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

Abstract

The present disclosure relates to a photosensitive laminate and a method of manufacturing the photosensitive laminate, the photosensitive laminate including: a support substrate; and a photosensitive resin layer formed on the support substrate, wherein 5 / mm 2 The following bubbles have a diameter of less than 1 pm.

Description

Technical Field

[0001] Cross-references to related applications

[0002] This application claims the benefits of Korean Patent Application No. 10-2019-0179860, filed on December 31, 2019, Korean Patent Application No. 10-2020-0099130, filed on August 7, 2020, and Korean Patent Application No. 10-2020-0125243, filed on September 25, 2020, the disclosures of which are incorporated herein by reference in their entirety.

[0003] This disclosure relates to a photosensitive laminate, a method for manufacturing the photosensitive laminate, and a method for manufacturing a circuit board. Background Technology

[0004] Photosensitive resin compositions are used in the form of dry film photoresist (DFR), liquid photoresist ink, etc., for printed circuit boards (PCBs) or lead frames.

[0005] In recent years, the trend of making semiconductor devices lighter, thinner, shorter, and smaller or multi-level packaged has led to the demand for high-density circuit boards. This has resulted in the application of processes such as direct exposure with ultra-high pressure mercury lamps or lasers, or the widespread use of circuit board manufacturing processes that utilize photosensitive laminates that include a support film and a photosensitive resin layer.

[0006] Therefore, there is an ongoing need to develop methods and processes that achieve high density and sensitivity while ensuring higher reliability and enabling the formation of finer lines. Summary of the Invention

[0007] Technical issues

[0008] This disclosure provides a photosensitive laminate capable of forming high-density circuits by ensuring high reliability during the development process while reducing defects in the formation of fine lines.

[0009] This disclosure also provides a method for manufacturing the above-described photosensitive laminate.

[0010] This disclosure also provides a method for manufacturing a circuit board using the above-described photosensitive laminate.

[0011] Technical solution

[0012] This disclosure provides a photosensitive laminate, comprising: a support substrate; and a photosensitive resin layer formed on the support substrate, wherein the photosensitive resin layer contains 5 particles per mm. 2 The following are bubbles with a diameter of less than 1 μm.

[0013] This disclosure also provides a method for manufacturing a circuit board using the above-described photosensitive laminate.

[0014] This disclosure also provides a method for manufacturing the above-described photosensitive laminate.

[0015] The following describes in more detail 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.

[0016] In this disclosure, weight-average molecular weight refers to the weight-average molecular weight converted to polystyrene as measured by GPC. In the measurement of weight-average molecular weight converted to polystyrene by GPC, known analytical apparatus, detectors such as refractive index detectors, and chromatographic columns for analysis can be used, and commonly used temperature conditions, solvents, and flow rates can be applied.

[0017] As a specific example of measurement conditions, the alkali-based developing binder resin was dissolved in tetrahydrofuran (THF) at a concentration of 1.0% (w / w) (approximately 0.5% (w / w)) based on solids content, filtered through a syringe filter with a pore size of 0.45 μm, and then 20 μl was injected into the GPC. The mobile phase of the GPC was tetrahydrofuran (THF) flowing at a flow rate of 1.0 mL / min. Measurements were performed at 40 °C using an Agilent 1260 Infinity II System, RIDetector, using a column consisting of one Agilent PLgel 5 μm Guard (7.5 x 50 mm) and two Agilent PLgel 5 μm Mixed D (7.5 x 300 mm) connected in series.

[0018] Polystyrene standard samples (STD A, B, C, D), obtained by dissolving polystyrene of different molecular weights in tetrahydrofuran at a concentration of 0.1 (w / w)%, were filtered through a syringe filter with a pore size of 0.45 μm and then injected into a GPC. The weight-average molecular weight (Mw) of the alkali-developing adhesive resin was obtained using the calibration curve thus formed.

[0019] STD A(Mp):791,000 / 27,810 / 945

[0020] STD B(Mp):282,000 / 10,700 / 580

[0021] STD C(Mp): 126,000 / 4,430 / 370

[0022] STD D(Mp):51,200 / 1,920 / 162

[0023] The terms “(photo)cured product” or “(photo)cured” include not only the complete curing, crosslinking or polymerization of components with curable or crosslinkable unsaturated groups in their chemical structure, but also the partial curing, crosslinking or polymerization of such components.

[0024] According to one embodiment of this disclosure, a photosensitive laminate is provided, comprising: a support substrate; and a photosensitive resin layer formed on the support substrate, wherein 5 particles / mm are present in the photosensitive resin layer. 2 The following are bubbles with a diameter of less than 1 μm.

[0025] The inventors have developed a new photosensitive laminate comprising a photosensitive resin layer, wherein the photosensitive resin layer contains 5 cells / mm. 2 The following are bubbles with a diameter less than 1 μm, or greater than 0.001 μm but less than 1 μm. They have experimentally confirmed that using this photosensitive laminate enables high sensitivity to exposure during circuit board manufacturing and improves reliability during development, thereby ensuring high reliability, achieving high density and sensitivity, and enabling the formation of finer lines.

[0026] The inventors have continuously researched and developed methods to remove trace amounts of microbubbles or micro byproducts that may occur during the manufacturing process due to various reasons. This is achieved using a resin composition comprising: a mixed solvent containing a high-boiling-point solvent with a boiling point above 115°C and a low-boiling-point solvent with a boiling point below 100°C; an alkaline developing adhesive resin containing carboxyl groups; and a photoinitiator, resulting in a photosensitive resin layer containing 5 microbubbles / mm². 2 Below, or 3 / mm 2 The following are bubbles with a diameter of less than 1 μm.

[0027] In addition, in the method of manufacturing photosensitive laminates, besides using a mixed solvent containing a high-boiling-point solvent with a boiling point above 115°C and a low-boiling-point solvent with a boiling point below 100°C, the amount of microbubbles formed in the photosensitive resin layer can be greatly reduced or can be essentially eliminated by adjusting the drying speed and / or drying temperature.

[0028] Meanwhile, 5 per mm can exist in the photosensitive resin layer. 2 Below, or 3 / mm 2 The following refers to bubbles, wherein the diameter of the bubbles is less than 1 μm. Specifically, bubbles with a diameter of less than 1 μm may be present in trace amounts or may be substantially absent on the opposing surfaces of the interface between the support substrate and the photosensitive resin layer, or on the outer surface of the photosensitive resin layer. More specifically, up to 3 bubbles / mm may be present within 50% of the total thickness of the photosensitive resin layer starting from the opposing surfaces of the interface between the support substrate and the photosensitive resin layer. 2 The following are bubbles with a diameter of less than 1 μm.

