KR102250828B1 - Photosensitive laminate, preparation method of photosensitive laminate, and preparation method of circuit board - Google Patents

Abstract

The present invention relates to a photosensitive laminate including a support substrate; and a photosensitive resin layer formed on the support substrate, wherein 5 bubbles/mm^2 or less with a diameter of 1 μm or less exist in the photosensitive resin layer, and a method for manufacturing the photosensitive laminate. The present invention can form high-density circuits.

Description

A photosensitive laminated body, a photosensitive laminated body manufacturing method, and a circuit board manufacturing method TECHNICAL FIELD [PHOTOSENSITIVE LAMINATE, PREPARATION METHOD OF PHOTOSENSITIVE LAMINATE, AND PREPARATION METHOD OF CIRCUIT BOARD}

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

The photosensitive resin composition is used in the form of dry film photoresist (DFR), liquid photoresist ink, etc., which are used for printed circuit boards (PCBs) or lead frames. .

In recent years, semiconductor devices tend to be light, thin, and short. According to multi-stage packaging, high-density of circuit boards is required, a process in which ultra-high pressure mercury or laser direct exposure is applied, or a photosensitive laminate including a support film and a photosensitive resin layer. The manufacturing process of a circuit board using the method is also widely used.

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

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

Further, the present invention is to provide a method for producing the photosensitive laminate.

Further, the present invention relates to a method of manufacturing a circuit board using the photosensitive laminate.

In this specification, the 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 1 μm or less are present in the photosensitive resin layer.

In addition, in the present specification, a method of manufacturing a circuit board using the photosensitive laminate may be provided.

In addition, in the present specification, a method of manufacturing the photosensitive laminate may be provided.

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

In this specification, 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 analysis device, a detector such as a Refractive Index Detector, and a column for analysis may be used. 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 to a concentration of 1.0 (w/w)% in THF (about 0.5 (w/w)% based on solid content), and a 0.45 μm pore size syringe After filtration using a filter, 20 µl was injected into GPC, and tetrahydrofuran (THF) was used as the mobile phase of the GPC, and flow rate was 1.0 mL/min, and the column was Agilent PLgel 5µm Guard (7.5 x 50 mm) and two Agilent PLgel 5㎛ Mixed D (7.5 x 300 mm) were connected in series and measured at 40℃ using an Agilent 1260 Infinity II System and RI Detector as a detector.

The polystyrene standard sample (STD A, B, C, D) in which polystyrene having various molecular weights is dissolved in tetrahydrofuran at a concentration of 0.1 (w/w)% as follows is filtered through a 0.45 μm 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 the calibration curve formed by injecting into.

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 constituents having a curable or crosslinkable unsaturated group in the chemical structure are cured, crosslinked or polymerized, but also partially cured. , Crosslinked or polymerized.

According to one embodiment of the invention, the support substrate; And a photosensitive resin layer formed on the paper substrate, wherein 5 cells/mm ² or less of bubbles having a diameter of 1 μm or less are present in the photosensitive resin layer.

In addition, according to one embodiment of the invention, the support substrate; And a photosensitive resin layer formed on the support base material, wherein 3 bubbles having a diameter of 1 μm or less within 50% of the total thickness of the photosensitive resin layer from the opposite surface of the interface between the support base material and the photosensitive resin layer. pieces / mm ² present at up to, and the photosensitive resin layer does not contain any air bubbles with a diameter of less than 5 1㎛ ㎛, the photosensitive resin layer is an alkali developability, a binder resin and a (meth) acrylate monomer containing the carboxyl group Alternatively, a photosensitive laminate including a crosslinked copolymer between photopolymerizable compounds including oligomers may be provided.

^{The present inventors have newly developed a photosensitive laminate including a photosensitive resin layer in which 5 cells/mm 2} or less of bubbles having a diameter of 1 μm or less exist, and using such a photosensitive laminate allows exposure to light in the manufacturing process of a circuit board. It has been confirmed through experiments that it is possible to achieve high sensitivity for the product, and the reliability is increased during development, thereby realizing high density and sensitivity while securing high reliability, and enabling the formation of finer wiring.

