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CN117120925A - Photosensitive laminate and method for manufacturing circuit board using the same - Google Patents

Photosensitive laminate and method for manufacturing circuit board using the same Download PDF

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Publication number
CN117120925A
CN117120925A CN202280024373.5A CN202280024373A CN117120925A CN 117120925 A CN117120925 A CN 117120925A CN 202280024373 A CN202280024373 A CN 202280024373A CN 117120925 A CN117120925 A CN 117120925A
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CN
China
Prior art keywords
photosensitive
acrylate
meth
photosensitive laminate
laminate according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202280024373.5A
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Chinese (zh)
Inventor
石想勋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kolon Industries Inc
Original Assignee
Kolon Industries Inc
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Filing date
Publication date
Application filed by Kolon Industries Inc filed Critical Kolon Industries Inc
Publication of CN117120925A publication Critical patent/CN117120925A/en
Pending legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/20—Esters containing oxygen in addition to the carboxy oxygen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/061—Etching masks
    • H05K3/064—Photoresists
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Laminated Bodies (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Materials For Photolithography (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

The present application relates to a photosensitive laminate, and a method of manufacturing a circuit board using the same, the photosensitive laminate comprising: a barrier layer having a haze of 2% or less; and a photosensitive resin layer comprising a photopolymerizable compound containing an ester monomer or oligomer, and a binder resin, wherein bubbles having a diameter of less than 1 μm are present at 5 bubbles/mm 2 The following exists in the photosensitive resin layer.

Description

Photosensitive laminate and method for manufacturing circuit board using the same
Technical Field
Cross Reference to Related Applications
The present application claims the benefit of korean patent application No.10-2021-0042140, filed 3 months 31 of 2021, to the korean intellectual property office, the disclosure of which is incorporated herein by reference in its entirety.
The present disclosure relates to a photosensitive laminate and a method of manufacturing a circuit board.
Background
The photosensitive resin composition is used in the form of a dry film photoresist (DFR), a liquid photoresist ink, etc. for a Printed Circuit Board (PCB) or a lead frame.
Recently, with the trend toward lighter, thinner, shorter and more compact semiconductor devices and multi-level packages, a high-density circuit board is required, and a process of applying direct exposure of an ultra-high pressure mercury lamp or laser, or a process of manufacturing a circuit board using a photosensitive laminate including a support film and a photosensitive resin layer, etc. are also widely used.
Accordingly, there is a continuing need to develop a method and process that achieves high density and sensitivity while ensuring higher reliability, and that is capable of forming finer wiring.
[ Prior Art literature ]
[ patent literature ]
(patent document 1) Japanese unexamined patent application publication No.2006-106287 (published 4/20/2006)
Disclosure of Invention
Technical problem
An object of the present disclosure is to provide a photosensitive laminate that can reduce defects at the time of fine wiring formation, ensure high reliability during development, and form a high-density circuit.
It is another object of the present disclosure to provide a method of manufacturing a circuit board using the photosensitive laminate.
Technical proposal
According to an aspect of the present disclosure, there may be provided a photosensitive laminate comprising: a barrier layer having a haze of 2% or less; and a photosensitive resin layer comprising a photopolymerizable compound containing an ester monomer or oligomer, and a binder resin, wherein bubbles having a diameter of less than 1 μm are present at 5 bubbles/mm 2 The following exists in the photosensitive resin layer.
According to another aspect of the present disclosure, a method of manufacturing a circuit board using the photosensitive laminated body may be provided.
Hereinafter, a photosensitive laminate and a method of manufacturing a circuit board according to specific embodiments of the present disclosure will be described in more detail.
As used herein, weight average molecular weight refers to weight average molecular weight as measured by GPC method in terms of polystyrene. In determining the weight average molecular weight in terms of polystyrene measured by GPC, a known analysis device, a detector such as a refractive index detector, and an analytical column can be used. The usual conditions of temperature, solvent and flow rate may be used.
Specific examples of measurement conditions are as follows: the alkali-developable binder resin was dissolved in tetrahydrofuran to a concentration of 1.0 (w/w)% (based on the solid content of about 0.5 (w/w)%) in THF, filtered using a syringe filter having a pore size of 0.45 μm, and then 20 μl was injected into GPC. The mobile phase of GPC was Tetrahydrofuran (THF), fed at a flow rate of 1.0mL/min, and the column was connected one Agilent PLgel5 μm Guard (7.5X100 mm) and two Agilent PLgel5 μm Mixed D (7.5X100 mm) in series, using the Agilent 1260 Infinicity II system, RI detector as detector, and measurements were made at 40 ℃.
Polystyrene standard samples (STD a, B, C, D) in which polystyrene having different molecular weights as described below were dissolved in tetrahydrofuran at a concentration of 0.1 (w/w)%, were filtered with an injection filter having a pore size of 0.45 μm, then injected into GPC, and the value of the weight average molecular weight (Mw) of the alkali-developable binder resin was determined using the calibration curve formed.
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
As used herein, the term "(photo) cured product" or "(photo) cured" is meant to include not only the case where a component having a curable or crosslinkable unsaturated group in the chemical structure is fully cured, crosslinked or polymerized, but also the case where such component is partially cured, crosslinked or polymerized.
According to another embodiment of the present disclosure, there may be provided a photosensitive laminate comprising: a barrier layer having a haze of 2% or less; and a photosensitive resin layer comprising a photopolymerizable compound containing an ester monomer or oligomer, and a binder resin, wherein bubbles having a diameter of less than 1 μm are present at 5 bubbles/mm 2 The following exists in the photosensitive resin layer.
The present inventors newly developed a photosensitive laminate comprising a barrier layer having a haze of 2% or less and wherein bubbles having a diameter of less than 1 μm, or 0.001 μm or more and less than 1 μm are present at 5 bubbles/mm 2 The photosensitive resin layer exists below, and it has been found through experiments that when such a photosensitive laminate is used in a manufacturing process of a circuit board, high sensitivity to exposure can be achieved, reliability in a developing process is improved, high density and sensitivity are achieved while ensuring high reliability, and finer wiring can be formed, and the present disclosure has been completed.
The present inventors have found that excellent circuit pattern resolution can be achieved in a dry film photoresist manufacturing process using a photosensitive laminate by including a barrier layer having a haze of 2% or less and having excellent optical characteristics. In particular, the present inventors have found that by including a blocking layer having a haze of 2% or less, the blocking layer can act as an oxygen blocking film blocking oxygen radical reaction, thereby minimizing the formation of foreign substances or bubbles in the photosensitive resin layer, improving the resolution and reliability of the finally manufactured dry film photoresist, and completed the present disclosure.
Specifically, in the photosensitive laminate of one embodiment, the barrier layer may have a haze of 2% or less, 0.001% or more and 2% or less, or 0.1% or more and 2% or less.
The method for measuring HAZE is not particularly limited, but may be measured according to the measurement method of ASTM D1003 using a HAZE METER (model name: NDH7000, nippon Denshoku corp.).
The thickness of the barrier layer whose haze is to be measured may be 0.1 μm to 10 μm, or 1 μm to 3 μm. The physical properties measured by the barrier layer may also change by a specific value when the thickness of the barrier layer increases or decreases by a specific value.
When the haze of the barrier layer exceeds 2%, there may be a problem in that the circuit performance and resolution are deteriorated.
In one embodiment of the photosensitive laminate, the barrier layer may have a volume of 10cc/m 2 Less than/day, 5cc/m 2 Less than/day, 4cc/m 2 Less than/day, 0.01cc/m 2 More than/day and 10cc/m 2 Less than/day, 0.01cc/m 2 Per day and 5cc/m 2 Less than/day, or 0.01cc/m 2 Per day and 4cc/m 2 Oxygen permeability per day or less. The method for measuring the oxygen permeability is not particularly limited, but, for example, it may be measured according to the measurement method of ASTM F1927 using OX-Tran (model 2/61, mocon Inc.).
The thickness of the barrier layer to be measured for oxygen permeability may be 0.1 μm to 10 μm, or 1 μm to 3 μm. The physical properties measured by the barrier layer may also change by a specific value when the thickness of the barrier layer increases or decreases by a specific value.
