TW201823304A - Method for manufacturing insulating layer and multilayered printed circuit board - Google Patents

Abstract

The present invention relates to a method for manufacturing an insulating layer which can realize a uniform and fine pattern while improving efficiency in terms of cost and productivity, and also secure excellent mechanical properties, and a method for manufacturing a multilayered printed circuit board using an insulating layer obtained from the method of manufacturing an insulating layer.

Description

   Insulating layer and manufacturing method of multilayer printed circuit board        Cross references in related applications    

This application is based on Korean Patent Application No. 10-2016-0101419 filed with the Korean Intellectual Property Office on August 9, 2016 and Korean Patent Application filed on July 28, 2017 Case No. 10-2017-0096355, the disclosure of these applications is incorporated herein by reference in its entirety.

The present invention relates to a method for manufacturing an insulating layer and a method for manufacturing a multilayer printed circuit board. More specifically, the present invention relates to a method of manufacturing an insulating layer, which can achieve a uniform and fine pattern, while improving efficiency in terms of cost and productivity, and ensuring excellent mechanical properties; and using the insulation obtained from the method of manufacturing the insulating layer Manufacturing method of multilayer printed circuit board.

Recently, electronic devices have been increasingly miniaturized, lightened, and highly functional. For this reason, as the application field of build-up PCB (build-up printed circuit board) is mainly expanded in small devices, the use of multilayer printed circuit boards is rapidly increasing.

The multilayer printed circuit board can be three-dimensionally wired from a planar wiring. Especially in the field of industrial electronic devices, multilayer printed circuit boards improve the integration of functional components such as integrated circuits (ICs) and large integrated circuits (LSIs), and are also used for miniaturization and weight reduction of electronic devices. , High functionality, integration of structural electrical function (integration of structural electrical function), shorten the assembly time and reduce the cost of favorable products.

The build-up PCBs used in these applications must form vias for connections between individual layers. The via hole corresponds to an inter-layer electrical connection path of the multilayer printed circuit board. In the past, it was machined with a mechanical drill. However, as the hole diameter became smaller due to the micromachining of the circuit, the processing cost caused by the limitations of mechanical drilling and fine hole machining increased, so the laser machining method appeared as an alternative. .

In the case of laser processing, a CO ₂ or YAG laser drill is used. However, since the size of the via hole is determined by a laser drill, for example, in the case of a CO ₂ laser drill, there is a limitation that it is difficult to manufacture a via hole having a diameter of 40 μm or less. In addition, there is a limitation that the cost burden is heavy when a large number of via holes must be formed.

Therefore, a method of forming a low-cost via hole having a fine diameter using a photosensitive insulating material has been proposed instead of the above-mentioned laser processing technology. In particular, as the photosensitive insulating material, a photosensitive insulating film called "solder resist" can be mentioned, and the photosensitive insulating film can form a fine opening pattern by utilizing the photosensitivity.

Such a photosensitive insulating material or solder resist can be divided into a case where a sodium carbonate developer is used and a case where another development is used to form a pattern. In the case of using another developer, the photosensitive insulating material or the solder resist has a limitation that it is difficult to apply to the actual process due to environmental and cost factors.

On the other hand, when a sodium carbonate developer is used, it has the advantage of environmental protection. In some cases, in order to impart photosensitivity, acid-modified acrylate resins containing a large amount of carboxylic acid and acrylic groups are used. However, since most acrylate groups and carboxyl groups are linked by ester bonds, polymerization inhibitors and the like are used for polymerization. Into advantageous forms, and additionally include photoinitiators and the like to cause free radical reactions by ultraviolet radiation.

However, polymerization inhibitors, photoinitiators, etc. diffuse outside the resin under high temperature conditions, which may cause interface separation between the insulating layer and the conductive layer during and after the semiconductor packaging process. In addition, the ester bonds in the resin cause a hydrolysis reaction under high humidity and reduce the crosslinking density of the resin, which results in an increase in the moisture absorption rate of the resin. When the moisture absorption rate is high as described above, polymerization inhibitors, photoinitiators, etc., are converted outside the resin under high temperature conditions and cause interface separation between the insulating layer and the conductive layer during and after the semiconductor packaging process, and HAST is present. Restrictions on deterioration of nature.