[0029] Because a small amount of air bubbles with a diameter of less than 1 μm are present or essentially absent on the opposing surfaces of the interface between the support substrate and the photosensitive resin layer, or on the outer surface of the photosensitive resin layer, reliability during the development process is increased, enabling the formation of high-density circuits and reducing defects in the formation of fine lines. Therefore, when using a photosensitive laminate, high sensitivity to exposure can be achieved, and the manufacturing yield of high-density printed circuit boards can be improved.

[0030] Furthermore, in photosensitive laminates, not only can bubbles with a diameter less than 1 μm exist in trace amounts or be essentially non-existent, but bubbles with a diameter greater than 1 μm and less than 5 μm can also be non-existent.

[0031] Therefore, when a photosensitive laminate containing a small number of bubbles with a diameter of less than 1 μm is used in the manufacturing of circuit boards, high density and high sensitivity can be achieved while ensuring high reliability, and finer lines can be formed.

[0032] More specifically, even when the photosensitive resin layer is exposed to ultraviolet light and developed with an alkaline solution, defects do not appear or appear in very small amounts over the entire area. Specifically, the upper surface of the photosensitive resin layer is essentially free of defects, while minute defects may be present on or inside the lower surface of the developed photosensitive resin layer.

[0033] Specifically, after exposing the photosensitive resin layer to ultraviolet light and then developing it with an alkaline solution, three defects per mm can be observed. 2 The following, or 1 defect / mm 2 The defects are either essentially nonexistent, or their cross-sectional diameter is between 0.3 μm and 4 μm, or greater than 0.5 μm and less than 3 μm. The cross-sectional diameter of a defect can be defined as the largest diameter among the diameters of defects defined in a cross-section in one direction on the photosensitive resin layer.

[0034] There are no particular restrictions on exposure and development conditions. For example, exposure can be performed for 1 to 60 minutes at an energy level that results in 15 remaining steps, with the light incident on the photosensitive laminate measured in the range of 340 nm to 420 nm using a 41-step tablet manufactured by Stouffer Graphic Arts Equipment. Alternatively, development can be performed using an alkaline aqueous solution, such as Na₂CO₃, with a concentration of 0.1 wt% to 3.0 wt%, via methods such as spraying.

[0035] Furthermore, when using photosensitive laminates, higher density and sensitivity can be achieved while using less energy. More specifically, this allows for an energy level of 300 mJ / cm² to be achieved when the number of remaining stages is 15. 2 Below, or 100mJ / cm 2 In the following, the light irradiated onto the photosensitive laminate is measured in the range of 340nm to 420nm using a 41-stage exposure meter manufactured by Stouffer Graphic Arts Equipment. Furthermore, the resolution after development can be less than 15μm or less than 10μm.

[0036] There are no particular limitations on the thickness of the support substrate and the thickness of the photosensitive resin layer in the photosensitive laminate, but the thickness of the support substrate can be from 1 μm to 100 μm or from 5 μm to 50 μm, and the thickness of the photosensitive resin layer can be from 1 μm to 100 μm or from 5 μm to 50 μm.

[0037] Meanwhile, the photosensitive laminate may contain 5 / mm 2 The structural characteristics of the photosensitive resin layer with bubbles less than 1 μm in diameter may be due to the manufacturing method described above, or it may be due to the properties of the photosensitive resin layer.

[0038] Specifically, the photosensitive resin layer may comprise an alkaline developing adhesive resin containing carboxyl groups. The alkaline developing adhesive may contain at least one carboxyl group in its molecule and may react with an alkali during the developing process.

[0039] There are no limitations on specific examples of alkaline developing adhesives, but an alkaline developing adhesive may be a polymer or copolymer comprising at least one repeating unit selected from repeating units represented by the following chemical formula 3, repeating units represented by the following chemical formula 4, repeating units represented by the following chemical formula 5, and repeating units represented by the following chemical formula 6.

[0040] [Chemical Formula 4]

[0041]

[0042] In chemical formula 4, R3 is hydrogen or a C1 to C10 alkyl group.

[0043] [Chemical Formula 5]

[0044]

[0045] In chemical formula 5, R4 is hydrogen or a C1 to C10 alkyl group, and R5 is a C1 to C10 alkyl group.

[0046] [Chemical Formula 6]

[0047]

[0048] In chemical formula 6, Ar is a C6 to C20 aryl group.

[0049] In chemical formulas 4 to 6, R3 and R4 are the same or different from each other and are each independently hydrogen or C1 to C10 alkyl, R5 is C1 to C10 alkyl, and Ar is C6 to C20 aryl.

[0050] In chemical formulas 2 to 4, R3 and R4 may be the same as or different from each other, and each is independently hydrogen or a C1 to C10 alkyl group, a specific example of which may be methyl.

[0051] R5 is a C1 to C10 alkyl group, and a specific example of a C1 to C10 alkyl group may be methyl.

[0052] Ar is a C6 to C20 aryl group, and a specific example of a C6 to C20 aryl group can be a phenyl group.

[0053] The repeating unit represented by chemical formula 4 can be a repeating unit derived from the monomer represented by the following chemical formula 4-1.

[0054] [Chemical Formula 4-1]

[0055]

[0056] In Formula 4-1, R3 is hydrogen or a C1 to C10 alkyl group. The description of R3 in Formula 4-1 is the same as that described in Formula 4 above. Specific examples of monomers represented by Formula 4-1 may include acrylic acid (AA) and methacrylic acid (MAA).

[0057] The repeating unit represented by chemical formula 5 can be a repeating unit derived from a monomer represented by the following chemical formula 5-1.

[0058] [Chemical Formula 5-1]

[0059]

[0060] In Formula 5-1, R4 is hydrogen or a C1 to C10 alkyl group, and R5 is a C1 to C10 alkyl group. In Formula 3-1, the descriptions of R4 and R5 are the same as those in Formula 3 above. Specific examples of monomers represented by Formula 3-1 may include methyl methacrylate (MMA) and butyl acrylate (BA).

[0061] The repeating unit represented by chemical formula 6 can be a repeating unit derived from a monomer represented by chemical formula 6-1 below.