Since the barrier layer has 10cc/m 2 An oxygen permeability of/day or less, and thus the barrier layer may serve as an oxygen barrier film blocking oxygen radical reaction, thereby minimizing the formation of foreign substances or bubbles in the photosensitive resin layer and improving resolution and reliability of the finally manufactured dry film photoresist.
The barrier layer may be formed of a composition for forming a barrier layer, and the composition for forming a barrier layer may include a polyvinyl alcohol resin.
That is, the barrier layer may include a polyvinyl alcohol resin having a weight average molecular weight of 5,000 to 1,000,000g/mol, 7,000 to 750,000g/mol, 7,000 to 700,000g/mol, 7,000 to 50,000g/mol, 7,000 to 30,000g/mol, or 10,000 to 30,000 g/mol. Since the barrier layer includes a polyvinyl alcohol resin having a weight average molecular weight of 10,000g/mol to 1,000,000g/mol, the haze of the barrier layer may satisfy 2% or less.
More specifically, the polyvinyl alcohol resin may have a viscosity of 1.0cP to 10.0cP, 3.0cP to 5.0 cP. Since the viscosity of the polyvinyl alcohol resin satisfies 1.0cP to 10.0cP, the haze of the barrier layer may satisfy 2% or less.
In addition, the composition for forming the barrier layer may include a high boiling point solvent having a boiling point of 115 ℃ or more.
Examples of the high boiling point solvent having a boiling point of 115 ℃ or higher may include: 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, propylene Glycol Monomethyl Ether Acetate (PGMEA), and a mixed solvent of one or more thereof.
Specifically, the composition for forming the barrier layer may include 60 parts by weight or more, 60 parts by weight or more and 200 parts by weight or less, 70 parts by weight or more and 200 parts by weight or less, 80 parts by weight or more and 100 parts by weight or less, or 90 parts by weight or more and 100 parts by weight or less of a high boiling point solvent having a boiling point of 115 ℃ or more, based on 100 parts by weight of the polyvinyl alcohol resin.
When the composition for forming a barrier layer contains 60 parts by weight or more of a high boiling point solvent having a boiling point of 115 ℃ or more based on 100 parts by weight of the polyvinyl alcohol resin, the haze of the barrier layer may satisfy 2% or less, and when the composition for forming a barrier layer contains less than 60 parts by weight of a high boiling point solvent having a boiling point of 115 ℃ or more based on 100 parts by weight of the polyvinyl alcohol resin, there may be a technical problem in that the haze of the barrier layer increases sharply.
The thicknesses of the barrier layer and the photosensitive resin layer in the photosensitive laminate are not particularly limited, but as a specific example, the barrier layer may have a thickness of 0.1 μm to 10 μm, or 1 μm to 3 μm, and the thickness of the photosensitive resin layer may be 1 μm to 100 μm, or 5 μm to 50 μm.
The photosensitive laminate of one embodiment may further include a support substrate formed on the barrier layer and having a thickness of 1 μm to 100 μm. As a specific example, the thickness of the support substrate may be 1 μm to 100 μm, or 5 μm to 50 μm. That is, the photosensitive laminate of one embodiment may have a laminated structure in which a support substrate, a barrier layer, and a photosensitive resin layer are laminated in this order. In the process of manufacturing the photosensitive laminate, the support substrate may function as a kind of carrier. Further, the support substrate may be optionally included or not included in the photosensitive laminate according to the semiconductor manufacturing process to which the photosensitive laminate is applied or the final manufactured product.
Further, the photosensitive laminate of one embodiment may further include a release layer formed on the photosensitive resin layer and having a thickness of 0.01 μm to 1 m. As specific examples, the thickness of the release layer may be 0.01 μm to 1m, 1 μm to 100 μm, or 5 μm to 50 μm. That is, the photosensitive laminate of one embodiment may have a laminate structure in which a support substrate, a barrier layer, a photosensitive resin layer, and a release layer are laminated in this order.
As described above, in the dry film photoresist manufacturing process using the photosensitive laminate, the support substrate and the release layer may be removed. Since the photosensitive laminate includes a barrier layer having a haze of 2% or less, the finally manufactured dry film photoresist can achieve excellent reliability and resolution even if the support substrate is removed.
Specifically, in the photosensitive laminate of one embodiment, since the bubbles having a diameter of less than 1 μm in the photosensitive resin layer are present at 5 bubbles/mm 2 The photosensitive laminate is suitable for use in a semiconductor manufacturing process even in a state where only a barrier layer having a haze of 2% or less is formed, and thus the same level or higher level of reliability and sensitivity than conventionally known photosensitive laminates can be achieved even with a thinner thickness.
Further, since the photosensitive laminate of one embodiment is applicable to a semiconductor manufacturing process in a case where a support substrate such as a polyethylene terephthalate (PET) film is peeled off, a process of separately peeling off the support substrate in the semiconductor manufacturing process can be omitted. Further, in a structure in which a support substrate such as a polyethylene terephthalate (PET) film is interposed or laminated, it is possible to improve the support substrate in such a point that there are limitations in optical characteristics, exposure, development, sensitivity realization, and the like.
Meanwhile, the present inventors have continuously conducted research and development to remove trace amounts of fine bubbles or fine byproducts that may occur due to various reasons in the manufacturing process. As described above, in the method for producing a photosensitive laminate described later, the inventors used a resin composition comprising: a mixed solvent comprising a high boiling point solvent having a boiling point of 115 ℃ or higher and a low boiling point solvent having a boiling point of 100 ℃ or lower, a binder resin, a photopolymerizable compound comprising an ester monomer or oligomer, a binder resin, and a photoinitiator, and such that bubbles having a diameter of less than 1 μm can be present in 5 bubbles/mm 2 Below or 3 bubbles/mm 2 The following is stored in the photosensitive resin layer.
Further, in the method for producing a photosensitive laminate, by adjusting the drying rate and/or the drying temperature, the volume of fine bubbles formed in the photosensitive resin layer can be significantly reduced or substantially absent, except for using a mixed solvent comprising a high boiling point solvent having a boiling point of 115 ℃ or more and a low boiling point solvent having a boiling point of 100 ℃ or less.
At the same time, the bubbles with the diameter smaller than 1 μm can be 5 bubbles/mm 2 Below or 3 bubbles/mm 2 The following is present in the photosensitive resin layer. In particular, bubbles having a diameter of less than 1 μm may be present in trace amounts or substantially absent on the opposite surface of the interface between the support substrate and the photosensitive resin layer or toward the outer surface of the photosensitive resin layer. From the opposite surface of the interface between the barrier layer and the photosensitive resin layer, bubbles having a diameter of less than 1 μm may be present in 3 bubbles/mm within 50% of the total thickness of the photosensitive resin layer 2 The following exists.
Since bubbles having a diameter of less than 1 μm may exist in trace amounts or substantially not exist on the opposite surface of the interface between the barrier layer and the photosensitive resin layer or toward the outer surface of the photosensitive resin layer, reliability in a developing process can be improved, a high-density circuit can be formed and defects in forming fine wirings can be reduced, whereby, when the photosensitive laminate is used, high sensitivity to exposure can be achieved and the production yield of a high-density printed circuit board can be improved.
Further, as described above, the photosensitive laminate may contain not only a trace amount or substantially no bubbles having a diameter of less than 1 μm, but also no bubbles having a diameter of 1 μm or more and 5 μm or less.
When a circuit board is produced by using the photosensitive laminate in which bubbles having a diameter of less than 1 μm exist in trace amounts in the photosensitive resin layer as described above, high density and sensitivity are achieved while ensuring high reliability, and finer wirings can be formed.
More specifically, even if the photosensitive resin layer is exposed to ultraviolet rays and developed using an alkaline solution, defects do not occur in the entire region, or even if they occur, they occur in very small amounts. In particular, the upper surface of the photosensitive resin layer is substantially free of defects, and after development, the lower surface or the inside of the photosensitive resin layer may have fine-sized defects.
Specifically, after exposing the photosensitive resin layer to ultraviolet rays and developing with an alkaline solution, the photosensitive resin layer can be developed with 3 defects/mm 2 Below, or 1 defect/mm 2 Defects having a cross-sectional diameter of 0.3 μm to 4 μm, or 0.5 μm or more and 3 μm or less, or substantially no defects may be observed below. The cross-sectional diameter of the defect may be defined as the largest diameter among the diameters of the defects defined in a cross-section in one direction on the photosensitive resin layer.