The present inventors have continued research and development to remove traces of fine bubbles or fine by-products that may occur for various reasons in the manufacturing process, and have a boiling point of 115° C. or higher as described above in the method of manufacturing a photosensitive laminate to be described later. Using a resin composition including a high boiling point solvent and a low boiling point solvent having a boiling point of 100° C. or less and an alkali developable binder resin including a carboxyl group and a photoinitiator together, the photosensitive resin layer has a diameter of 1 μm or less. Air bubbles were made to be present in 5 / mm ² or less, or 3 / mm ² or less.

In addition, in the method of manufacturing 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, drying speed and/or drying temperature Through the adjustment of, the amount of fine bubbles formed in the photosensitive resin layer may be greatly reduced or may not be substantially present.

Meanwhile, bubbles having a diameter of 1 μm or less may be present in the photosensitive resin layer in 5 / mm ² or less, or 3 / mm ² or less, in particular, the opposite side of the interface between the supporting substrate and the photosensitive resin layer, or The photosensitive resin layer may have a small amount or substantially no air bubbles having a diameter of 1 μm or less toward the outer surface, and more specifically, the entire photosensitive resin layer from the opposite surface of the interface between the supporting substrate and the photosensitive resin layer. Within 50% of the thickness, bubbles having a diameter of 1 μm or less may be present ^{at 3/mm 2 or less.}

As the opposite surface of the interface between the supporting substrate and the photosensitive resin layer, or the photosensitive resin layer toward the outer surface thereof, bubbles having a diameter of 1 μm or less are present in a trace amount or are substantially absent, High reliability during development makes it possible to form high-density circuits and reduce defects 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 are manufactured. The yield can be improved.

In addition, the photosensitive laminate may not include a very small amount or substantially not include bubbles having a diameter of 1 μm or less, and may not include bubbles having a diameter of more than 1 μm and 5 μm or less.

In this way, by using the photosensitive laminate in which bubbles having a diameter of 1 μm or less exist in a trace amount in the photosensitive resin layer, high density and sensitivity are achieved while securing high reliability when manufacturing a circuit board, and formation of finer wiring is possible. can do.

More specifically, even if the photosensitive resin layer is exposed to ultraviolet rays and developed with an alkali solution, defects may not occur or occur in a very small amount over the entire area, and in particular, defects may occur on the upper surface of the photosensitive resin layer. It does not exist substantially, and microscopic defects may exist on the lower surface or the inner side of the photosensitive resin layer after development.

Specifically, after exposing the photosensitive resin layer to ultraviolet rays and developing with an alkali solution, defects having a cross-sectional diameter of 0.3 μm to 4 μm, or 0.5 μm or more and 3 μm or less are 3/mm ² or less, or It may be observed to be less than 1/mm ^{2, and may not be substantially present.} The cross-sectional diameter of the defect may be defined as the largest diameter among the diameters of the bonding defined in the cross-section in one direction on the photosensitive resin layer.

The exposure and development conditions are not largely limited. For example, the exposure is an energy amount of 15 remaining steps measured using a 41 step step tablet manufactured by Stouffer Graphic Arts Equipment in the range of 340 nm to 420 nm in the wavelength of the light irradiated to the photosensitive laminate. It can proceed from 1 minute to 60 minutes. In addition, the above phenomenon may be performed through a method such as a spray spray method with an alkaline aqueous 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, a higher density and sensitivity can be realized while using lower energy. More specifically, when the wavelength of the light irradiated to the photosensitive laminate is in the range of 340 nm to 420 nm, the amount of energy that the remaining step number is 15 steps measured using a 41 step step tablet manufactured by Stouffer Graphic Arts Equipment is 300 mJ/cm 2 It may be less than or equal to 100 mJ/cm 2, and the resolution after development may be less than or equal to 15 μm or less than or equal to 10 μm.