[0062] [Chemical Formula 6-1]

[0063]

[0064] In Formula 6-1, Ar is a C6 to C20 aryl group. The description of Ar in Formula 6-1 is the same as that in Formula 4 above. Specific examples of monomers represented by Formula 6-1 may include styrene (SM).

[0065] Meanwhile, alkaline developing adhesive resins containing carboxyl groups can be used as a base for photosensitive resin layers, and therefore should have a minimized molecular weight, for example, 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.

[0066] In addition, alkaline developing adhesive resins containing carboxyl groups should have a certain level of heat resistance, so the glass transition temperature can be above 20°C and below 150°C.

[0067] In addition, considering the developability of the photosensitive resin layer, the acid value of the alkaline developing adhesive resin containing carboxyl groups can be in the range of 100 mg KOH / g to 300 mg KOH / g.

[0068] Meanwhile, the photosensitive resin layer may comprise: a crosslinked copolymer between an alkaline developing adhesive resin containing carboxyl groups and a photopolymerizable compound containing (meth)acrylate monomers or oligomers.

[0069] Photopolymerizable compounds containing (meth)acrylate monomers or oligomers can act as crosslinking agents to improve the mechanical strength of photosensitive resin layers, or they can improve resistance to developers and impart flexibility to the cured film.

[0070] Depending on the specific application or properties of the photosensitive resin layer, the content of photopolymerizable compounds containing (meth)acrylate monomers or oligomers can be adjusted. For example, based on 100 parts by weight of a carboxyl-containing alkali-developing adhesive resin, the content of photopolymerizable compounds containing (meth)acrylate monomers or oligomers can be from 1 part by weight to 80 parts by weight.

[0071] Photopolymerizable compounds can be monofunctional or polyfunctional (meth)acrylate monomers or oligomers.

[0072] As photopolymerizable compounds, known monofunctional or polyfunctional (meth)acrylate monomers or oligomers can be used. To satisfy the above characteristics, 2- to 10-functional (meth)acrylate monomers or oligomers containing aromatic functional groups in the molecule can be used as monofunctional or polyfunctional (meth)acrylate monomers or oligomers.

[0073] Specifically, the photopolymerizable compound can be a bifunctional (meth)acrylate compound represented by the following chemical formula 1.

[0074] [Chemical Formula 1]

[0075]

[0076] In chemical formula 1, R1 and R2 are the same or different from each other and are H or CH3, and j and k are each integers from 1 to 20.

[0077] More specifically, the difunctional (meth)acrylate compound of Formula 1 may include the difunctional (meth)acrylate compound of Formula 11 and the difunctional (meth)acrylate compound of Formula 12.

[0078] [Chemical Formula 11]

[0079]

[0080] In chemical formula 11, R 11 and R 12 They are either the same or different and are either H or CH3, J1 and K1 are each an integer from 1 to 8.

[0081] [Chemical Formula 12]

[0082]

[0083] In chemical formula 12, R 21 and R 22 They are either the same or different from each other and are either H or CH3, J2 and K2 are each integers from 10 to 20.

[0084] More specifically, the difunctional (meth)acrylate compound of Formula 1 may comprise a difunctional (meth)acrylate compound of Formula 11 and a difunctional (meth)acrylate compound of Formula 12 in a weight ratio of 1:1 to 1:30.

[0085] Since the difunctional (meth)acrylate compound of formula 12 is used at an equal or greater weight than the difunctional (meth)acrylate compound of formula 11, it improves adhesion to the substrate and resistance to the developer, thereby ensuring excellent line adhesion and resolution.

[0086] In addition to the difunctional (meth)acrylate compounds of Formula 1, photopolymerizable compounds may also include monofunctional or polyfunctional (meth)acrylate compounds. In this case, the monofunctional or polyfunctional (meth)acrylate compounds that can be used are not included in the difunctional (meth)acrylate compounds of Formula 1.

[0087] There are no limitations on examples of photopolymerizable compounds that may be used, but may include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, glycerol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate, etc. Tetramethylol trimethacrylate, dipentaerythritol pentamethacrylate, 2,2-bis(4-methacryloyloxydiethoxyphenyl)propane, 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane, 2-hydroxy-3-methacryloyloxypropyl methacrylate, ethylene glycol diglycidyl ether dimethacrylate, diethylene glycol diglycidyl ether dimethacrylate, diglycidyl phthalate diglycidyl ether dimethacrylate, glycerol polyglycidyl ether polymethacrylate, and polyfunctional (meth)acrylates containing carbamates.

[0088] Meanwhile, the support substrate can be used as a support for the photosensitive laminate and can facilitate the treatment of the photosensitive resin layer with adhesive strength during exposure.

[0089] Various plastic films can be used as base films. For example, at least one plastic film selected from acrylic film, polyethylene terephthalate (PET) film, triacetyl cellulose (TAC) film, polynorbornene (PNB) film, cyclic olefin polymer (COP) film, and polycarbonate (PC) film can be used.

[0090] Additionally, the photosensitive laminate may include a protective film formed with the photosensitive resin layer centered on the supporting substrate. The protective film prevents damage to the photoresist during processing and serves as a protective layer against foreign matter such as dust. It may also be laminated onto the other surface of the photosensitive resin layer where no base film is formed.

[0091] The protective film serves to protect the photosensitive resin layer from external influences and is required to have appropriate release properties and adhesion so that it can be easily peeled off when applying the dry film photoresist to subsequent processes, and does not peel off during storage and distribution.

[0092] Various plastic films can be used as protective films. For example, at least one plastic film selected from acrylic film, polyethylene (PE) film, polyethylene terephthalate (PET) film, triacetyl cellulose (TAC) film, polynorbornene (PNB) film, cyclic olefin polymer (COP) film, and polycarbonate (PC) film can be used. There is no particular limitation on the thickness of the protective film; for example, it can be freely adjusted within the range of 0.01 μm to 1 μm.

[0093] According to another embodiment of this disclosure, a method for manufacturing a photosensitive laminate is provided, comprising the steps of: coating a resin composition comprising: a mixed solvent comprising a high-boiling-point solvent having a boiling point above 115°C and a low-boiling-point solvent having a boiling point below 100°C; an alkaline developing adhesive resin comprising carboxyl groups; and a photoinitiator onto a support substrate, and then drying it.

[0094] In one embodiment, the photosensitive laminate described above can be provided according to the manufacturing method.