The conditions for exposure and development are not particularly limited. For example, the photosensitive laminate is irradiated with light having a wavelength in the range of 340nm to 420nm, and exposure may be performed for 1 to 60 minutes with the energy at which the number of stages of the remaining stages measured becomes 15 stages using a 41-stage exposure meter of Stouffer Graphic Arts Equipment. In addition, the concentration of 0.1 to 3.0 wt% can be used by a method such as a spray jet methodAn alkaline aqueous solution such as Na 2 CO 3 Development is performed.
Further, when the photosensitive laminate is used, higher density and sensitivity can be achieved even with lower energy. More specifically, the photosensitive laminate is irradiated with light having a wavelength in the range of 340nm to 420nm, and using a 41-stage exposure meter of Stouffer Graphic Arts Equipment, the energy at which the number of stages of the remaining stages measured becomes 15 stages may be 300mJ/cm 2 Below or 100mJ/cm 2 Hereinafter, and the resolution after development may be 15 μm or less, or 10 μm or less, or 7 μm or less, or 5 μm or less.
At the same time, the characteristic of the photosensitive laminate or the bubbles having a diameter of less than 1 μm are present in 5 bubbles/mm 2 The following structural characteristics present in the photosensitive resin layer can be attributed to the above-described production method, and can be attributed to the characteristics of the photosensitive resin layer.
Specifically, the photosensitive resin layer may include an alkali-developable binder resin containing a carboxyl group. The alkali developable binder contains at least one carboxyl group in one molecule and can react with a base during development.
Specific examples of the alkali developable adhesive are not limited, but may be a polymer or copolymer containing at least one repeating unit selected from the group consisting of a repeating unit represented by the following chemical formula 4, a repeating unit represented by the following chemical formula 5, and a repeating unit represented by the following chemical formula 6.
[ chemical formula 4]
Wherein, in chemical formula 4, R 3 Is hydrogen or an alkyl group having 1 to 10 carbon atoms,
[ chemical formula 5]
Wherein, in chemical formula 5, R 4 Is hydrogen or alkyl having 1 to 10 carbon atoms, R 5 Is an alkyl group having 1 to 10 carbon atoms.
[ chemical formula 6]
Wherein, in chemical formula 6, ar is an aryl group having 6 to 20 carbon atoms.
In chemical formulas 4 to 6, R 3 And R is 4 Are identical or different from one another and are each independently of one another hydrogen or alkyl having 1 to 10 carbon atoms, R 5 Ar is an aryl group having from 6 to 20 carbon atoms.
In chemical formulas 2 to 4, R 3 And R is 4 And may each be independently any one of hydrogen or an alkyl group having 1 to 10 carbon atoms, wherein specific examples of the alkyl group having 1 to 10 carbon atoms include methyl groups.
R 5 Specific examples of the alkyl group which is an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms include methyl groups.
Ar is an aryl group having 6 to 20 carbon atoms, and specific examples of the aryl group having 6 to 20 carbon atoms include phenyl groups.
The repeating unit represented by chemical formula 4 may be a repeating unit derived from a monomer represented by chemical formula 4-1 below.
[ chemical formula 4-1]
Wherein, in chemical formula 4-1, R 3 Is hydrogen or an alkyl group having 1 to 10 carbon atoms. In chemical formula 4-1, R is 3 The content of (2) is the same as that described in the above chemical formula 4. Specific examples of the monomer represented by chemical formula 4-1 include Acrylic Acid (AA) and methacrylic acid (MAA).
The repeating unit represented by chemical formula 5 may be a repeating unit derived from a monomer represented by chemical formula 5-1 below.
[ chemical formula 5-1]
Wherein, in chemical formula 5-1, R 4 Is hydrogen or alkyl having 1 to 10 carbon atoms, and R5 is alkyl having 1 to 10 carbon atoms. In chemical formula 5-1, R 4 And R is 5 The same as described in the above chemical formula 5. Specific examples of the monomer represented by chemical formula 5-1 include Methyl Methacrylate (MMA) and Butyl Acrylate (BA).
The repeating unit represented by chemical formula 6 may be a repeating unit derived from a monomer represented by chemical formula 6-1 below.
[ chemical formula 6-1]
Wherein, in chemical formula 6-1, ar is an aryl group having 6 to 20 carbon atoms. In chemical formula 6-1, the content of Ar is the same as that described in chemical formula 4 above. One specific example of the monomer represented by chemical formula 6-1 may include Styrene (SM).
Meanwhile, the binder resin may serve as a base of the photosensitive resin layer, and thus, must have a minimum molecular weight. For example, the weight average molecular weight thereof may be 20,000 to 300,000g/mol, 30,000 to 250,000g/mol, 30,000 to 200,000g/mol, or 30,000 to 150,000g/mol.
Further, the binder resin should have at least a certain level of heat resistance, and thus, the glass transition temperature may be 20 ℃ or more and 150 ℃ or less, 50 ℃ or more and 150 ℃ or less, 70 ℃ or more and 120 ℃ or less, 80 ℃ or more and 120 ℃ or less, or 100 ℃ or more and 120 ℃ or less.
Further, in view of developability of the photosensitive resin layer, the acid value of the binder resin may be 100mgKOH/g or more and 300mgKOH/g or less, 120mgKOH/g or more and 250mgKOH/g or less, 120mgKOH/g or more and 200mgKOH/g or less, or 150mgKOH/g or more and 200mgKOH/g or less.
Meanwhile, the binder resin may include two or more alkali-developable binders having different types or different properties. In particular, the binder resin may include a first alkali-developable binder resin and a second alkali-developable binder resin.
The weight average molecular weight of the first and second alkali developable binder resins may be 20,000g/mol to 300,000g/mol, 30,000g/mol to 250,000g/mol, 30,000g/mol to 200,000g/mol, or 30,000g/mol to 150,000g/mol, and the glass transition temperature may be 20 ℃ or more and 150 ℃ or less, 50 ℃ or more and 150 ℃ or less, 70 ℃ or more and 120 ℃ or less, 80 ℃ or more and 120 ℃ or less or 100 ℃ or more and 120 ℃ or less. They may each have a different weight average molecular weight, glass transition temperature, or acid number.
For example, the first alkali-developable binder resin may have an acid value of 140mgKOH/g or more and 160mgKOH/g or less. Further, the second alkali-developable binder resin may have an acid value of 160mgKOH/g or more and 200mgKOH/g or less.
Further, the ratio of the glass transition temperature of the first alkali-developable binder resin to the second alkali-developable binder resin may be 1:1.5 or more and 1:5 or less, 1:1.5 or more and 1:3 or less, 1:1.5 or more and 1:2 or less, 1:1.5 or more and 1:1.8 or less, 1:1.5 or more and 1:75 or 1:1.6 or more and 1:7 or less.
Further, the acid value ratio of the first alkali-developable binder resin to the second alkali-developable binder resin may be 1:1.01 or more and 1:1.5 or less, 1:1.1 or more and 1:1.5 or less, 1:1.25 or more and 1:1.5 or more and 1:1.4 or less and 1:1.5 or less.
Meanwhile, the photosensitive resin layer may include a crosslinked copolymer between the binder resin and the photopolymerizable compound including the ester monomer or oligomer.
The photopolymerizable compound containing an ester monomer or oligomer may serve as a crosslinking agent for improving the mechanical strength of the photosensitive resin layer, etc., or serve to increase the resistance to a developer and impart flexibility to the cured film.
Further, by using a photopolymerizable compound containing an ester monomer or oligomer, the photosensitive resin layer can have higher adhesion with the barrier layer, and the development time or peeling time of the photosensitive laminate can be greatly shortened.
Specific examples of the ester monomer or oligomer include (meth) acrylates having one or more hydroxyl groups, epoxy groups or amino groups bonded thereto.
The (meth) acrylate to which one or more hydroxyl, epoxy or amino groups are bonded has the following structure: the (meth) acrylate functionality is located at either terminus, while any one or more of the hydroxyl, epoxy, or amino groups may be located at one or more different termini, and the divalent organic functionality may be bonded as a mediator between the (meth) acrylate functionality and the hydroxyl, epoxy, or amino groups.