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

On the other hand, the characteristics of the photosensitive layered product or the ^{constitutional feature in which 5 bubbles/mm 2} or less having a diameter of 1 μm or less exist in the photosensitive resin layer may be due to the above-described manufacturing method, and the photosensitive resin layer It may be due to the characteristics of the stratum.

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 and react with alkali during development.

Although a specific example of the alkali developable binder is not limited, a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), a repeating unit represented by the following formula (5), and a repeating unit represented by the following 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 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 an 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 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 aryl of.

In Formulas 2 to 4, R ₃ and R ₄ are the same as or different from each other, and each independently hydrogen or alkyl having 1 to 10 carbon atoms, and specific examples of the alkyl having 1 to 10 carbon atoms are methyl Can be mentioned.

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 a C6-C20 aryl, and a specific example of the C6-C20 aryl includes phenyl.

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

[Chemical Formula 4-1]

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

The repeating unit represented by Formula 5 may be a repeating unit derived from a monomer represented by Formula 5-1 below.

[Chemical 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 Chemical Formula 3-1, _{the contents of R 4} and R ₅ are the same as those described in Chemical Formula 3. Specific examples of the monomer represented by Chemical Formula 3-1 include methylmethacrylate (MMA) and butyl acrylate (BA).

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

[Chemical Formula 6-1]

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

On the other hand, the alkali developable binder resin including the carboxyl group may serve as a base material for the photosensitive resin layer, and thus must 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 may have a weight average molecular weight.

In addition, the alkali developable binder resin including the carboxyl group must have heat resistance of a certain level or higher, 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 including a carboxyl group may have an acid value of 100 mgKOH/g or more and 300 mgKOH/g in consideration of developability of the photosensitive resin layer.

Meanwhile, the photosensitive resin layer may include a crosslinked copolymer between an alkali developable binder resin containing a carboxyl group and a photopolymerizable compound containing a (meth)acrylate monomer or oligomer.

The photopolymerizable compound including the (meth)acrylate monomer or oligomer may serve as a crosslinking agent to increase the mechanical strength of the photosensitive resin layer, or to increase resistance to a developer and 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 may be adjusted, for example, compared to 100 parts by weight of the alkali developable binder resin including the carboxyl group. It may contain 1 to 80 parts by weight of a photopolymerizable compound including a (meth)acrylate monomer or oligomer. That is, the photosensitive resin layer may include a crosslinked copolymer between 100 parts by weight of the alkali developable binder resin including the carboxyl group and 1 to 80 parts by weight of the photopolymerizable compound including the (meth)acrylate monomer or oligomer.

The photopolymerizable compound may be a monofunctional or polyfunctional (meth)acrylate monomer or oligomer.

The photopolymerizable compound may be a commonly known monofunctional or polyfunctional (meth)acrylate monomer or oligomer, but in order to satisfy the above-described characteristics, the monofunctional or polyfunctional (meth)acrylate monomer or oligomer may be used. It is possible to use a 2 to 10 functional (meth)acrylate monomer or oligomer containing an aromatic functional group in the molecule.

Specifically, the photopolymerizable compound may include a difunctional (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, H or CH ₃ , and j and k are each an integer of 1 to 20.

More specifically, the difunctional (meth)acrylate compound of Formula 1 may include a difunctional (meth)acrylate compound of Formula 11 below and a difunctional (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, 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, H or CH ₃ , and J2 and K2 are each an integer of 10 to 20.

More specifically, the difunctional (meth)acrylate compound of Formula 1 is the difunctional (meth)acrylate compound of Formula 11: The difunctional (meth)acrylate compound of Formula 12 is 1:1 to 1:30. It can be included in a weight ratio.

Compared to the difunctional (meth)acrylate compound of Chemical Formula 11, the difunctional (meth)acrylate compound of Chemical Formula 12 is used in an equivalent weight or more than that of the difunctional (meth)acrylate compound, thereby increasing the adhesion to the substrate and improving the resistance to the developer. 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 difunctional (meth)acrylate compound of Formula 1 above. In this case, the monofunctional or polyfunctional (meth)acrylate compound that can be used excludes the compound contained in the difunctional (meth)acrylate compound of Formula 1 above.