[0095] As described above, the photosensitive laminate includes: a support substrate; and a photosensitive resin layer formed on the support substrate, wherein the photosensitive resin layer contains 5 particles per mm. 2 The following are bubbles with a diameter of less than 1 μm.

[0096] During the formation of the photosensitive resin layer, bubbles with a diameter of less than 1 μm may form in the photosensitive resin layer due to factors such as bubbles generated during the preparation or drying of the photosensitive resin composition solution. However, methods for manufacturing photosensitive laminates use a mixed solvent comprising a high-boiling-point solvent (boiling point above 115°C) and a low-boiling-point solvent (boiling point below 100°C) to delay the evaporation time of the photosensitive resin composition solution, thereby preventing bubbles from being trapped in the resin layer. Therefore, bubbles with a diameter of 5 / mm can exist in the photosensitive resin layer. 2 The following are bubbles with a diameter of less than 1 μm.

[0097] More specifically, 5 air bubbles / mm can exist in the photosensitive resin layer. 2 Below, or 3 bubbles / mm 2 In the following, the diameter of the bubble is less than 1 μm.

[0098] Additionally, up to 3 per mm of the total thickness of the photosensitive resin layer, starting from the opposite side of the interface between the support substrate and the photosensitive resin layer, can exist. 2 The following are bubbles with a diameter of less than 1 μm.

[0099] Because bubbles with a diameter of less than 1 μm are present in trace amounts or are virtually non-existent on the opposing surfaces of the interface between the support substrate and the photosensitive resin layer, or on the outer surface of the photosensitive resin layer, the reliability of the development process is increased, thereby enabling the formation of high-density circuits and reducing defects in the formation of fine lines. Therefore, when using a photosensitive laminate, high sensitivity to exposure can be achieved, and the manufacturing yield of high-density printed circuit boards can be improved.

[0100] As mentioned above, high-boiling-point solvents with a boiling point above 115°C can delay the evaporation time of the liquid component in the photosensitive resin composition, preventing bubbles from being trapped in the resin layer. Therefore, 5 bubbles / mm can exist in the photosensitive resin layer. 2 The following are bubbles with a diameter of less than 1 μm.

[0101] The mixed solvent may contain a predetermined amount or more of a high-boiling-point solvent with a boiling point of 115°C or higher. For example, based on 100 parts by weight of the mixed solvent, the content of the high-boiling-point solvent with a boiling point of 115°C or higher may be 3 parts by weight or more, 5 parts by weight or more, 3 to 50 parts by weight, or 5 to 40 parts by weight.

[0102] The solubility of the photosensitive resin composition can be improved by using low-boiling-point solvents with boiling points below 100°C and high-boiling-point solvents with boiling points above 115°C.

[0103] The mixed solvent contains a higher proportion of low-boiling-point solvents with a boiling point below 100°C than high-boiling-point solvents with a boiling point above 115°C.

[0104] More specifically, the mixed solvent comprises a high-boiling-point solvent with a boiling point of 115°C or higher and a low-boiling-point solvent with a boiling point of 100°C or lower, in a weight ratio of 1:2 to 1:20, or 1:3 to 1:15. Because it comprises the aforementioned weight ratio of high-boiling-point solvent with a boiling point of 115°C or higher and low-boiling-point solvent with a boiling point of 100°C or lower, the solubility of the photosensitive resin composition can be increased.

[0105] Examples of high-boiling-point solvents with a boiling point above 115°C may include butanol, dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone, butyl carbitol, 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-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol methyl ether propionate, dipropylene glycol dimethyl ether, cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), and mixtures thereof.

[0106] Examples of low-boiling-point solvents with a boiling point below 100°C may include methyl ethyl ketone, methanol, ethanol, acetone, tetrahydrofuran, isopropanol, and mixtures thereof.

[0107] In a resin composition comprising: a mixed solvent comprising a high-boiling-point solvent having a boiling point above 115°C and a low-boiling-point solvent having a boiling point below 100°C; an alkaline developing adhesive resin comprising a carboxyl group; and a photoinitiator, the solid content may be controlled according to the specific use or application field. For example, the resin composition may contain 10% to 99% by weight of the mixed solvent.

[0108] Furthermore, there are no particular limitations on the methods or apparatus that can be used in the step of coating the resin composition onto a support substrate and then drying it. For example, the resin composition can be coated onto a conventional substrate film, such as polyethylene terephthalate, using conventional coating methods, and then dried to prepare a dry film.

[0109] There are no particular limitations on the method of coating the resin composition, and, for example, methods such as the coating bar method can be used.

[0110] In the method of manufacturing photosensitive laminates, in addition to using a mixed solvent containing a high-boiling-point solvent with a boiling point above 115°C and a low-boiling-point solvent with a boiling point below 100°C, the amount of microbubbles formed in the photosensitive resin layer can be greatly reduced or can be essentially eliminated by adjusting the drying speed and / or drying temperature.

[0111] More specifically, the step of drying the coated resin composition can be carried out by heating means such as a hot air oven, hot plate, hot air circulating furnace, or infrared furnace at a temperature of 50°C to 100°C, 60°C to 90°C, or 70°C to 85°C.

[0112] The drying time can vary depending on the drying temperature, and can be, for example, 30 seconds to 20 minutes, more specifically 1 minute to 10 minutes, or 3 minutes to 7 minutes.

[0113] The description of the carboxyl-containing alkaline developing adhesive resin included in the resin composition is as described in the description of the photosensitive laminate of the embodiment.

[0114] The weight-average molecular weight of the alkali developing adhesive resin containing carboxyl groups can be from 20,000 g / mol to 300,000 g / mol, or from 30,000 g / mol to 150,000 g / mol, and the glass transition temperature can be above 20°C and below 150°C.

[0115] The acid value of alkali developing adhesive resin containing carboxyl groups can be above 100 mg KOH / g and below 300 mg KOH / g.

[0116] Together with the alkali-developing adhesive resin containing carboxyl groups, the resin composition may also contain: a photopolymerizable compound containing (meth)acrylate monomers or oligomers.

[0117] Based on 100 parts by weight of a carboxyl-containing alkaline developing adhesive resin, the resin composition may contain 1 to 80 parts by weight of a photopolymerizable compound containing (meth)acrylate monomers or oligomers.

[0118] As photopolymerizable compounds, known monofunctional or polyfunctional (meth)acrylate monomers or oligomers can be used. To satisfy the above characteristics, 2- to 10-functional (meth)acrylate monomers or oligomers containing aromatic functional groups within the molecule can be used as monofunctional or polyfunctional (meth)acrylate monomers or oligomers.