In addition, a more specific example of the ester monomer or oligomer may include a compound of the following chemical formula 1:
[ chemical formula 1]
CH 2 ＝CR 1 -COO-R 2 -OH
Wherein, in chemical formula 1, R 1 Is hydrogen or alkyl having 1 to 10 carbon atoms, R 2 Is a divalent saturated aliphatic hydrocarbon group having 1 to 100 carbon atoms, wherein the saturated aliphatic hydrocarbon group may optionally include a halogen atom, an ether bond (-O-), an ester bond (-COO-or O-CO-), an amide bond (-NHCO-or CONH-) or an aryl group.
More specifically, the ester monomer or oligomer may include glycerol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol monoacrylate, hydroxypropyl (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol monoacrylate, poly (ethylene glycol propylene glycol) -mono (meth) acrylate, polyethylene glycol polypropylene glycol-mono (meth) acrylate, poly (ethylene glycol butylene glycol) -mono (meth) acrylate (product name: blemmer 55PET-800, etc.), poly (propylene glycol butylene glycol) -mono (meth) acrylate, propylene glycol polytetramethylene glycol-mono (meth) acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 1, 4-cyclohexanedimethanol monoacrylate, or a mixture of two or more thereof.
The weight average molecular weight of the ester monomer or oligomer is not particularly limited, but for example, the weight average molecular weight thereof may be 50g/mol to 10,000g/mol, or 70g/mol to 5,000g/mol, or 80g/mol to 1,200g/mol, or 100g/mol to 1,000g/mol.
The content of the photopolymerizable compound including the ester monomer or oligomer may be adjusted according to the specific use or characteristics of the photosensitive resin layer. For example, the content of the photopolymerizable compound including the ester monomer or oligomer may be 1 to 80 parts by weight, 1 to 50 parts by weight, 1 to 30 parts by weight, 1 to 20 parts by weight, 1 to 10 parts by weight, 2 to 50 parts by weight, 2 to 30 parts by weight, 2 to 20 parts by weight, 2 to 10 parts by weight, 5 to 50 parts by weight, 5 to 30 parts by weight, 5 to 20 parts by weight, 5 to 10 parts by weight, based on 100 parts by weight of the alkali developable binder resin.
That is, as described in a production method described later, when the photosensitive laminate of the embodiment is used by mixing two or more solvents having different boiling points and depending on the selection of the photopolymerizable compound containing the ester monomer or oligomer, fine bubbles may exist in trace amounts or substantially not exist in the photosensitive resin layer.
In particular, due to the structure and characteristics of the photopolymerizable compound containing the ester monomer or oligomer, bubbles having a diameter of 1 μm or less may exist in trace amounts in the photosensitive resin layer, and thus, a photosensitive laminate may be provided which may reduce defects in fine wiring formation, may ensure high reliability during development, and thus may be capable of forming a high-density circuit.
Meanwhile, the photopolymerizable compound may further include a monofunctional (meth) acrylate compound or a multifunctional (meth) acrylate compound. As the photopolymerizable compound, a known monofunctional or polyfunctional (meth) acrylate monomer or oligomer may be used.
Examples of the photopolymerizable compound that can be additionally used are not particularly limited, but include: ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1, 6-hexane diol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, glycerol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentamethacrylate, 2-bis (4-methacryloxydiethoxyphenyl) propane, 2-bis (4-methacryloxypolyethoxyphenyl) propane, 2-hydroxy-3-methacryloxypropyl methacrylate, ethylene glycol diglycidyl ether dimethacrylate, diethylene glycol diglycidyl ether dimethacrylate, diglycidyl phthalate dimethacrylate, glycerol polyglycidyl ether polymethacrylate, polyfunctional (meth) acrylates containing urethane groups, and the like.
The content of the monofunctional (meth) acrylate compound or the polyfunctional (meth) acrylate compound may be adjusted according to the specific use or characteristics of the photosensitive resin layer. For example, the photopolymerizable compound may include 50 to 1500 parts by weight, 100 to 1500 parts by weight, 110 to 1000 parts by weight, 110 to 900 parts by weight, 50 to 500 parts by weight of a monofunctional (meth) acrylate compound or a multifunctional (meth) acrylate compound based on 100 parts by weight of the ester monomer or oligomer.
Meanwhile, as the base film, various plastic films may be used, examples of which include one or more plastic films selected from the group consisting of an acrylic film, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a Polynorbornene (PNB) film, a Cyclic Olefin Polymer (COP) film, and a Polycarbonate (PC) film.
Meanwhile, the peeling layer may include a protective film.
That is, the photosensitive laminate may further include a protective film formed so as to be opposed to the support substrate at the center of the photosensitive resin layer. The protective film serves as a protective cover that prevents damage to the resist during processing and protects the photosensitive resin layer from foreign substances such as dust, and may be laminated on the back surface of the photosensitive resin layer where the barrier layer is not formed.
The protective film is used to protect the photosensitive resin layer from the outside, and is required to have proper peelability and adhesiveness so that it is easily separated when the dry film photoresist is applied to a post-treatment process, and not to be separated from a mold during storage and distribution.
Various plastic films may be used as the protective film, examples of which include: at least one plastic film selected from the group consisting of an acrylic film, a Polyethylene (PE) film, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a Polynorbornene (PNB) film, a Cyclic Olefin Polymer (COP) film, and a Polycarbonate (PC) film. The thickness of the protective film is not particularly limited, but may be freely adjusted in a range of, for example, 0.01 μm to 1 m.
According to another embodiment of the present disclosure, there may be provided a method of manufacturing a photosensitive laminate, the method including the steps of: a resin composition including a mixed solvent containing a high boiling point solvent having a boiling point of 115 ℃ or more and a low boiling point solvent having a boiling point of 100 ℃ or less, a binder resin, a photopolymerizable compound including an ester monomer or oligomer, and a photoinitiator is applied and dried on the barrier layer.
According to the manufacturing method, the photosensitive laminate of the above-described one embodiment can be provided.
As described above, the photosensitive laminate includes: mist sprayA barrier layer having a degree of 2% or less; and a photosensitive resin layer comprising a photopolymerizable compound containing an ester monomer or oligomer, and a binder resin, wherein bubbles having a diameter of less than 1 μm are present at 5 bubbles/mm 2 The following exists in the photosensitive resin layer.
In the process of forming the photosensitive resin layer, bubbles having a diameter of less than 1 μm may be formed in the photosensitive resin layer due to bubbles generated, for example, in the process of preparing a solution of the photosensitive resin composition or in the process of drying a solution of the composition. In the method for producing the photosensitive laminate, since a mixed solvent comprising a high boiling point solvent having a boiling point of 115 ℃ or more and a low boiling point solvent having a boiling point of 100 ℃ or less is used, it is possible to lengthen the evaporation time of the solution of the photosensitive resin composition and to prevent bubbles from remaining in the resin layer, whereby bubbles having a diameter of less than 1 μm are present at 5 bubbles/mm 2 The following exists in the photosensitive resin layer.
More specifically, bubbles smaller than 1 μm in diameter may be present at 5 bubbles/mm 2 Below or 3 bubbles/mm 2 The following is present in the photosensitive resin layer.
Further, from the opposite surface of the interface between the barrier layer and the photosensitive resin layer, bubbles having a diameter of less than 1 μm may be present in 3 bubbles/mm within 50% of the total thickness of the photosensitive resin layer 2 The following exists.
Since bubbles having a diameter of less than 1 μm may be present in trace amounts or substantially absent on the opposite surface of the interface between the barrier layer and the photosensitive resin layer or on the outer surface facing the photosensitive resin layer, reliability during development can be improved, high-density circuits can be formed and defects in fine wiring formation can be reduced, whereby high sensitivity to exposure can be achieved and the production yield of high-density printed circuit boards can be improved when the photosensitive laminate is used.
As described above, the high boiling point solvent having a boiling point of 115 ℃ or more can function to prolong the evaporation time of the liquid component of the photosensitive resin composition and prevent bubbles from being retained in the resin layer. Thus, bubbles with a diameter of less than 1 μm can be treated with 5 bubbles +.mm 2 The following exists in the photosensitive resin layer.