Therefore, there is a need to develop a manufacturing method of an insulating layer capable of obtaining a uniform and fine pattern at a low cost while preventing the interface between the insulating layer and the conductive layer from being separated.

1‧‧‧ polymer resin layer

2‧‧‧ copper wire

3‧‧‧ copper foil laminate

4‧‧‧ ultra-thin copper foil

5‧‧‧ carrier copper foil

6‧‧‧Photosensitive Dry Film Resistant (DFR)

7‧‧‧via hole

8‧‧‧ seed layer

9‧‧‧ photosensitive resin pattern

10‧‧‧ metal substrate

<1> to <8> ‧‧‧ Process sequence

FIG. 1 is a schematic view showing a method for manufacturing an insulating layer of Example 1. FIG.

FIG. 2 schematically illustrates a method for manufacturing a multilayer printed circuit board according to the second embodiment.

    [Summary of the Invention] and [Embodiment]    

An object of the present invention is to provide a manufacturing method of an insulating layer capable of achieving uniform and fine patterns while improving efficiency in terms of cost and productivity, and ensuring excellent mechanical properties.

Another object of the present invention is to provide a method for manufacturing a multilayer printed circuit board using an insulating layer obtained from the method for manufacturing the insulating layer.

An embodiment of the present invention provides a method for manufacturing an insulating layer, the method including the following steps: adhering an opposite surface of a metal layer to a surface of a carrier film adhered to a polymer resin layer containing an alkali-soluble resin and a heat-curable adhesive Forming a patterned photosensitive resin layer on the carrier film; removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer; from the patterned The metalized layer separates and removes the carrier film; performs alkaline development on the polymer resin layer exposed by the patterned metal layer; and thermally cures the polymer resin layer after the alkaline development.

Another aspect of the present invention provides a method for manufacturing a multilayer printed circuit board, the method including the step of forming a patterned metal substrate on an insulating layer obtained from the method for manufacturing the insulating layer.

A method for manufacturing an insulating layer and a method for manufacturing a multilayer printed circuit board according to specific embodiments of the present invention will be described in more detail below.

In the present specification, the halogen group includes fluorine, chlorine, bromine, and iodine.

In the present specification, the alkyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tertiary butyl, secondary butyl, 1-methyl-butyl Base, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4 -Methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, Octyl, n-octyl, tertiary octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl -Propyl, 1,1-dimethylpropyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In this specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to another embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be phenyl, biphenyl, bitriphenyl, or the like as the monocyclic aryl group, but is not limited thereto. Specific examples of the polycyclic aryl group include, but are not limited to, naphthyl, anthracenyl, phenanthryl, fluorenyl, fluorenyl, crycenyl, fluorenyl, and the like.

According to an embodiment of the present invention, a method for manufacturing an insulating layer is provided. The method includes the following steps: adhering the opposite surface of a metal layer to a surface of a carrier film adhered to a polymer containing an alkali-soluble resin and a thermosetting adhesive A resin layer; forming a patterned photosensitive resin layer on the carrier film; removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer; from the The patterned metal layer separates and removes the carrier film; performs alkaline development on the polymer resin layer exposed by the patterned metal layer; and thermally cures the polymer resin layer after the alkaline development.

According to a method for manufacturing an insulating layer according to an embodiment, the inventors have found that when a patterned metal layer introduced onto an alkali-soluble polymer resin layer is used as a mask for alkaline development of the polymer resin layer, the The polymer resin layer is removed by alkaline development after the metal layer pattern is exposed, and the portion of the polymer resin layer that is not exposed by the metal layer pattern is protected from the influence of the alkaline developer, so that the polymer can be polymerized through the chemical method. A fine pattern is formed in the resin layer.