[0119] Specifically, the photopolymerizable compound can be a bifunctional (meth)acrylate compound represented by the following chemical formula 1.

[0120] [Chemical Formula 1]

[0121]

[0122] In chemical formula 1, R1 and R2 are the same or different from each other and are H or CH3, and j and k are each integers from 1 to 20.

[0123] More specifically, the difunctional (meth)acrylate compound of Formula 1 may include the difunctional (meth)acrylate compound of Formula 11 and the difunctional (meth)acrylate compound of Formula 12.

[0124] [Chemical Formula 11]

[0125]

[0126] In chemical formula 11, R 11 and R 12 They are either the same or different and are either H or CH3, J1 and K1 are each an integer from 1 to 8.

[0127] [Chemical Formula 12]

[0128]

[0129] In chemical formula 12, R 21 and R 22 They are either the same or different from each other and are either H or CH3, J2 and K2 are each integers from 10 to 20.

[0130] More specifically, the difunctional (meth)acrylate compound of Formula 1 may comprise a difunctional (meth)acrylate compound of Formula 11 and a difunctional (meth)acrylate compound of Formula 12 in a weight ratio of 1:1 to 1:30.

[0131] Since the difunctional (meth)acrylate compound of Formula 12 is used at the same or higher weight than the difunctional (meth)acrylate compound of Formula 11, the adhesion to the substrate and the resistance to the developer are improved, thereby ensuring excellent line adhesion and resolution.

[0132] Photoinitiators are materials that initiate the chain reaction of photopolymerizable monomers through ultraviolet light and other radiation, and play an important role in the curing of resin compositions and photosensitive resin layers in photosensitive laminates.

[0133] Compounds that can be used as photoinitiators may include anthraquinone derivatives such as 2-methylanthraquinone and 2-ethylanthraquinone; and benzoin derivatives such as benzoin methyl ether, benzophenone, phenanthrenequinone, and 4,4'-bis-(dimethylamino)benzophenone.

[0134] The following can be used: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethyl-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoprop-1-one, 2-benzyl-2-dimethylamino-1-[4-morpholinophenyl]but-1-one, 2-hydroxy-2-methyl-1-phenylprop-1-one, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 1-[ [4-(2-hydroxymethoxy)phenyl]-2-hydroxy-2-methylprop-1-one, 2,4-diethylthioxanone, 2-chlorothioxanone, 2,4-dimethylthioxanone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxythioxanone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylprop-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylprop-1-one, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethyl... Aminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, 2,2-diethoxyacetophenone, benzyl ketone dimethyl acetal, benzyl ketone β-methoxydiethyl acetal, 1-phenyl-1,2-propyldioxime-o,o'-(2-carbonyl)ethoxy ether, methyl o-benzoylbenzoate, bis[4-dimethylaminophenyl)ketone, 4,4'-bis(diethylamino) Compounds of benzophenone, 4,4'-dichlorobenzophenone, benzyl, benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzoin, isobutoxybenzoin, tert-butoxybenzoin, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, α,α-dichloro-4-phenoxyacetophenone, and 4-dimethylaminobenzoate pentyl ester can be used as photoinitiators, but are not limited to these.

[0135] Based on the solids content, the photoinitiator content relative to the total weight of the resin composition can be from 0.1% to 20% by weight, or more than 1% by weight and less than 10% by weight. When the photoinitiator content is within the above range, sufficient sensitivity can be obtained.

[0136] If the photoinitiator content is too low, the exposure needs to be increased due to low light efficiency, which will greatly reduce production efficiency. If the photoinitiator content is too high, the film will become brittle and the developer will be easily contaminated, leading to defects such as short circuits.

[0137] In addition, the resin composition may contain other additives as needed. For example, phthalate forms such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, and diallyl phthalate; glycol ester forms such as triethylene glycol diacetate and tetraethylene glycol diacetate; acid amide forms such as p-toluenesulfonamide, benzenesulfonamide, and n-butylbenzenesulfonamide; and triphenyl phosphate, etc., as plasticizers.

[0138] To facilitate the processing of the resin composition, a colorless dye or colorant may be added. Examples of colorless dyes include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2-methylphenyl)methane, and fluorane dyes. Colorless crystal violet is preferred because of its good contrast. When a colorless dye is included, its content in the photosensitive resin composition can be 0.1% by weight or more and 10% by weight or less. For better contrast, 0.1% by weight or more is preferred, and for maintaining storage stability, 10% by weight or less is preferred.

[0139] Colorants may include toluenesulfonic acid monohydrate, fuchsin, phthalocyanine green, auramine base, parafuchsin, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, malachite green, diamond green, basic blue 20, etc. When colorants are included, the amount added to the photosensitive resin composition may be 0.001% by weight or more and 1% by weight or less. If the content is 0.001% by weight or more, it has the effect of improving processability; if the content is less than 1% by weight, it has the effect of maintaining storage stability.

[0140] Other additives may include heat-inhibiting agents, dyes, decolorizing agents, and adhesion promoters.

[0141] According to another embodiment of this disclosure, a method for manufacturing a circuit board using the photosensitive laminate of the embodiment can be provided.

[0142] The photosensitive laminate of the implementation scheme can be used to laminate onto a copper-clad laminate.

[0143] As an example of the manufacturing process of a circuit board or printed circuit board (PCB), a pretreatment process is first performed to laminate the copper-clad laminate, which is the raw material of the PCB. The sequence of the pretreatment processes is drilling, deburring, and brushing in the outer layer process, and brushing or acid pickling in the inner layer process. In the brushing process, brushes and pumice blasting are mainly used, while acid pickling can be performed using soft etching and sulfuric acid pickling.

[0144] To form circuits on a pre-processed copper-clad laminate, a photosensitive laminate or dry film photoresist (DFR) is typically laminated onto the copper layer of the copper-clad laminate. In this process, the DFR photoresist layer is laminated onto the copper surface while a laminator is used to peel off the protective film of the DFR. Typically, this is performed at lamination speeds of 0.5 m / min to 3.5 m / min, temperatures of 100°C to 130°C, and heated roller pressures of 10 psi to 90 psi.