The mixed solvent may contain a certain amount or more of a high boiling point solvent having a boiling point of 115 ℃ or more. For example, the content of the high boiling point solvent having a boiling point of 115 ℃ or higher may be 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, with respect to 100 parts by weight of the mixed solvent.
When a low boiling point solvent having a boiling point of 100 ℃ or less is used together with a high boiling point solvent having a boiling point of 115 ℃ or more, the solvency of the photosensitive resin composition can be improved.
The mixed solvent may contain a low boiling point solvent having a boiling point of 100 ℃ or less in an amount higher than that of the high boiling point solvent having a boiling point of 115 ℃ or more.
More specifically, the mixed solvent may comprise 1:2 to 1: 20. or 1:3 to 1:15 a high boiling point solvent having a boiling point of 115 ℃ or higher: a low boiling point solvent having a boiling point of 100 ℃ or lower. When the high boiling point solvent having a boiling point of 115 ℃ or higher is contained in the above content: when the boiling point is 100 ℃ or lower, the solubility of the photosensitive resin composition can be improved.
Examples of the high boiling point solvent having a boiling point of 115 ℃ or higher include: 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, propylene Glycol Monomethyl Ether Acetate (PGMEA), and a mixed solvent of one or more thereof.
Examples of the low boiling point solvent having a boiling point of 100 ℃ or lower include: methyl ethyl ketone, methanol, ethanol, acetone, tetrahydrofuran, isopropanol and a mixed solvent of one or more of them.
The solvent mixture comprises a high boiling point solvent with a boiling point of 115 ℃ or higher and a low boiling point solvent with a boiling point of 100 ℃ or lower; a binder resin; a photopolymerizable compound comprising an ester monomer or oligomer; and the solid content of the resin composition of the photoinitiator may be adjusted in consideration of specific uses or application fields, for example, the resin composition may contain 10 to 99% by weight of the mixed solvent.
Meanwhile, there is no particular limitation on a method or apparatus that may be used in the step of applying the resin composition onto the barrier layer and drying, and for example, the resin composition may be coated on the barrier layer using a conventional coating method and then dried to prepare a dry film.
There is no particular limitation on the method of coating the resin composition, and for example, a method such as coating a rod may be used.
In the method of manufacturing the photosensitive laminate, by adjusting the drying rate and/or the drying temperature, the volume of fine bubbles formed in the photosensitive resin layer can be significantly reduced or substantially absent, except for using a mixed solvent comprising a high boiling point solvent having a boiling point of 115 ℃ or more and a low boiling point solvent having a boiling point of 100 ℃ or less.
More specifically, the drying step of the coated resin composition may be performed by heating means such as a hot air oven, a hot plate, a hot air circulation oven, an infrared oven, and the drying may be performed at a temperature of 50 to 100 ℃, or a temperature of 60 to 90 ℃, and a temperature of 70 to 85 ℃.
The time for performing the drying 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 regarding the binder resin included in the resin composition includes the content described in the photosensitive laminate of the above-described one embodiment.
The weight average molecular weight of the binder resin may be 20,000g/mol to 300,000g/mol, 30,000g/mol to 250,000g/mol, 30,000g/mol to 200,000g/mol, or 30,000g/mol to 150,000g/mol, and the glass transition temperature may be 20 ℃ or more and 150 ℃ or less, 50 ℃ or more and 150 ℃ or less, 70 ℃ or more and 120 ℃ or less, 80 ℃ or more and 120 ℃ or 100 ℃ or more and 120 ℃ or less.
The acid value of the binder resin may be 100 to 300mgKOH/g, 120 to 250mgKOH/g, 120 to 200mgKOH/g, or 150 to 200 mgKOH/g.
The resin composition may include a photopolymerizable compound including an ester monomer or oligomer, and an alkali developable binder resin.
The resin composition may include the photopolymerizable compound including the ester monomer or oligomer in an amount of 1 to 80 parts by weight, 1 to 50 parts by weight, 1 to 30 parts by weight, 1 to 20 parts by weight, 1 to 10 parts by weight, 2 to 50 parts by weight, 2 to 30 parts by weight, 2 to 20 parts by weight, 2 to 10 parts by weight, 5 to 50 parts by weight, 5 to 30 parts by weight, 5 to 20 parts by weight, 5 to 10 parts by weight, based on 100 parts by weight of the alkali developable binder resin.
The content regarding the photopolymerizable compound includes the content described in the photosensitive laminate of the above-described one embodiment.
In the method for producing a photosensitive laminate of one embodiment, two or more solvents having different boiling points are mixed and used, and depending on the choice of the photopolymerizable compound to be used, a photosensitive resin layer in which fine bubbles are present in trace amounts or substantially absent may be formed.
In particular, specific examples of the ester monomer or oligomer may include a compound of chemical formula 1.
The photopolymerizable compound containing an ester monomer or oligomer may serve as a crosslinking agent for improving the mechanical strength of the photosensitive resin layer, etc., or serve to increase the resistance to a developer and impart flexibility to the cured film. Further, by using a photopolymerizable compound containing an ester monomer or oligomer, the photosensitive resin layer can have higher adhesion with the barrier layer, and the development time or peeling time of the photosensitive laminate can be greatly shortened.
Due to the structure and characteristics of the ester monomer or oligomer, bubbles having a diameter of 1 μm or less may exist in trace amounts in the photosensitive resin layer, and thus, a photosensitive laminate may be provided which may reduce defects in fine wiring formation, may ensure high reliability during development, and thus may be capable of forming a high-density circuit.
Meanwhile, the photopolymerizable compound may further include a monofunctional (meth) acrylate compound or a multifunctional (meth) acrylate compound.
The content of the monofunctional (meth) acrylate compound or the polyfunctional (meth) acrylate compound may be adjusted according to the specific use or characteristics of the photosensitive resin layer. For example, the photopolymerizable compound may include 50 to 1500 parts by weight, 100 to 1500 parts by weight, 110 to 1000 parts by weight, 110 to 900 parts by weight, 50 to 500 parts by weight of a monofunctional (meth) acrylate compound or a polyfunctional (meth) acrylate compound based on 100 parts by weight of the ester monomer or oligomer.
The photoinitiator is a substance that initiates a chain reaction of a photopolymerizable monomer by ultraviolet rays and other radiation, and plays an important role in curing of the resin composition of the photosensitive laminate and the photosensitive resin layer.
Compounds that may be used as photoinitiators include: anthraquinone derivatives such as 2-methylanthraquinone and 2-ethylanthraquinone; benzoin derivatives such as benzoin methyl ether, benzophenone, phenanthrenequinone and 4,4' -bis- (dimethylamino) benzophenone.
In addition, as the photoinitiator, a compound selected from the following may be used, but is not limited thereto: 2,2' -bis (2-chlorophenyl) -4,4', -5,5' -tetraphenylbisimidazole, 1-hydroxycyclohexylphenyl ketone, 2-dimethoxy-1, 2-diphenyl-1-ethanone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- [ 4-morpholinophenyl ] -1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4, 6-trimethylbenzoyldiphenyl phosphine oxide, 1- [4- (2-hydroxymethoxy) phenyl ] -2-hydroxy-2-methyl-1-propanone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propylthioxanthone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-butanone, 1- (4-hydroxy-2-methyl-1-hydroxy-4-methyl-1-phenylketone, 1 ' -hydroxy-2-hydroxymethyl-2-methyl-1-propanone, 4-dimethylthioxanthone, 4-dimethyl-phenylcarbamate, 4-dimethyl-thioxanthone, 4-methyl-phenylketone and 4' -dimethylthioxanthone, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isopentyl 4-dimethylaminobenzoate, 2-diethoxyacetophenone, benzyl ketone dimethyl acetal, benzyl ketone β -methoxydiethyl acetal, 1-phenyl-1, 2-propandioxime-o, o ' - (2-carbonyl) ethoxyether, methyl o-benzoylbenzoate, bis [ 4-dimethylaminophenyl ] ketone, 4' -bis (diethylamino) benzophenone, 4' -dichlorobenzophenone, benzyl, benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzoin, isobutoxybenzoin, t-butoxybenzoin, p-dimethylaminoacetophenone, p-t-butyltrichloroacetophenone, p-t-butyldichloroacetophenone, thioxanthone, 2-methyl thioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, α -dichloro-4-phenoxyand 4-dimethylaminobenzoate.