Examples of additionally usable photopolymerizable compounds are not 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 (trimethyolpropane 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 diglycidyl ether dimethacrylate Acrylate (phthalic acid diglycidyl ester dimethacrylate), glycerin polyglycidyl ether polymethacrylate, and a polyfunctional (meth)acrylate containing a urethane group.

On the other hand, the support substrate can serve as a support for the photosensitive laminate, and can be easily handled when the photosensitive resin layer having adhesive strength is exposed to light.

Various plastic films can be used as the base film, 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 photosensitive laminate may further include a protective film formed to face the supporting substrate with the photosensitive resin layer as the center. The protective film prevents damage to the resist during handling and serves as a protective covering to protect 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 requires proper releasability and adhesion so that it is easily released when applying a dry film photoresist to a post process, and is not released when stored and distributed.

Various plastic films can be used as the protective film, for example, an acrylic film, a polyethylene (PE) film, a polyethylene terephthalate (PET) film, a triacetylcellulose (TAC) film, a polynorbornene (PNB) film, and 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. Although the thickness of the protective film is not largely limited, for example, it can be freely adjusted within the range of 0.01 μm to 1 m.

According to another embodiment of the present invention, 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; Alkali developable binder resin containing a carboxyl group; And a photoinitiator; comprising the step of applying and drying a resin composition including a support substrate, it may be provided a method of manufacturing a photosensitive laminate.

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 formed on the paper substrate, and bubbles having a diameter of 1 μm or less may be present in ^{the photosensitive resin layer in an amount of 5 /mm 2 or less.}

In the process of forming the photosensitive resin layer, a diameter of 1 μm or less may be formed in the photosensitive resin layer due to bubbles generated during the process of preparing a solution of the photosensitive resin composition or drying the solution 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 lower, the evaporation time of the solution of the photosensitive resin composition is delayed so that bubbles are not trapped in the numerical layer. Accordingly, there may be ^{5 bubbles/mm 2} or less in the photosensitive resin layer having a diameter of 1 μm or less.

More specifically, bubbles having a diameter of 1 μm or less may be present in the photosensitive resin layer in an amount of 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 1 μm or less may be present.

As the opposite side of the interface between the supporting substrate and the photosensitive resin layer, or the photosensitive resin layer toward the outer side of the outer surface, there is no air bubbles having a diameter of 1 μm or less exist in a small amount or substantially, so that the reliability during development is increased, and thus a high-density circuit Formation is possible and defects in the formation of fine wiring can be reduced. 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 play a role of delaying the evaporation time of the liquid component of the photosensitive resin composition to prevent air bubbles from being trapped in the numerical layer. Accordingly, 5 or less air bubbles having a diameter of 1 μm or less may exist in the photosensitive resin layer.

The mixed solvent may include a high boiling point solvent having a boiling point of 115°C or higher in a predetermined amount or more, and for example, the content of a high boiling point 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 solubility of the photosensitive resin composition may be increased.

The mixed solvent may include a lower boiling point solvent having a boiling point of 100° C. or lower than the high boiling point solvent having a boiling point of 115° C. or higher in a higher content.

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 lower 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 amount described above, 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, butylcapitol, 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 Cyanate, dipropyrene 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 lower; Alkali developable binder resin containing a carboxyl group; And a photoinitiator; in consideration of specific uses or fields of application, the solid content may be adjusted, and for example, the resin composition may contain 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 a supporting substrate is not largely 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 of manufacturing 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, adjustment of the drying rate and/or drying temperature Through this, the amount of fine bubbles formed in the photosensitive resin layer may be greatly reduced or may not be substantially present.

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

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

The content of the alkali developable binder resin including a carboxyl group included in the resin composition includes the above-described content in the photosensitive laminate of the embodiment.

The alkali developable binder resin including the carboxyl group 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 including the carboxyl group 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 including a carboxyl group.