[0145] The laminated printed circuit board can be left to stand for 15 minutes or longer to stabilize the substrate. Then, a photomask with the desired circuit pattern formed on it can be used to expose the DFR photoresist. During this process, when the photomask is irradiated with ultraviolet light, the UV-irradiated photoresist can initiate polymerization in the irradiated area through the included photoinitiator. Initially, oxygen in the photoresist is consumed, and then the activated monomers polymerize to induce a crosslinking reaction. Subsequently, as a large amount of monomer is consumed, the polymerization reaction can proceed, and the unexposed areas will exist in a state where no crosslinking reaction has occurred.

[0146] Next, a development process is performed to remove the unexposed portions of the photoresist. In the case of alkaline-developed DFR, an aqueous solution of potassium carbonate and sodium carbonate at 0.8% to 1.2% by weight can be used as the developer. During this process, the unexposed portions of the photoresist are washed away by a saponification reaction between the carboxylic acid of the binder polymer and the developer, and the cured photoresist can remain on the copper surface.

[0147] Subsequently, circuits can be formed using different processes depending on the inner and outer layer processes. In the inner layer process, circuits can be formed on the substrate through etching and stripping processes. In the outer layer process, circuits can be formed through electroplating and masking processes, followed by etching and solder stripping.

[0148] For exposure, conventional and known light sources can be used; more specifically, ultra-high pressure mercury lamps or laser direct exposure machines can be used.

[0149] Beneficial effects

[0150] According to this disclosure, a photosensitive laminate capable of forming high-density circuits by ensuring high reliability during the development process while reducing defects in the formation of fine lines, a method for manufacturing the aforementioned photosensitive laminate, and a method for manufacturing a circuit board using the aforementioned photosensitive laminate can be provided. Attached Figure Description

[0151] Figure 1These are photographs of the surface and cross-section of the photosensitive resin layer of Example 1, confirmed by field emission scanning electron microscopy (FE-SEM, 3000x) using a polarizing microscope.

[0152] Figure 2 These are photographs of the surface and cross-section of the photosensitive resin layer of Comparative Example 2, confirmed by field emission scanning electron microscopy (FE-SEM, 3000x) using a polarizing microscope.

[0153] Figure 3 The photographs show the defects formed on the photosensitive resin layer of Comparative Example 1 after ultraviolet irradiation and alkaline development, as confirmed by field emission scanning electron microscopy (FE-SEM, 3000x).

[0154] Figure 4 The photographs show the defects formed on the photosensitive resin layer of Comparative Example 1 after ultraviolet irradiation and alkaline development, as confirmed by field emission scanning electron microscopy (FE-SEM, 3000x).

[0155] Figure 5 The photographs are images of defects formed on the photosensitive resin layer of Comparative Example 3 after ultraviolet irradiation and alkaline development, confirmed using field emission scanning electron microscopy (FE-SEM, 3000x). Detailed Implementation

[0156] The invention will be described in more detail in the following embodiments. However, the following embodiments are provided for illustrative purposes only, and the scope of the invention is not limited to these embodiments.

[0157] <Preparation Example: Preparation of Alkali-Developing Adhesive Resin>

[0158] Preparation Example 1

[0159] A mechanical stirrer and reflux device were installed in a four-necked round-bottom flask, and the inside of the flask was purged with nitrogen. 170 g of methyl ethyl ketone (MEK) and 12.5 g of methanol (MeOH) were added to the nitrogen-purged flask, followed by the addition of 2.25 g of azobisisobutyronitrile (AIBN) to ensure complete dissolution. Then, a monomer mixture of 60 g of methacrylic acid (MAA), 100 g of benzyl methacrylate (BzMA), 15 g of methyl methacrylate (MMA), and 75 g of styrene (SM) was added as monomers. The mixture was heated to 80 °C and polymerized for 6 hours to prepare alkali-developing adhesive resin 2 (weight-average molecular weight 40,000 g / mol, glass transition temperature 102 °C, solids content 50% by weight, acid value 156 mg KOH / g).

[0160] The alkali-based developing binder resin prepared in the preparation example was dissolved in tetrahydrofuran (THF) at a concentration of 1.0% (w / w) (approximately 0.5% (w / w) based on solids content), filtered through a syringe filter with a 0.45 μm pore size, and then 20 μl was injected into a GPC. The mobile phase of the GPC was tetrahydrofuran (THF), the flow rate was 1.0 mL / min, and analysis was performed at 40 °C. A single Agilent PLgel 5 μm Guard column (7.5 x 50 mm) and two Agilent PLgel 5 μm Mixed D columns (7.5 x 300 mm) connected in series were used. Measurements were performed using an Agilent 1260 Infinity II System with an RIDetector at 40 °C.

[0161] Polystyrene standard samples (STD A, B, C, D), obtained by dissolving polystyrene of different molecular weights in tetrahydrofuran at a concentration of 0.1 (w / w)%, were filtered through a syringe filter with a pore size of 0.45 μm and then injected into a GPC. The weight-average molecular weight (Mw) of the alkali-developing adhesive resin was obtained using the calibration curve thus formed.

[0162] STD A(Mp):791,000 / 27,810 / 945

[0163] STD B(Mp):282,000 / 10,700 / 580

[0164] STD C(Mp): 126,000 / 4,430 / 370

[0165] STD D(Mp):51,200 / 1,920 / 162

[0166] <Examples and Comparative Examples: Preparation of Photosensitive Resin Compositions and Dry Film Photoresists>

[0167] According to the composition shown in Table 1 below, the photoinitiator was dissolved in an organic solvent, and then a photopolymerizable compound and an alkaline developing adhesive resin were added to it. The mixture was then stirred using a mechanical stirrer for about 1 hour to prepare a photosensitive resin composition.

[0168] The obtained photosensitive resin composition was coated onto a 25 μm PET film using a coating rod. The coated photosensitive resin composition layer was then dried in a hot air oven at 80°C for 5 minutes, resulting in a dried photosensitive resin layer thickness of 25 μm.

[0169] A photosensitive laminate (dry film photoresist) is manufactured by laminating a protective film (polyethylene) onto a dry photosensitive resin composition layer.