It has also been found through experiments that, compared to using an insulating layer manufactured by laser processing, an insulating layer on which a fine pattern is formed by the above method can be quickly formed at low cost, and the final insulating layer manufactured can achieve excellent physical properties. . The present invention has been developed based on this finding.

In addition, since the final insulation layer contains a cured product of a heat-curable resin that is a non-photosensitive insulation material, the content of the photoinitiator or polymerization inhibitor is greatly reduced compared to the case where the insulation layer is manufactured using a conventional photosensitive insulation material. This makes it possible to manufacture an insulating layer having excellent mechanical properties, such as a property of reducing an interface separation between the insulating layer and the conductive layer which may be caused by a photoinitiator or a polymerization inhibitor.

In particular, in the manufacturing method of the insulating layer of the embodiment, when the metal layer is introduced as a mask on the polymer resin layer, the process is performed while the carrier film is adhered to the metal layer, not only the metal The layer can be easily laminated by the carrier film, and the carrier film can be simultaneously removed as the metal layer is removed by the same etchant. Therefore, the metal layer can be easily etched even in a state where the carrier film is adhered.

In addition, in order to form a pattern on the carrier film and the metal layer, the photosensitive resin layer introduced onto the carrier film can be easily removed through physical peeling between the carrier film and the metal layer. As such, it is advantageous in terms of process efficiency even if the photosensitive resin layer is removed without using a separate peeling liquid treatment.

In addition, since the alkali-soluble resin used in the manufacturing method of the insulating layer according to one embodiment contains a characteristic cyclic fluorene imine functional group together with an acid functional group in the molecular structure, the alkali solubility can be achieved by the acid functional group. And, when reacting with a heat-curable adhesive, the curing density can be increased by the cyclic fluorene imide group substituted with an amine group, thereby improving the reliability of heat resistance and mechanical properties, and improving the adhesion at another interface.

Therefore, the polymer resin layer containing the alkali-soluble resin may have improved interface adhesion with the metal layer on the upper side of the laminate, and in particular, may have an interface between the metal layer and the carrier film laminated on the upper portion of the metal layer. Higher adhesion. Therefore, as described below, physical separation may occur between the carrier film and the metal layer.

Specifically, the method for manufacturing the insulating layer may include the following steps: adhering the opposite surface of the metal layer to which one surface of the carrier film is adhered to a polymer resin layer containing an alkali-soluble resin and a heat-curable adhesive; on the carrier; Forming a patterned photosensitive resin layer on the film; removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer; and from the patterned metal layer Separating and removing the carrier film; subjecting the polymer resin layer exposed by the patterned metal layer to alkaline development; and thermally curing the polymer resin layer after the alkaline development.

The details of each step will be explained below.

Step of adhering the opposite surface of the metal layer to which one surface of the carrier film is adhered to a polymer resin layer containing an alkali-soluble resin and a heat-curable adhesive

In the step of adhering the opposite surface of the metal layer to which one surface of the carrier film is adhered to a polymer resin layer containing an alkali-soluble resin and a heat-curable adhesive, the polymer resin layer means that the alkali-soluble resin and A film formed by drying a polymer resin composition of a heat-curable adhesive.

The polymer resin layer may exist alone or in a state formed on a substrate (such as a circuit board, a sheet, a multilayer printed circuit board, and the like) containing a semiconductor material. Examples of the method of forming a polymer resin layer on a substrate are not particularly limited, but, for example, a method of directly coating a polymer resin composition on the substrate, or coating the polymer resin composition on a carrier film or adhering A method of laminating a carrier film on a metal layer and then laminating the substrate.

In addition, an example of a method of adhering the opposite surface of the metal layer to which one surface of the carrier film is adhered to the polymer resin layer containing an alkali-soluble resin and a heat-curable adhesive may include an alkali-soluble resin and a heat-curable adhesive The polymer resin composition is applied to the opposite surface of the metal layer to which one surface of the carrier film is adhered and the coating is dried.