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

The photopolymerizable compound may be a commonly known monofunctional or polyfunctional (meth)acrylate monomer or oligomer, but in order to satisfy the above-described characteristics, the monofunctional or polyfunctional (meth)acrylate monomer or oligomer may be used. It is possible to use a 2 to 10 functional (meth)acrylate monomer or oligomer containing an aromatic functional group in the molecule.

Specifically, the photopolymerizable compound may include a difunctional (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, H or CH ₃ , and j and k are each an integer of 1 to 20.

More specifically, the difunctional (meth)acrylate compound of Formula 1 may include a difunctional (meth)acrylate compound of Formula 11 below and a difunctional (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, 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, H or CH ₃ , and J2 and K2 are each an integer of 10 to 20.

More specifically, the difunctional (meth)acrylate compound of Formula 1 is the difunctional (meth)acrylate compound of Formula 11: The difunctional (meth)acrylate compound of Formula 12 is 1:1 to 1:30. It can be included in a weight ratio.

Compared to the difunctional (meth)acrylate compound of Chemical Formula 11, the difunctional (meth)acrylate compound of Chemical Formula 12 is used in an equivalent weight or more than that of the difunctional (meth)acrylate compound, thereby increasing the adhesion to the substrate and improving the resistance to the developer. As a result, excellent fine wire adhesion and resolution can be secured.

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

Compounds that can be used as the photoinitiator include anthraquinone derivatives such as 2-methyl anthraquinone and 2-ethyl anthraquinone; Benzoin derivatives, such as benzoin methyl ether, benzophenone, phenanthrene quinone, and 4,4'-bis-(dimethylamino)benzophenone, are mentioned.

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-chloro thioxanthone, 2,4-dimethyl thioxanthone, 3, 3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxyoxanthone, 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 Toxicbenzoin, isobutoxybenzoin, tert-butoxybenzoin, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylti A compound selected from oxantone, 2-isopropylthioxanthone, dibenzosuberone, α,α-dichloro-4-phenoxyacetophenone, and pentyl 4-dimethylaminobenzoate may be used as a photoinitiator, but is limited thereto. no.

The content of the photoinitiator is contained 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 total weight of the resin composition. When the content of the photoinitiator is within the above range, sufficient sensitivity can be obtained.

If the content of the photoinitiator is too low, the light efficiency is low and the exposure amount must be large, so that the production efficiency may be extremely reduced. If the content of the photoinitiator is too high, the film may be brittle and contaminated with the developer may be increased, resulting in defects such as a short circuit.

In addition, the resin composition may further include other additives as necessary. 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 the form of acid amide; Triphenyl phosphate and the like can be used.

In order to improve the handling properties of the resin composition, a Leuco dye or a colored substance may be added. Examples of the Leuico dye include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2methylphenyl)methane, and fluorane dyes. Among them, in the case of using a Ruiko crystal violet, the contrast is good, which is preferable. In the case of containing a Leuco dye, the content may be 0.1% by weight or more and 10% by weight or less in the photosensitive resin composition. From the viewpoint of expression of contrast, 0.1% by weight or more is preferable, and from the viewpoint of maintaining storage stability, 10% by weight or less is preferable.

As a coloring substance, for example, toluenesulfonic acid monohydrate, fuxine, phthalocyanine green, oramine base, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, diamond green, basic blue 20, etc. Can be lifted. When the colored material is included, the amount added may be 0.001% by weight or more and 1% by weight or less in the photosensitive resin composition. When the content is 0.001% by weight or more, there is an effect of improving handling properties, and when the content is less than 1% by weight, storage stability is maintained.

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 the manufacturing process of a circuit board or a printed circuit board (PCB), a pre-treatment process is first performed in order to laminate the copper clad laminate, which is the original material of the PCB. The pretreatment process is in the order of drilling, deburing, and front in the outer layer process, and the front or pickling in the inner layer process. In the frontal process, bristle brush and jet pumice processes are mainly used, and the pickling can be subjected to soft etching and sulfuric acid pickling.