[0170] [Table 1]

[0171]

[0172] (1) M2101: Bisphenol A (EO) 10 Dimethacrylate (Miwon Specialty Chemical)

[0173] (2) M281: Polyethylene glycol dimethacrylate (Miwon Specialty Chemical)

[0174] (3) M241: Bisphenol A (ethoxy) 4-dimethacrylate (Miwon Specialty Chemical)

[0175] (4) BCIM: 2,2'-bis-(2-chlorophenyl-4,5,4',5'-tetraphenylbisimidazole (Aldrich Chemical)

[0176] [Table 2]

[0177]

[0178] [Comparative Example 3: Preparation of Photosensitive Resin Composition and Dry Film Photoresist]

[0179] Experiments were conducted to replicate Example 4 of Patent Document 1 (Japanese Patent Publication No. 2006-106287), based on

[0088] and

[0093] of Patent Document 1.

[0180] 1. Preparation of photosensitive resin composition

[0181] According to Example 4 of Patent Document 1, a photosensitive resin composition was prepared by mixing the following components for about 1 hour using a mechanical stirrer based on 300 parts by weight of the "alkali-developing adhesive resin" obtained in Preparation Example 1.

[0182] <Components of the photosensitive resin composition>

[0183] (1) 100 parts by weight of 2,2-bis(4-(methacryloyloxypentethoxy)phenyl)propane

[0184] (2) 50 parts by weight of EO,PO modified urethane dimethacrylate

[0185] (3) 50 parts by weight of polypropylene glycol diacrylate (number of propylene glycol chains: 7)

[0186] (4) Photoinitiator: 25 parts by weight of benzophenone, 1.0 part by weight of 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer and 1.0 part by weight of diethylaminobenzophenone

[0187] (5) 5.0 parts by weight of photochromic agent

[0188] (6) 0.15 parts by weight of dye

[0189] (7) Mixed solvent: 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) [weight ratio of low-boiling-point solvent (boiling point below 100°C) to high-boiling-point solvent (boiling point above 115°C) = 19:1]

[0190] 2. Preparation of dry film photoresist

[0191] The obtained photosensitive resin composition was coated onto a 25 μm PET film using a coating rod. The coated photosensitive resin composition layer was then dried in a hot air oven at 80°C for 5 minutes, resulting in a dried photosensitive resin layer thickness of 25 μm.

[0192] <Experimental Example>

[0193] The physical properties of the dry film photoresists prepared in the examples and comparative examples were measured using the following methods, and the results are shown in Table 3.

[0194] 1. Measure the exposure (unit: mJ / cm) 2 )

[0195] The dry film photoresist prepared in one of the examples and comparative examples was laminated onto a brush-polished copper-clad laminate with a thickness of 1.6 mm. Here, a HAKUTO MACH 610i laminator was used for lamination, with a substrate preheating roller temperature of 120°C, a laminator roller temperature of 115°C, and a roller pressure of 4.0 kgf / cm². 2 The roller speed is 2.0 min / m.

[0196] A 41-stage exposure meter manufactured by Stouffer Graphic Arts Equipment and an FDi-3 laser manufactured by ORC were used to expose the dry film photoresist laminated on a copper-clad laminate to 405 nm ultraviolet light, resulting in a remaining exposure of 15 stages. The substrate was then allowed to stand for 15 minutes. Development was then performed using a 1.0 wt% Na₂CO₃ aqueous solution under spray-on development conditions. At this point, the energy of the remaining stages (representing 15 stages) was measured.

[0197] 2. Measurement at 1:1 resolution (unit: μm)

[0198] The dry film photoresist prepared in one of the examples and comparative examples was laminated onto a brush-polished copper-clad laminate with a thickness of 1.6 mm. Here, a HAKUTO MACH 610i laminator was used for lamination, with a substrate preheating roller temperature of 120°C, a laminator roller temperature of 115°C, and a roller pressure of 4.0 kgf / cm². 2 The roller speed is 2.0 min / m.

[0199] Using data ranging from 4 μm to 20 μm in 0.5 μm intervals to ensure that the width of the circuit lines and the spacing between them become 1:1 after development in the laminate, an exposure of 405 nm wavelength ultraviolet light was applied using a 41-stage exposure meter manufactured by Stouffer Graphic Arts Equipment and an FDi-3 manufactured by ORC to achieve an exposure of 15 stages. The area was then allowed to stand for 15 minutes. Subsequently, development was performed using a 1.0 wt% Na₂CO₃ aqueous solution under spray development conditions.

[0200] The resolution was then determined using a ZEISS AXIOPHOT microscope by measuring values ​​that were set to a 1:1 ratio between the spacing of the circuit lines and the spacing of the non-circuit lines.

[0201] 3. Confirm air bubbles (unit: air bubbles / mm) 2 )

[0202] For the dry film photoresist prepared in one of the examples and comparative examples, after removing the PET film and PE film, the number of bubbles with a diameter of less than 1 μm in the photosensitive resin layer (unit area: 1 mm * 1 mm) was confirmed using a polarizing microscope (bubbles / mm). 2 ).

[0203] 4. Confirm defects after exposure / development (unit: defects / mm) 2 )

[0204] The dry film photoresist prepared in one of the examples and comparative examples was laminated onto a brush-polished copper-clad laminate with a thickness of 1.6 mm. Here, a HAKUTO MACH 610i laminator was used for lamination, with a substrate preheating roller temperature of 120°C, a laminator roller temperature of 115°C, and a roller pressure of 4.0 kgf / cm². 2 The roller speed is 2.0 min / m.

[0205] The laminate was irradiated with 405 nm ultraviolet light using a 41-stage exposure meter manufactured by Stouffer Graphic Arts Equipment and an FDi-3 laser manufactured by ORC, resulting in an exposure level of 15 stages remaining. After development, the width of the circuit lines was 1:1 with the spacing between them, and the laminate was allowed to stand for 15 minutes. Then, it was developed using a 1.0 wt% Na₂CO₃ aqueous solution under spray development conditions.

[0206] For each developed dry film photoresist prepared in the examples and comparative examples, the number of defects larger than 0.5 μm and smaller than 3 μm was examined on the upper and lower surfaces of the photoresist within a unit area (1 mm * 1 mm) using an electron microscope (defects / mm). 2 The surface and cross-section of the photosensitive resin layers obtained in the various embodiments and comparative examples were observed using a field emission scanning electron microscope (FE-SEM, manufactured by Hitachi, magnification 3000).

[0207] [Table 3]

[0208]

[0209] Refer to Table 1 and Figure 1 It can be confirmed that in the photosensitive resin layer of the photosensitive laminate in the embodiment, there are 1 / mm 2 The following bubbles have a diameter of less than 1 μm, and there are no large bubbles with a diameter of more than 1 μm but less than 5 μm. Furthermore, even after exposing the photosensitive resin layer of the example to ultraviolet light and developing it with an alkaline solution, it can be confirmed that defects with a diameter of more than 0.5 μm but less than 3 μm are essentially absent, or are present in quantities of 1 defect / mm. 2 The following will appear.