The polymer resin layer may include an alkali-soluble resin and a heat-curable adhesive.

The polymer resin layer may include a heat-curable adhesive in an amount of 1 to 150 parts by weight, 10 to 100 parts by weight, or 20 to 50 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the content of the heat-curable adhesive is too high, the developability of the polymer resin layer is deteriorated and the strength is reduced. Conversely, when the content of the heat-curable adhesive is too low, not only the polymer resin layer is excessively developed, but also the uniformity of the coating layer may be reduced.

The heat-curable adhesive may include at least one functional group selected from the group consisting of: a heat-curable functional group, an oxycyclobutane group, a cyclic ether group, a cyclic thioether group, a cyano group, and cis-butyl Arylene diimide, and benzo And epoxy. That is, the heat-curable adhesive must include an epoxy group, and in addition to the epoxy group, it may also contain an oxycyclobutane group, a cyclic ether group, a cyclic thioether group, a cyano group, and maleic acid. Amine, benzo Base, or a mixture of two or more thereof. These heat-curable adhesives can form a cross-linking bond with an alkali-soluble resin or the like by heat curing, thereby ensuring heat resistance or mechanical properties of the insulating layer.

More specifically, a polyfunctional resin compound containing two or more of the above-mentioned functional groups in a molecule may be used as the heat-curable adhesive.

The polyfunctional resin compound may include a resin containing two or more cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in the molecule.

The thermosetting adhesive containing two or more cyclic (thio) ether groups in the molecule may be any one having 3, 4, or 5 member cyclic ether groups or cyclic thioether groups in the molecule or A compound of two or more of the two.

Examples of the compound having two or more cyclic sulfide groups in the molecule include bisphenol A-type episulfide resin YL 7000 (manufactured by Japan Epoxy Resins Co., Ltd.) and the like.

In addition, the polyfunctional resin compound may include a polyfunctional epoxy compound containing at least two or more epoxy groups in a molecule, and a polyfunctional epoxy compound containing at least two or more oxycyclobutane groups in a molecule. Functional oxycyclobutane compounds, or episulfide resins containing at least two thioether groups, polyfunctional cyanate compounds containing at least two or more cyano groups in the molecule, or at least two or more in the molecule Multiple benzo Polyfunctional benzo Compounds etc.

Specific examples of the polyfunctional epoxy compound may include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol F epoxy resin, and bisphenol S Type epoxy resin, novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, N-epoxypropyl epoxy resin, bisphenol A novolac Epoxy resin, biphenol epoxy resin, biphenol epoxy resin, chelate epoxy resin, glyoxal epoxy resin, amine-containing epoxy resin, rubber modified epoxy resin, bicyclic Pentadiene phenolic epoxy resin, phthalic acid diglycidyl resin, heterocyclic epoxy resin, tetraglycidyl xylenoyl ethane resin, polysiloxane modified ring Epoxy resin, epoxy resin modified by ε-caprolactone, etc. Further, in order to impart flame retardancy, a compound having a structure in which an atom such as phosphorus is introduced may be used. These epoxy resins can be improved by heat curing such as adhesion of cured coating film, soldering heat resistance, electroless plating resistance, and the like.

Examples of the polyfunctional oxycyclobutane compound may include polyfunctional oxycyclobutane, such as bis [(3-methyl-3-oxocyclobutylmethoxy) methyl] ether, bis [(3 -Ethyl-3-oxocyclobutylmethoxy) methyl] ether, 1,4-bis [(3-methyl-3-oxocyclobutylmethoxy) methyl] benzene, 1, 4-bis [(3-ethyl-3-oxocyclobutylmethoxy) methyl] benzene, (3-methyl-3-oxocyclobutyl) methyl acrylate, (3-ethyl- (3-Oxycyclobutane) methyl acrylate, (3-methyl-3-oxocyclobutyl) methyl methacrylate, (3-ethyl-3-oxocyclobutyl) methacrylate Esters, and their oligomers or copolymers, and in addition, may include etherified products of oxycyclobutanol and hydroxyl-containing resins such as novolac resins, poly (p-hydroxystyrene), Cardo type Cardo-type bisphenol, calixarene, calixresorcinarene, silsesquioxane, etc. Further, a copolymer of an unsaturated monomer having an oxocyclobutane ring and an alkyl (meth) acrylate may be included.