The content of the photoinitiator is contained in an amount of 0.1 to 20% by weight, or 1 to 10% by weight based on the total weight of the resin composition. When the content of the photoinitiator is within the above range, sufficient sensitivity can be obtained.
When the content of the photoinitiator is too low, since the light efficiency is low, a large amount of exposure is required, and the production efficiency is greatly reduced. When the content of the photoinitiator is too high, there is a disadvantage in that the film becomes brittle and contamination of the developing solution increases, which may cause defects such as short circuits.
In addition, the resin composition may further contain other additives as needed. Other additives that may be used include: dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate in the form of phthalates as plasticizers; triethylene glycol diacetate in the form of ethylene glycol esters, tetraethylene glycol diacetate; para-toluenesulfonamide, benzenesulfonamide, n-butylbenzenesulfonamide in amide form; triphenyl phosphate, and the like.
In order to improve the processability of the resin composition, a leuco dye or a coloring substance may also be added. Leuco dyes may include tris (4-dimethylamino-2-methylphenyl) methane, fluoran dyes, and the like. In particular, when colorless crystal violet (Leuco Crystal Violet) is used, contrast is advantageous and thus preferable. When the leuco dye is contained, the content in the photosensitive resin composition may be 0.1% by weight or more and 10% by weight or less. From the viewpoint of expressing contrast, 0.1% by weight or more is preferable, and from the viewpoint of maintaining storage stability, 10% by weight or less is preferable.
Examples of the coloring substance include toluene sulfonic acid monohydrate, fuchsin, phthalocyanine green, auramine base, parared, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite green, adamantine green, basic blue 20, and the like.
When the coloring matter substance is contained, the addition amount in the photosensitive resin composition may be 0.001% by weight or more and 1% by weight or less. The content of 0.001 wt% or more has an effect of improving workability, and the content of 1 wt% or less has an effect of maintaining storage stability.
In addition, other additives may also include thermal polymerization inhibitors, dyes, color changing agents, adhesion promoters, and the like.
Meanwhile, according to another embodiment of the present disclosure, a method of manufacturing a circuit board using the photosensitive laminated body of the embodiment may be provided.
The photosensitive laminate of the embodiments may be used for lamination on copper clad laminates.
As an example of a manufacturing process of a circuit board or a Printed Circuit Board (PCB), a pretreatment process is first performed in order to laminate a copper clad laminate as a raw material of the PCB. The pretreatment process is carried out in the outer layer process according to the sequence of drilling, deburring, scrubbing and the like. In the inner layer process, scrubbing or acid washing is performed. In the scrubbing process, a bristle brush and a jet pumice process are mainly used, and the pickling may be performed by soft etching and sulfuric acid pickling.
In order to form a circuit on a copper-clad laminate subjected to a pretreatment process, a photosensitive laminate or a dry film photoresist (hereinafter referred to as DFR) may be generally laminated on a copper layer of the copper-clad laminate. In this process, a laminator is used to laminate a photoresist layer of DFR on a copper surface while peeling a protective film of DFR. Typically, lamination can be performed at a lamination speed of 0.5m/min to 3.5m/min, a temperature of 100 ℃ to 130 ℃ and a roll pressure of 10psi to 90psi and heated roll pressure.
The printed circuit board subjected to the lamination process may be left for more than 15 minutes to stabilize the substrate, and then the photoresist of the DFR is exposed using a photomask on which a desired circuit pattern is formed. When the photomask is irradiated with ultraviolet rays in this process, the photoresist irradiated with ultraviolet rays may initiate polymerization by a photoinitiator contained in the irradiated portion. First, oxygen in the photoresist is consumed at an initial stage, and then the activated monomer is polymerized to cause a crosslinking reaction, and then, the polymerization reaction may be continued while a large amount of monomer is consumed, and an unexposed portion may exist in a state where the crosslinking reaction is not performed.
Next, a developing process is performed to remove the unexposed portions of the photoresist. In the case of an alkali developable DFR, an aqueous solution of 0.8 to 1.2% by weight of potassium carbonate and sodium carbonate may be used as the developer. In this process, the unexposed portions of the photoresist are washed away in a developer solution by saponification reaction between the carboxylic acid of the binder polymer and the developer solution, and the cured photoresist can remain on the copper surface.
Next, the circuit may be formed by different processes according to the inner and outer layer processes. In the inner layer process, a circuit may be formed on a substrate through an etching and stripping process, and in the outer layer process, after being subjected to a plating and masking (masking) process, etching and solder stripping may be performed to form a predetermined circuit.
For exposure, a known light source, more specifically, an ultra-high pressure mercury lamp or a laser direct exposure apparatus or the like may be used.
Advantageous effects
According to the present disclosure, it is possible to provide a photosensitive laminate capable of reducing defects at the time of fine wiring formation, improving reliability in a developing process, and capable of forming a high-density circuit, a method of manufacturing the photosensitive laminate, and a method of manufacturing a circuit board.
Drawings
FIG. 1 is a photograph for confirming the surface and cross section of the photosensitive resin layer of example 1 using a field emission scanning electron microscope (FE-SEM, 800 times);
FIG. 2 is a photograph for confirming the surface and cross section of the photosensitive resin layer of comparative example 1 using a field emission scanning electron microscope (FE-SEM, 800 times);
FIG. 3 is a photograph for confirming the surface and cross section of the photosensitive resin layer of comparative example 2 using a field emission scanning electron microscope (FE-SEM, 800 times);
fig. 4 is a photograph for confirming the surface and cross section of the photosensitive resin layer of comparative example 3 using a field emission scanning electron microscope (FE-SEM, 800 times).
Detailed Description
Hereinafter, the present disclosure will be described in more detail with reference to examples. However, the following examples are for illustrative purposes only, and the scope of the present invention is not intended to be limited thereto.
< preparation example >
Preparation example 1: preparation of alkali developable binder resins
A mechanical stirrer and reflux unit was mounted to a 4-neck round bottom flask and the flask interior was then purged with nitrogen. 170g of Methyl Ethyl Ketone (MEK) and 12.5g of methanol (MeOH) were added to a flask purged with nitrogen, followed by 2.25g of Azobisisobutyronitrile (AIBN) and completely dissolved. A monomer mixture of 60g of methacrylic acid (MAA), 100g of benzyl methacrylate (BzMA), 15g of Methyl Methacrylate (MMA) and 75g of Styrene (SM) was added thereto as monomers, heated to 80℃and then polymerized for 6 hours to prepare an alkali developable binder resin (weight average molecular weight: 40,000g/mol, glass transition temperature: 102 ℃, solid content: 50% by weight, acid value: 156 mgKOH/g).
The alkali developable binder resin prepared in preparation example 1 was dissolved in tetrahydrofuran to have a concentration of 1.0 (w/w)% (based on the solid content of about 0.5 (w/w)%) in THF, filtered using a syringe filter having a pore size of 0.45 μm, and then 20 μl was injected into GPC. The mobile phase of GPC was Tetrahydrofuran (THF), which was flowed in at a flow rate of 1.0mL/min, and analyzed at 40 ℃. The column connects one Agilent PLgel 5 μm Guard (7.5 mm. Times.50 mm) in series with two Agilent PLgel 5 μm Mixed D (7.5 mm. Times.300 mm). Measurements were made at 40 ℃ using the Agilent 1260Infinity II system, RI detector as detector.
Polystyrene standard samples (STD a, B, C, D) in which polystyrene having different molecular weights as shown below were dissolved in tetrahydrofuran at a concentration of 0.1 (w/w)%, were filtered through a syringe filter having a pore size of 0.45 μm, then injected into GPC, and the value of the weight average molecular weight (Mw) of the alkali-developable binder resin was determined using the calibration curve formed.