[0210] In other words, it was also observed that, due to the presence of a small number of bubbles with a diameter of less than 1 μm in the photosensitive resin layer of the embodiment, high density and sensitivity can be achieved when using this photosensitive laminate to manufacture circuit boards, while ensuring high reliability, thereby enabling the formation of finer lines.

[0211] On the other hand, in the comparative example of the photosensitive resin laminate, even when using the same energy as in the example, it is difficult to achieve a resolution similar to that of the example, and there are 10 particles / mm in the photosensitive resin layer. 2 The above refers to bubbles with a diameter of less than 1 μm.

[0212] Refer to Table 3 and Figure 5As shown, it can be confirmed that after exposing the photosensitive resin layer obtained in either Comparative Example 1 or Comparative Example 2 and then developing it with an alkaline solution, many defects with a diameter of 0.5 μm or more and 3 μm or less appear.

Claims

1. A photosensitive laminate, comprising: Support substrate; and the photosensitive resin layer formed on the support substrate, Among them, there are 5 per mm in the photosensitive resin layer. 2 The following bubbles have a diameter of less than 1 μm. The photosensitive resin layer does not contain air bubbles with a diameter of 1 μm or more but less than 5 μm.

2. The photosensitive laminate according to claim 1, in, There are 3 per mm within 50% of the total thickness of the photosensitive resin layer, starting from the opposing surface of the interface between the supporting substrate and the photosensitive resin layer. 2 The following are bubbles with a diameter of less than 1 μm.

3. The photosensitive laminate according to claim 1 or claim 2, in, The thickness of the supporting substrate is from 1 μm to 100 μm, and The thickness of the photosensitive resin layer is from 1 μm to 100 μm.

4. The photosensitive laminate according to claim 1, in, After ultraviolet exposure and alkaline development, the photosensitive resin layer has 3 defects per mm with a cross-sectional diameter of 0.3 μm to 4 μm. 2 the following.

5. The photosensitive laminate according to claim 1, in, The photosensitive resin layer comprises: an alkaline developing adhesive resin containing carboxyl groups.

6. The photosensitive laminate according to claim 5, in, The photosensitive resin layer comprises a crosslinked copolymer between an alkaline developing adhesive resin containing carboxyl groups and a photopolymerizable compound containing (meth)acrylate monomers or oligomers.

7. The photosensitive laminate according to claim 6, in, The photopolymerizable compound comprising (meth)acrylate monomers or oligomers comprises 2 to 10 functional (meth)acrylate monomers or oligomers containing aromatic functional groups in the molecule.

8. The photosensitive laminate according to claim 6, in, The photopolymerizable compound comprising (meth)acrylate monomers or oligomers comprises a bifunctional (meth)acrylate compound of Formula 1: [Chemical Formula 1] In chemical formula 1, R1 and R2 are the same or different from each other and are H or CH3, and j and k are each integers from 1 to 20.

9. The photosensitive laminate according to claim 8, in, The bifunctional (meth)acrylate compound of Formula 1 comprises, by weight ratio of, the following bifunctional (meth)acrylate compound of Formula 11 and the following bifunctional (meth)acrylate compound of Formula 12: 1:1 to 1:30: [Chemical Formula 11] In chemical formula 11, R 11 and R 12 They are either the same or different and are either H or CH3, J1 and K1 are each an integer from 1 to 8. [Chemical Formula 12] In chemical formula 12, R 21 and R 22 They are either the same or different from each other and are either H or CH3, J2 and K2 are each integers from 10 to 20.

10. The photosensitive laminate according to claim 6, in, The carboxyl-containing alkaline developing adhesive resin 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 higher and 150°C or lower.

11. The photosensitive laminate according to claim 6, in, The acid value of the alkali developing adhesive resin containing carboxyl groups is in the range of 100 mg KOH / g to 300 mg KOH / g.

12. A method for manufacturing a circuit board using the photosensitive laminate of claim 1.

13. A method for manufacturing the photosensitive laminate of claim 1, comprising the following steps: A resin composition comprising: a mixed solvent containing a high-boiling-point solvent with a boiling point above 115°C and a low-boiling-point solvent with a boiling point below 100°C; an alkaline developing adhesive resin containing carboxyl groups; and a photoinitiator is coated onto a support substrate and then dried. The mixed solvent comprises a high-boiling-point solvent with a boiling point of 115°C or higher and a low-boiling-point solvent with a boiling point of 100°C or lower, in a weight ratio of 1:3 to 1:

15.

14. The method for manufacturing a photosensitive laminate according to claim 13, in, The content of high-boiling-point solvents with a boiling point of 115°C or higher in the mixed solvent is 3% by weight or more.

15. The method for manufacturing a photosensitive laminate according to claim 13, in, The high-boiling-point solvent with a boiling point of 115°C or higher includes at least one organic solvent selected from butanol, dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone, butyl carbitol, butyl cellosolve, methyl cellosolve, butyl acetate, diethylene glycol methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol methyl ether propionate, dipropylene glycol dimethyl ether, cyclohexanone, and propylene glycol monomethyl ether acetate (PGMEA).

16. The method for manufacturing a photosensitive laminate according to claim 13, in, The low-boiling-point solvent with a boiling point below 100°C includes at least one organic solvent selected from methyl ethyl ketone, methanol, ethanol, acetone, tetrahydrofuran, and isopropanol.

17. The method for manufacturing a photosensitive laminate according to claim 13, in, The resin composition further comprises: a photopolymerizable compound containing (meth)acrylate monomers or oligomers.

18. The method for manufacturing a photosensitive laminate according to claim 17, in, The photopolymerizable compound comprising (meth)acrylate monomers or oligomers comprises 2 to 10 functional (meth)acrylate monomers or oligomers containing aromatic functional groups in the molecule.

19. The method for manufacturing a photosensitive laminate according to claim 13, in, The carboxyl-containing alkaline developing adhesive resin 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 higher and 150°C or lower.

20. The method for manufacturing a photosensitive laminate according to claim 13, in, The acid value of the alkali developing adhesive resin containing carboxyl groups is above 100 mg KOH / g and below 300 mg KOH / g.

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