In order to form a circuit on the copper clad laminate that has undergone the pretreatment 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 be carried out at a lamination rate 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 15 minutes or more for stabilization of the substrate, and then exposure to the photoresist of DFR may be performed using a photomask having a desired circuit pattern formed thereon. In this process, when ultraviolet rays are irradiated to the photomask, polymerization of the photoresist to which ultraviolet rays are irradiated may be initiated by the photomodifier contained in the irradiated region. Initially, 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 may proceed. Can exist.

Next, a developing process is performed to remove the unexposed portion of the photoresist. 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 portion is washed away by the saponification reaction between the carboxylic acid of the binder polymer and the developer in the developer, and the cured photoresist may remain on the copper surface.

The circuit may be formed through different processes depending on the next inner 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, and a predetermined circuit may be formed.

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

According to the present invention, a photosensitive laminate capable of reducing defects in the formation of fine wiring and capable of forming a high-density circuit due to increased reliability during development, a method of manufacturing the photosensitive laminate, and a circuit board using the photosensitive laminate A manufacturing method of may be provided.

1 is a photograph obtained by confirming the surface and cross section of the photosensitive resin layer of Example 1 with a field emission scanning electron microscope (FE-SEM, 3000 times) using a polarizing microscope.
FIG. 2 is a photograph obtained by confirming the surface and cross section of the photosensitive resin layer of Comparative Example 2 with a field emission scanning electron microscope (FE-SEM, 3000 times) using a polarization microscope.
3 is a photograph of a photosensitive resin layer of Comparative Example 1 being exposed to ultraviolet rays and alkali developed, and a defect formed by a field emission scanning electron microscope (FE-SEM, 3000 times).
4 is a photograph of a photosensitive resin layer of Comparative Example 1 that was exposed to ultraviolet rays and alkali developed, and the defects formed were confirmed with a field emission scanning electron microscope (FE-SEM, 3000 times).

The invention will be described in more detail in the following examples. However, the following examples are merely illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

<Production Example: Preparation of alkali developable binder resin>

Manufacturing Example 1

A mechanical stirrer and a reflux device were attached to 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 (MEK) and 12.5 g of methanol (Methanol, MeOH) were added, and then 2.25 g of azobisisobutyronitrile (AIBN) was added to completely dissolve. Made 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 (SM) as monomers Was added, the temperature was raised to 80 °C, and then polymerized for 6 hours to prepare an alkali developable binder resin 2 (weight average molecular weight of 40,000 g/mol, glass transition temperature of 102 °C, solid content 50% by weight, acid value 156 mgKOH/g). I did.

The alkali developable binder resin prepared in the above Preparation Example was dissolved in tetrahydrofuran to a concentration of 1.0 (w/w)% in THF (about 0.5 (w/w)% based on solid content), and a 0.45㎛ Pore Size Syringe Filter After filtration using, 20 µl was injected into the GPC. Tetrahydrofuran (THF) was used as the mobile phase of GPC, and flow rate was 1.0 mL/min, and analysis was performed at 40°C. As 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, an Agilent 1260 Infinity II System, RI Detector was used to measure at 40°C.

The polystyrene standard sample (STD A, B, C, D) in which polystyrene having various molecular weights is dissolved in tetrahydrofuran at a concentration of 0.1 (w/w)% as follows is filtered through a 0.45 μm 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 the calibration curve formed by injecting into.

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 a photoinitiator in an organic solvent, a photopolymerizable compound and an alkali developable binder resin were added and mixed for about 1 hour using a mechanical stirrer 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, at which time 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 laminating the dried photosensitive resin composition layer using a protective film (polyethylene).

ingredient
(weight%) product name
(Or ingredient name) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Alkali developable binder resin Manufacturing 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 ℃) 2 2 4 4 n-butanol (boiling point 117.7℃)) 2 5 Propylene glycol monomethyl ether acetate
(PGMEA, boiling point about 120℃) 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 1 Comparative Example 2 Alkali developable binder resin Manufacturing 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℃) Propylene glycol monomethyl ether acetate (PGMEA, boiling point about 120℃)

<Experimental Example>

For the dry film photoresist prepared in Examples and Comparative Examples, physical properties were measured by the following method, and the results are shown in Table 3.

