's FDi-3, using a 41-layer step tablet from Stouffer Graphic Arts Equipment, and the remaining number of steps became 15 steps and left for 15 minutes. 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 using data 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 from Stouffer Graphic Arts Equipment, the remaining number of steps was 15 steps. After irradiating UV rays with a wavelength of 405 nm, it was left for 15 minutes. After that, development was carried out under the development conditions of a spray injection method 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 the 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 the 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 with 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 after exposure/development [number/㎟]
Example 1	50	7	0	0
Example 2	50	8	0	0
Example 3	50	9	One	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 are 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 large bubble having a diameter.

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 even after exposure to ultraviolet light and development with an alkaline solution. has been confirmed to occur.

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.

In contrast, 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.

Moreover, 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 (28)

1. support substrate; and

   A photosensitive resin layer comprising a photopolymerizable compound comprising a trifunctional or higher polyfunctional (meth)acrylate compound and an alkali developable binder resin;

   The number of bubbles having a diameter of less than 1 μm in the photosensitive resin layer 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 ^{exist in 3/mm 2} or less.
6. According to claim 1,

   The trifunctional or more polyfunctional (meth)acrylate compound,

   A photosensitive laminate having a structure in which three or more alkylene oxide groups having 1 to 10 carbon atoms and (meth)acrylate functional groups are each bonded to a central group having 1 to 20 carbon atoms.
7. According to claim 1,

   The trifunctional or more multifunctional (meth) acrylate compound is a photosensitive laminate comprising a compound of Formula 1:

   [Formula 1]

   

   In Formula 1,

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

   R ₅ is alkylene having 1 to 10 carbon atoms,

   R ₆ is a p-valent functional group including a central group having 1 to 20 carbon atoms,

   n2 is an integer from 1 to 20,

   p is the _{number of functional groups substituted for R 6} , and is an integer of 3 to 10.
8. According to claim 1,

   The photopolymerizable compound further comprises a monofunctional (meth) acrylate compound or a bifunctional (meth) acrylate compound, the photosensitive laminate.
9. 9. The method of claim 8,

   The monofunctional (meth) acrylate compound comprises a (meth) acrylate containing an alkylene oxide group having 1 to 10 carbon atoms, the photosensitive laminate.
10. 9. The method of claim 8,

    The photopolymerizable compound may include a monofunctional (meth)acrylate compound including (meth)acrylate including an alkylene oxide group having 1 to 10 carbon atoms; And a polyfunctional (meth) acrylate compound having a trifunctional or higher function having a structure in which at least three alkylene oxide groups and (meth)acrylate functional groups having 1 to 10 carbon atoms are bonded to a central group having 1 to 20 carbon atoms; containing; , a photosensitive laminate.
11. 9. The method of claim 8,

    The photopolymerizable compound comprises 110 parts by weight or more and 500 parts by weight or less of the trifunctional or more polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound.
12. 9. The method of claim 8,

    The photopolymerizable compound is a photosensitive laminate comprising 500 parts by weight or more and 1000 parts by weight or less of the bifunctional (meth)acrylate compound with respect to 100 parts by weight of the trifunctional or more polyfunctional (meth)acrylate compound.
13. 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.
14. 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.
15. The manufacturing method of a circuit board using the photosensitive laminated body of Claim 1.
16. 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; a photopolymerizable compound comprising a trifunctional or more polyfunctional (meth)acrylate compound; alkali developable binder resin; And a photoinitiator; including the step of applying and drying the resin composition comprising a support substrate,

    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 1:2 to 1:18,

    The method for producing the photosensitive laminate of claim 1 .
17. 17. The method of claim 16,

    The method for producing a photosensitive laminate, wherein 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.
18. 17. The method of claim 16,

    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.
19. 17. The method of claim 16,

    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.
20. 17. The method of claim 16,

    The trifunctional or more polyfunctional (meth)acrylate compound,

    A method for producing a photosensitive laminate, having a structure in which three or more alkylene oxide groups having 1 to 10 carbon atoms and (meth)acrylate functional groups are each bonded to a central group having 1 to 20 carbon atoms.
21. 17. The method of claim 16,

    The trifunctional or higher polyfunctional (meth) acrylate compound comprises a compound of the following formula (2), a method for producing a photosensitive laminate:

    [Formula 2]

    

    In the above formula (2),

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

    R ₅ is alkylene having 1 to 10 carbon atoms,

    R ₆ is a p-valent functional group including a central group having 1 to 20 carbon atoms,

    n2 is an integer from 1 to 20,

    p is the _{number of functional groups substituted for R 6} , and is an integer of 3 to 10.
22. 17. The method of claim 16,

    The photopolymerizable compound further comprises a monofunctional (meth) acrylate compound or a bifunctional (meth) acrylate compound, the method for producing a photosensitive laminate.
23. 23. The method of claim 22,

    The monofunctional (meth) acrylate compound comprises a (meth) acrylate containing an alkylene oxide group having 1 to 10 carbon atoms, the photosensitive laminate.
24. 23. The method of claim 22,

    The photopolymerizable compound may include a monofunctional (meth)acrylate compound including (meth)acrylate including an alkylene oxide group having 1 to 10 carbon atoms; And a polyfunctional (meth) acrylate compound having a trifunctional or higher function having a structure in which at least three alkylene oxide groups and (meth)acrylate functional groups having 1 to 10 carbon atoms are bonded to a central group having 1 to 20 carbon atoms; containing; , a photosensitive laminate.
25. 23. The method of claim 22,

    The photopolymerizable compound comprises 110 parts by weight or more and 500 parts by weight or less of the trifunctional or more polyfunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound.
26. 23. The method of claim 22,

    The photopolymerizable compound is a photosensitive laminate comprising 500 parts by weight or more and 1000 parts by weight or less of the bifunctional (meth)acrylate compound with respect to 100 parts by weight of the trifunctional or more polyfunctional (meth)acrylate compound.
27. 17. The method of claim 16,

    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.
28. 17. The method of claim 16,

    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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