Examples of the polyfunctional cyanate compound may include bisphenol A type cyanate resin, bisphenol E type cyanate resin, bisphenol F type cyanate resin, bisphenol S type cyanate resin, bisphenol M type cyanate resin, novolac type cyanate resin, phenol novolac type cyanate resin, cresol novolac type cyanate resin, bisphenol A novolac type cyanate resin, biphenol type Cyanate resin, its oligomer or copolymer, and the like.

Examples of the polyfunctional cis-butene difluorene imine compound may include 4,4'-diphenylmethane bis-cis-butene difluorene imine, toluene bis-cis-butene difluorene imine, m-toluene bis-cis butylene difluorene Imine, bisphenol A diphenyl ether biscis-butene diimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane biscis-butene di Fluorenimine, 4-methyl-1,3-phenylenebiscis-butenedifluoreneimine, 1,6'-biscisbutenedifluorenimine- (2,2,4-trimethyl) Hexane) and the like.

The multifunctional benzo Examples of the compound may include bisphenol A type benzo Resin, bisphenol F type benzo Resin, phenolphthalein type benzo Resin, thiodiol type benzo Resin, dicyclopentadiene type benzo Resin, 3,3- (methylene-1,4-biphenylene) bis (3,4-dihydro-2H-1,3-benzo ) Resin and so on.

More specific examples of the multifunctional resin compound may include YDCN-500-80P (Kukdo Chemical Co. Ltd.), a phenol-based novolac cyanide ester resin PT-30S (Lonza Ltd.), and toluene-type maleic acid Perylene imine resin BMI-2300 (Daiwa Kasei Co., Ltd.), Pd type benzo Resin (Shikoku Chemicals) and the like.

Meanwhile, the alkali-soluble resin may include at least one or more, or two or more selected from acid functional groups and cyclic amidine imine functional groups substituted with amine groups. Examples of the acid functional group may include, but are not limited to, a carboxyl group or a phenol group. The alkali-soluble resin includes at least one or more, or two or more acid-functional groups, so the polymer resin layer exhibits higher alkaline developing properties and the development rate of the polymer resin layer can be controlled.

The amine-substituted cyclic amidine imide functional group includes an amine group and a cyclic amidine imine group in the functional group structure, and may include at least one or more, or two or more thereof. Since the alkali-soluble resin contains at least one or more, or two or more cyclic fluorene imine functional groups substituted with an amine group, the alkali-soluble resin has a structure in which a large amount of active hydrogen contained in the amine group is present. Therefore, when the reactivity with the heat-curable adhesive is improved during heat curing, the curing density can be increased, thereby improving the reliability of heat resistance and mechanical properties.

In addition, since a large number of cyclic fluorene imine functional groups are present in the alkali-soluble resin, the polarity is increased by the carbonyl group and tertiary amine group contained in the cyclic fluorene imine functional group, so the interface adhesion of the alkali-soluble resin Can be improved. The polymer resin layer containing an alkali-soluble resin may therefore have improved interface adhesion with the metal layer on the upper side of the laminate, and in particular, may have a ratio between the metal layer and the carrier film of the laminate above the metal layer. Interface adhesion is higher. Therefore, as described below, physical separation may occur between the carrier film and the metal layer.

More specifically, the cyclic amidine imide functional group substituted with an amine group may include a functional group represented by Chemical Formula 1 shown below.