1. Exposure amount (unit: mJ/cm ² ) Of the measurement

The dry film photoresist prepared in Examples and Comparative Examples was laminated on a copper clad laminate having a thickness of 1.6 mm subjected to brush polishing treatment. At this time, the lamination was performed using HAKUTO MACH 610i, the substrate preheating roll temperature 120 ℃, the laminator roll temperature 115 ℃, the roll pressure 4.0kgf/㎠ And a roll speed of 2.0 min/m was applied.

Dry film photoresist laminated on a copper clad laminate is irradiated with ultraviolet rays at a wavelength of 405nm using a 41-step step tablet of Stouffer Graphic Arts Equipment Co., Ltd. using ORC's FDi-3, and allowed to stand for 15 minutes after irradiating UV rays with a wavelength of 405nm with an exposure amount of 15 steps remaining by Stouffer Graphic Arts Equipment Co., Ltd. I did. After that, development was carried out under the development conditions of a spray spray method with a 1.0 wt% aqueous solution of _{Na 2} CO _3. At this time, the amount of energy at which the determined number of remaining steps becomes 15 steps was measured.

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

The dry film photoresist prepared in Examples and Comparative Examples was laminated on a copper clad laminate having a thickness of 1.6 mm subjected to brush polishing treatment. At this time, the lamination was performed using HAKUTO MACH 610i, the substrate preheating roll temperature 120 ℃, the laminator roll temperature 115 ℃, the roll pressure 4.0kgf/㎠ And a roll speed of 2.0 min/m was applied.

Using the data formed at intervals of 0.5 μm from 4 to 20 μm so that the width of the circuit line and the space between the circuit lines after development on the stacked body become 1:1, ORC's Through FDi-3, a 41-step step tablet of Stouffer Graphic Arts Equipment was used, and the remaining step was irradiated with ultraviolet rays at a wavelength of 405 nm with an exposure amount of 15 steps and left for 15 minutes. After that, development was performed under the development conditions of a spray spray method with 1.0 wt% Na2CO3 aqueous solution.

After that, the resolution was determined by using a ZEISS AXIOPHOT Microscope to measure the space between the circuit line and the non-circuit line as 1:1.

3. Air bubbles (unit: number/mm ² ) Confirm

With respect to the dry film photoresist prepared in the above Examples and Comparative Examples, after removing the PET film and the PE film, 1㎛ existing in the photosensitive resin layer (unit area (1mm*1mm)) using a polarizing microscope The number of bubbles (number/mm ² ) having the following diameter was confirmed.

3. Defect after exposure/development (unit: number/mm ² ) Confirm

The dry film photoresist prepared in Examples and Comparative Examples was laminated on a copper clad laminate having a thickness of 1.6 mm subjected to brush polishing treatment. At this time, the lamination was performed using HAKUTO MACH 610i, the substrate preheating roll temperature 120 ℃, the laminator roll temperature 115 ℃, the roll pressure 4.0kgf/㎠ And a roll speed of 2.0 min/m was applied.

A 41-step step tablet from Stouffer Graphic Arts Equipment is used through ORC's FDi-3 so that the width of the circuit line and the space between the circuit lines after development can be 14㎛:14㎛ on the laminate. Thus, after irradiating ultraviolet rays with a wavelength of 405 nm at an exposure amount of 15 remaining steps, it was allowed to stand for 15 minutes. After that, development was carried out under the development conditions of a spray spray method with a 1.0 wt% aqueous solution of _{Na 2} CO _3.