STD A(Mp)：791,000/27,810/945
STD B(Mp)：282,000/10,700/580
STD C(Mp)：126,000/4,430/370
STD D(Mp)：51,200/1,920/162
Preparation example 2: preparation of a composition for Forming a Barrier layer
A mechanical stirrer and reflux unit was mounted to a 4-neck round bottom flask and the flask interior was then purged with nitrogen. 200g of distilled water and 20g of Butyl Cellosolve (BC) were placed in a flask purged with nitrogen and completely dissolved. 20g of PVA-205 (KURARAY, polyvinyl alcohol, viscosity: 3.5cP, weight average molecular weight: 22,000 g/mol) and 1.5g of BYK-349 (BYK) were added thereto to prepare a composition for forming a barrier layer.
Preparation example 3: preparation of a composition for Forming a Barrier layer
A mechanical stirrer and reflux unit was mounted to a 4-neck round bottom flask and the flask interior was then purged with nitrogen. 200g of distilled water and 10g of Butyl Cellosolve (BC) were placed in a flask purged with nitrogen and completely dissolved. 20g of PVA-205 (KURARAY, polyvinyl alcohol, viscosity: 3.5cP, weight average molecular weight: 22,000 g/mol) and 1.5g of BYK-349 (BYK Chemie) were added thereto to prepare a composition for forming a barrier layer.
< examples and comparative examples: preparation of photosensitive resin composition and Dry film Photoresist >
Examples 1 to 3
The composition for forming a barrier layer obtained in preparation example 2 was coated onto a 25 μm PET film using a coating bar. The coated barrier layer was dried using a hot air oven, wherein the drying temperature was 80 ℃, the drying time was 10 minutes, the thickness of the barrier layer after drying was 2 to 3 μm, the haze value of the barrier layer was 1%, and the oxygen permeability was 3.5cc/m 2 Day.
Then, according to the composition shown in table 1 below, a photoinitiator was dissolved in an organic solvent, and then a photopolymerizable compound and an alkali developable binder resin were added, and mixed using a mechanical stirrer for about 1 hour to prepare a photosensitive resin composition.
The resulting photosensitive resin composition was coated on the barrier layer using a coating bar. The coated photosensitive resin composition layer was dried using a hot air oven. At this time, the drying temperature was 80 ℃, the drying time was 5 minutes, and the thickness of the photosensitive resin composition layer after drying was 25 μm.
A protective film (polyethylene) is laminated on the dried photosensitive resin composition layer to prepare a photosensitive laminate (dry film photoresist).
The HAZE of the barrier layer is a value obtained by peeling the PET film and measuring using a HAZE METER (model name: NDH7000, nippon Denshoku corp.) according to ASTM D1003 test method after peeling the PET film.
The barrier layer had an oxygen permeability of 3.5cc/m 2 Day and was measured according to ASTM F1927 test method using an OX-Tran (model 2/61, mocon Inc.) instrument.
Comparative example 1
According to the composition described in example 1 of table 1 below, a photoinitiator was dissolved in an organic solvent, and then a photopolymerizable compound and an alkali developable binder resin were added thereto, and mixed using a mechanical stirrer for about 1 hour to prepare a photosensitive resin composition.
The obtained photosensitive resin composition was coated on a 25 μm PET film using a coating bar. The coated photosensitive resin composition layer was dried using a hot air oven, wherein the drying temperature was 80 ℃, the drying time was 5 minutes, and the thickness of the dried photosensitive resin layer was 25 μm.
A protective film (polyethylene) is laminated on the dried photosensitive resin composition layer to prepare a photosensitive laminate (dry film photoresist).
Comparative example 2
A photosensitive laminate (dry film photoresist) was produced in the same manner as in example 1, except that the composition for forming a barrier layer obtained in preparation example 3 was used instead of the composition for forming a barrier layer obtained in preparation example 2.
The HAZE of the prepared barrier layer was 5%, which is a value obtained by peeling the PET film before applying the photosensitive resin composition and measuring using a HAZE METER (model name: NDH7000, nippon Denshoku corp.) according to ASTM D1003 test method. The oxygen permeability of the barrier layer produced was 4.0cc/m 2 Day and was measured according to ASTM F1927 test method using an OX-Tran (model 2/61, mocon Inc.) instrument.
Comparative example 3
A photosensitive laminate (dry film photoresist) was manufactured in the same manner as in the above examples, except that a photosensitive resin composition was prepared according to the composition shown in table 1 below.
TABLE 1
Comparative example 4
Except for the description of example 4 based on patent document 1, a photosensitive laminate (dry film photoresist) was produced in the same manner as the above-described example, with respect to 300 parts by weight of the "alkali developable binder resin" obtained in preparation example 1 of the present disclosure, the following components were mixed using a mechanical stirrer for about 1 hour to prepare a photosensitive resin composition.
< component of photosensitive resin composition >
(1) 100 parts by weight of 2, 2-bis (4- (methacryloxypentaethoxy) phenyl) propane
(2) 50 parts by weight of EO, PO modified polyurethane di (meth) acrylate
( 3) 50 parts by weight of polypropylene glycol diacrylate (number of propylene glycol chains: 7 )
(4) And (3) a photoinitiator: 25 parts by mass of benzophenone, 1.0 part by mass of 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer and 1.0 part by mass of diethylaminobenzophenone
(5) 5.0 parts by mass of a photochromic agent
(6) 0.15 part by mass of dye
(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 a low boiling point solvent having a boiling point of 100 ℃ or less to a high boiling point solvent having a boiling point of 115 ℃ or more ] =19:1 ]
< test example >
Physical properties of the dry film photoresists prepared in examples and comparative examples were measured by the following methods, and the results are shown in table 2 below.
1. Measuring exposure (unit: mJ/cm) 2 )
The dry film photoresists prepared in examples and comparative examples were laminated on a 1.6mm thick copper-clad laminate subjected to brush polishing treatmentAnd on the plate. At this time, the substrate preheating roll temperature at 120℃and the laminator roll temperature at 115℃were used, 4.0kgf/cm, using HAKUTO MACH 610i 2 Lamination was carried out at a roll speed of 2.0 min/m.
The PET film of the dry film photoresist laminated on the copper-clad laminate was removed, and ultraviolet rays having a wavelength of 405nm were irradiated with an exposure amount at which the number of steps of the remaining steps became 15 using a 41-step exposure table from Stouffer Graphic Arts Equipment using ORC FDi-3, and left for 15 minutes. Thereafter, under development conditions by spray jet method, 1.0 wt% Na was used 2 CO 3 The aqueous solution was developed. At this time, the energy at which the determined remaining number of stages becomes 15 stages is measured.
For comparative example 1, on a PET film of a dry film photoresist laminated on a copper clad laminate, ultraviolet rays having a wavelength of 405nm were irradiated with an exposure amount at which the number of steps of the remaining steps becomes 15 using ORC FDi-3 and a 41-step exposure table from Stouffer Graphic Arts Equipment, and left for 15 minutes. Thereafter, under development conditions by spray jet method, 1.0 wt% Na was used 2 CO 3 The aqueous solution was developed. At this time, the energy at which the determined remaining number of stages becomes 15 stages is measured.
2. Measurement 1:1 resolution (Unit: μm)
The dry film photoresists prepared in examples and comparative examples were laminated on a 1.6mm thick copper clad laminate subjected to brush polishing treatment. At this time, the substrate preheating roll temperature at 120℃and the laminator roll temperature at 115℃were used, 4.0kgf/cm, using HAKUTO MACH 610i 2 Lamination was carried out at a roll speed of 2.0 min/m.
After the PET film of the laminate was removed and developed on the barrier layer, the circuit line width and the space interval between the circuit lines were made 1 by using data formed at intervals of 0.5 μm from 4 μm to 20 μm: 1, using a 41-stage exposure meter of ORCFDi-3, stouffer Graphic Arts Equipment, ultraviolet rays having a wavelength of 405nm were irradiated with an exposure amount such that the number of steps of the remaining stages was 15, and left for 15 minutes. Thereafter, under development conditions by spray jet method, 1.0 wt% Na was used 2 CO 3 The aqueous solution was developed.
Resolution was then determined by using the ZEISS axioport microscope with a pitch of 1 between the circuit lines and the non-circuit lines: the value measured at 1 is determined.
For comparative example 1, on a PET film of a dry film photoresist laminated on a copper clad laminate, ultraviolet rays having a wavelength of 405nm were irradiated with an exposure amount at which the number of steps of the remaining steps becomes 15 using ORC FDi-3 and a 41-step exposure table from Stouffer Graphic Arts Equipment, and left for 15 minutes. Thereafter, under development conditions by spray jet method, 1.0 wt% Na was used 2 CO 3 The aqueous solution was developed. At this time, the energy at which the determined remaining number of stages becomes 15 stages is measured.