In Chemical Formula 1, R ₁ is an alkylene or alkenyl group having 1 to 10 carbon atoms, 1 to 5 carbon atoms, or 1 to 3 carbon atoms, and "*" means a bonding point. Dialkylene is a divalent functional group derived from an alkane, such as a linear, branched, or cyclic group, and includes methylene, ethylidene, propylidene, isobutylene, dibutylene, Tertiary butyl, pentyl, and hexyl. One or more hydrogen atoms contained in the alkylene group may be substituted with another substituent. Examples of the other substituent include an alkyl group having 1 to 10 carbon atoms, and an olefin having 2 to 10 carbon atoms. Radical, alkynyl radical having 2 to 10 carbon atoms, aryl radical having 2 to 12 carbon atoms, heteroaryl radical having 2 to 12 carbon atoms, arylalkyl radical having 6 to 12 carbon atoms, halogen Atoms, cyano, amine, formamyl, nitro, sulfonylamino, carbonyl, hydroxyl, sulfonyl, carbamate, alkoxy groups having 1 to 10 carbon atoms, and the like.

The term "substituted" as used herein means that another functional group is bonded to replace a hydrogen atom in a compound, and the position to be substituted is not limited as long as it is a position where a hydrogen atom is substituted (i.e., a position where a substituent can be substituted ). When two or more substituents are substituted, the two or more substituents may be the same as or different from each other.

Alkenyl means the aforementioned alkylene group containing at least one carbon-carbon double bond at its middle or terminal, and examples thereof include ethylene, propylene, butene, hexene, acetylene, and the like. One or more hydrogen atoms in the alkenyl group may be substituted with a substituent in the same manner as in the alkylene group.

Preferably, the cyclic amidine imide functional group substituted with an amine group may be a functional group represented by Chemical Formula 2 shown below.

In Chemical Formula 2, "*" means a bonding site.

As described above, the alkali-soluble resin includes an amine-substituted cyclic amidine imine functional group together with an acid functional group. Specifically, an acid functional group may be bonded to at least one terminal of the amine substituted cyclic amidine imine functional group. At this time, the cyclic fluoreneimine functional group substituted with the amine group and the acid functional group may be bonded through a substituted or unsubstituted alkylene group or a substituted or unsubstituted aryl group. For example, an acid functional group may be bonded to an amino group contained in the amine-substituted amidine functional group via a substituted or unsubstituted alkylene group or a substituted or unsubstituted alkylene group. End. The acid functional group may be bonded to the cyclic amidine imide contained in the amido-substituted amidine functional group via a substituted or unsubstituted alkylene group or a substituted or unsubstituted alkylene group. The end of the functional group.

More specifically, the terminal of the amine group contained in the amine-substituted cyclic amidine imide functional group means a nitrogen atom contained in the amine group in Chemical Formula 1, and the amine-substituted cyclic group The terminal of the fluorene imine functional group contained in the fluorene imine functional group means a nitrogen atom contained in the cyclic fluorene imine functional group in Chemical Formula 1.

Dialkylene is a divalent functional group derived from an alkane, such as a linear, branched, or cyclic group, and includes methylene, ethylidene, propylidene, isobutylene, dibutylene, Tertiary butyl, pentyl, and hexyl. One or more hydrogen atoms contained in the alkylene group may be substituted with another substituent. Examples of the other substituent include an alkyl group having 1 to 10 carbon atoms, and an olefin having 2 to 10 carbon atoms. Radical, alkynyl radical having 2 to 10 carbon atoms, aryl radical having 2 to 12 carbon atoms, heteroaryl radical having 2 to 12 carbon atoms, arylalkyl radical having 6 to 12 carbon atoms, halogen Atoms, cyano, amine, formamyl, nitro, sulfonylamino, carbonyl, hydroxyl, sulfonyl, carbamate, alkoxy groups having 1 to 10 carbon atoms, and the like.

The aryl group means a divalent functional group derived from an aromatic hydrocarbon, such as a cyclic group, and may include a phenyl group, a naphthyl group, and the like. One or more hydrogen atoms contained in the arylene group may be substituted with another substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 2 to 12 carbon atoms, Heteroaryl groups with 2 to 12 carbon atoms, arylalkyl groups with 6 to 12 carbon atoms, halogen atoms, cyano, amine, formamidine, nitro, amido, carbonyl, hydroxyl, sulfo A fluorenyl group, a urethane group, an alkoxy group having 1 to 10 carbon atoms, and the like.