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

division Exposure amount
[mJ/cm ² ] 1:1 resolution
[㎛] 1㎛ or less
Bubbles of diameter
[Number/㎟] Defect after exposure/development
[Number/㎟] Example 1 50 8 0 0 Example 2 60 8 0 0 Example 3 50 8 0 0 Example 4 50 8 0 0 Example 5 50 8 One One Example 6 50 8 0 0 Comparative Example 1 50 10 36 15 Comparative Example 2 50 9 18 8

As can be seen in Table 1 and Fig. 1, in the photosensitive resin layer of the photosensitive laminate of the examples, there are 1 /mm ² or less bubbles having a diameter of 1 µm or less, and more than 1 µm and 5 µm or less. It was confirmed that there were also no giant bubbles having a diameter of. In addition, even after the photosensitive resin layer of the above embodiments is exposed to ultraviolet rays and developed with an alkali solution, defects having a diameter of 0.5 µm or more and 3 µm or less do not substantially occur, or 1 piece/mm ² or less. It has been confirmed that it occurs.

That is, since a small amount of air bubbles having a diameter of 1 μm or less exist in the photosensitive resin layer of the above embodiments, a high density and sensitivity are achieved while securing high reliability when manufacturing a circuit board using the photosensitive laminate. It was also observed that wiring could be formed.

On the other hand, in the photosensitive resin laminate of the comparative example, it is difficult to achieve the resolution of the example level even when using the same level of energy as the example, and in the photosensitive resin layer, 10 bubbles having a diameter of 1 μm or less are present/mm. ^{There were 2} or more.

In addition, as shown in FIGS. 3 and 4, after exposing the photosensitive resin layers obtained in Comparative Examples 1 and 2, respectively, and developing with an alkali solution, a number of defects having a diameter of 0.5 μm or more and 3 μm or less were observed. It was confirmed that it appeared.

Claims (10)

Supporting substrate; And a photosensitive resin layer formed on the supporting substrate,
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, there ^{are 3 bubbles/mm 2 or less having a diameter of 1 μm or less,}
The photosensitive resin layer does not contain bubbles having a diameter of more than 1 µm and less than 5 µm,
The photosensitive resin layer includes a crosslinked copolymer between an alkali developable binder resin containing a carboxyl group and a photopolymerizable compound containing a (meth)acrylate monomer or oligomer,
The photopolymerizable compound containing the (meth)acrylate monomer or oligomer comprises a 2 to 10 functional (meth)acrylate monomer or oligomer containing an aromatic functional group in the molecule,
Photosensitive laminate.
The method of claim 1,
The thickness of the supporting substrate is 1 μm to 100 μm,
The photosensitive resin layer has a thickness of 1 µm to 100 µm.
The method of claim 1,
The photosensitive resin layer has a defect having a cross-sectional diameter of 0.3 µm to 4 µm at 3 /mm ² or less after UV exposure and alkali development.
delete The method of claim 1,
The photopolymerizable compound comprising the (meth)acrylate monomer or oligomer is a photosensitive laminate comprising a difunctional (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 are H or CH 3} ,
j and k are each an integer of 1 to 20.
The method of claim 5,
The bifunctional (meth)acrylate compound of Formula 1 includes a difunctional (meth)acrylate compound of Formula 11 below: a difunctional (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 Formula 11,
R ₁₁ and R ₁₂ are the same as or different from each other _{and are H or CH 3} ,
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} ,
J2 and K2 are each an integer of 10 to 20.
The method of claim 1,
The alkali developable binder resin including the carboxyl group has a weight average molecular weight of 20,000 g/mol to 300,000 g/mol and a glass transition temperature of 20° C. or more and 150° C. or less,
Photosensitive laminate.
The method of claim 1,
The alkali developable binder resin containing a carboxyl group has an acid value of 100 mgKOH/g or more and 300 mgKOH/g, a photosensitive laminate.
The method of claim 1,
The photosensitive resin layer comprises a crosslinked copolymer between 100 parts by weight of the alkali developable binder resin including the carboxyl group and 1 to 80 parts by weight of the photopolymerizable compound including the (meth)acrylate monomer or oligomer.
The method of claim 1,
The supporting substrate is one selected from the group consisting of a polyethylene terephthalate (PET) film, a triacetylcellulose (TAC) film, a polynorbornene (PNB) film, a cycloolefin polymer (COP) film, and a polycarbonate (PC) film. A photosensitive laminate comprising the above plastic film.

Images