3. Confirm the bubble (unit: number/mm) 2 )
For the dry film photoresists prepared in examples and comparative examples, the PET film and the PE film were removed, and then the number (number/mm) of bubbles having a diameter of less than 1 μm present in the photosensitive resin layer (1 mm×1 mm) was confirmed using a polarizing microscope 2 )。
4. Confirmation of substrate defect after exposure/development (unit: number/mm 2 )
The dry film photoresists prepared in examples and comparative examples were laminated on a brush-polished copper clad laminate of 1.6mm thickness. At this time, the substrate preheating roll temperature at 120℃and the laminator roll temperature at 115℃were used, 4.0kgf/cm, using HAKUTO MACH 610i 2 Lamination was carried out at a roll speed of 2.0 min/m.
After removing the PET film of the laminate and developing on the barrier layer, ultraviolet rays having a wavelength of 405nm were irradiated with an exposure amount such that the number of steps of the remaining steps was 15 steps using a 41-step exposure table of ORC FDi-3, stouffer Graphic Arts Equipment, so that the circuit line width and the space interval between circuit lines could be 14 μm:14 μm and left for 15 minutes. Thereafter, under development conditions by spray jet method, 1.0 wt% Na was used 2 CO 3 The aqueous solution was developed.
For each dry film light prepared in examples and comparative examples The photoresist was observed in a unit area (1 mm. Times.1 mm) using an electron microscope, and the number of defects present (number/mm) of 0.5 μm or more and 3 μm or less was confirmed 2 ). The surfaces and cross sections of the photosensitive resin layers obtained in the respective examples and comparative examples were observed using a field emission scanning electron microscope (FE-SEM, hitachi, magnification 3000 times).
For comparative example 1, on a PET film of a dry film photoresist laminated on a copper clad laminate, ultraviolet rays having a wavelength of 405nm were irradiated with an exposure amount at which the number of steps of the remaining steps becomes 15 using ORC FDi-3 and a 41-step exposure table from Stouffer Graphic Arts Equipment, and left for 15 minutes. Thereafter, under development conditions by spray jet method, 1.0 wt% Na was used 2 CO 3 The aqueous solution was developed. At this time, the energy at which the determined remaining number of stages becomes 15 stages is measured.
TABLE 2
As confirmed in Table 2 and FIG. 1, it was confirmed that bubbles having a diameter of less than 1 μm were present at 1 bubble/mm 2 The following exists in the photosensitive resin layer of the photosensitive laminate of the example. Further, it was confirmed that defects having a diameter of 0.5 μm or more and 3 μm or less were not substantially generated in the photosensitive resin layer of the example even after exposure to ultraviolet rays and development with an alkaline solution.
That is, since there are trace amounts of bubbles having a diameter of less than 1 μm in the photosensitive resin layer of the embodiment and a blocking layer having a haze of 2% or less is contained, it is also observed that when a circuit board is produced by using the photosensitive laminate, high density and sensitivity can be achieved while ensuring high reliability, and finer wirings can be formed.
On the other hand, it was confirmed that, in the photosensitive resin laminate of the comparative example, even when the same level of energy as in the example was used, it was difficult to achieve not only the resolution at the example level but also a diameter of less than 1 μmThe bubbles were 10 bubbles/mm 2 The above exists in the photosensitive resin layer.
Further, as shown in fig. 2 to 5, it was confirmed that a large number of defects having a diameter of 0.5 μm or more and 3 μm or less occurred after the photosensitive resin layer obtained in the comparative example was exposed to an alkaline solution and developed.

Claims (17)

1. A photosensitive laminate comprising:
a barrier layer having a haze of 2% or less; and
a photosensitive resin layer including a photopolymerizable compound containing an ester monomer or oligomer, and a binder resin,
wherein the bubbles with a diameter smaller than 1 μm are 5 bubbles/mm 2 The following exists in the photosensitive resin layer.
2. The photosensitive laminate according to claim 1, wherein,
the barrier layer has a volume of 10cc/m 2 Oxygen permeability per day or less.
3. The photosensitive laminate according to claim 1, wherein,
the barrier layer includes a polyvinyl alcohol resin having a weight average molecular weight of 5,000g/mol to 1,000,000 g/mol.
4. The photosensitive laminate according to claim 3, wherein,
the polyvinyl alcohol resin has a viscosity of 1.0cP to 10.0 cP.
5. The photosensitive laminate according to claim 1, wherein,
the barrier layer has a thickness of 0.1 μm to 10 μm,
the photosensitive resin layer has a thickness of 1 μm to 100 μm.
6. The photosensitive laminate according to claim 1,
it further includes a support substrate formed on the barrier layer and having a thickness of 1 μm to 100 μm.
7. The photosensitive laminate according to claim 1,
it further includes a peeling layer formed on the photosensitive resin layer and having a thickness of 0.01 μm to 1 m.
8. The photosensitive laminate according to claim 1, wherein,
starting from the opposite surface of the interface between the barrier layer and the photosensitive resin layer, bubbles having a diameter of less than 1 μm are present at 3 bubbles/mm within 50% of the total thickness of the photosensitive resin layer 2 The following exists.
9. The photosensitive laminate according to claim 1, wherein,
the photosensitive resin layer does not contain bubbles having a diameter of 1 μm to 5 μm.
10. The photosensitive laminate according to claim 1, wherein,
after UV exposure and alkaline development, defects with a cross-sectional diameter of 0.3 μm to 4 μm were detected as 3 defects/mm 2 The following exists in the photosensitive resin layer.
11. The photosensitive laminate according to claim 1, wherein,
the ester monomers or oligomers include (meth) acrylates having one or more hydroxyl, epoxy or amino groups bonded thereto.
12. The photosensitive laminate according to claim 1, wherein,
the ester monomer or oligomer includes a compound of the following chemical formula 1:
[ chemical formula 1]
CH 2 ＝CR 1 -COO-R 2 -OH
Wherein, in the chemical formula 1,
R 1 is hydrogen or an alkyl group having 1 to 10 carbon atoms,
R 2 is a divalent saturated aliphatic hydrocarbon group having 1 to 100 carbon atoms,
wherein the saturated aliphatic hydrocarbon group may optionally include a halogen atom, an ether bond (-O-); ester linkages (-COO-or O-CO-), amide linkages (-NHCO-or CONH-) or aryl groups.
13. The photosensitive laminate according to claim 1, wherein,
the ester monomers or oligomers include glycerol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol monoacrylate, hydroxypropyl (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol monoacrylate, poly (ethylene glycol propylene glycol) -mono (meth) acrylate, polyethylene glycol polypropylene glycol-mono (meth) acrylate, poly (ethylene glycol butylene glycol) -mono (meth) acrylate, poly (propylene glycol butylene glycol) -mono (meth) acrylate, propylene glycol polytetramethylene glycol-mono (meth) acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 1, 4-cyclohexanedimethanol monoacrylate, or a mixture of two or more thereof.
14. The photosensitive laminate according to claim 1, wherein,
the photopolymerizable compound further comprises a monofunctional (meth) acrylate compound or a multifunctional (meth) acrylate compound.
15. The photosensitive laminate according to claim 14, wherein,
the photopolymerizable compound includes 50 to 500 parts by weight of the monofunctional (meth) acrylate compound or the multifunctional (meth) acrylate compound based on 100 parts by weight of the ester monomer or oligomer.
16. The photosensitive laminate according to claim 1, wherein,
the binder resin has a weight average molecular weight of 20,000g/mol to 300,000g/mol and a glass transition temperature of 20 ℃ or more and 150 ℃ or less.
17. A method of manufacturing a circuit board using the photosensitive laminate according to claim 1.
CN202280024373.5A 2021-03-31 2022-03-29 Photosensitive laminate and method for manufacturing circuit board using the same Pending CN117120925A (en)

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JP2006106287A (en) 2004-10-04 2006-04-20 Hitachi Chem Co Ltd Photosensitive resin composition, photosensitive element and method for manufacturing photosensitive element
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