Examples of the method for producing the alkali-soluble resin are not particularly limited, but, for example, the alkali-soluble resin can be produced through a reaction between a cyclic unsaturated fluorene imine compound and an amine compound. In this case, at least one of the cyclic unsaturated fluorene imine compound and the amine compound may contain an acid functional group substituted at its terminal. That is, the acid functional group may be substituted at the terminal of the cyclic unsaturated fluorene imine compound, the amine compound, or both of these compounds. The details of the acid functional group are as described above.

A cyclic fluorene imine compound is a compound containing the above cyclic fluorene imine functional group, and a cyclic unsaturated fluorene imine compound means that the cyclic fluorene imine compound contains at least one unsaturated bond (i.e., a double bond or Triple bond).

The alkali-soluble resin can be produced through a reaction between an amine group contained in the amine compound and a double or triple bond contained in the cyclic unsaturated fluorene imine compound.

The weight ratio of the cyclic unsaturated fluorene imine compound to the amine compound is not particularly limited, but for example, the amine compound may be 10 by mixing 100 parts by weight of the cyclic unsaturated fluorene imine compound. To 80 parts by weight, or 30 to 60 parts by weight.

Examples of the cyclic unsaturated fluorene imine compound include an N-substituted cis-butene difluorene imine compound. The term "N substituted" as used herein means that a functional group is bonded to a nitrogen atom contained in a maleimide compound instead of a hydrogen atom, and is regarded as an N substituted maleimide compound Depending on the number, N-substituted maleimide compounds can be classified into monofunctional N-substituted maleimide compounds and polyfunctional N-substituted maleimide compounds Compound.

A monofunctional N-substituted maleimide compound is a compound in which a nitrogen atom contained in a maleimide compound is a functional group substituted, and a polyfunctional N-substituted maleimide The difluorene imine compound is a compound in which a nitrogen atom contained in each of two or more maleimide diimine compounds is bonded via a functional group.

In the monofunctional N-substituted maleimide compound, the functional group substituted on the nitrogen atom contained in the maleimide compound may include, but is not limited to, various known aliphatic compounds. , Alicyclic, or aromatic functional group, and the functional group substituted on the nitrogen atom may include a functional group in which an aliphatic, alicyclic, or aromatic functional group is substituted with an acid functional group. The details of the acid functional group are as described above.

Specific examples of the monofunctional N-substituted maleimide compound include o-tolyl maleimide diimide, p-hydroxyphenyl maleimide diimide, p-carboxyphenyl maleimide Fluorene imine, dodecyl cis butene difluorene imine and the like.

In the polyfunctional N-substituted maleimide compound, the functional group that mediates the nitrogen-nitrogen bond contained in each of the two or more maleimide compounds may include, but not It is limited to a variety of known aliphatic, alicyclic, or aromatic functional groups. In a specific example, a 4,4'-diphenylmethane functional group and the like can be used. The functional group substituted on the nitrogen atom may include a functional group in which an aliphatic, alicyclic, or aromatic functional group is substituted with an acid functional group. The details of the acid functional group are as described above.

Specific examples of the polyfunctional N-substituted maleimide compound include 4,4'-diphenylmethanebismaleimide diimide (BMI-1000, BMI-1100, etc., available from Daiwakasei Industry Co. ., Ltd.), Toluene bis-butene difluorene imine, m-phenylene methane bis-butene difluorene imine, bisphenol A diphenyl ether biscis-butene difluorene imine, 3,3 ' -Dimethyl-5,5'-diethyl-4,4'-diphenylmethane biscis butylene diimide, 4-methyl-1,3-phenylene biscis butylene diimide Amines, 1,6'-biscisbutene diamidine- (2,2,4-trimethyl) hexane and the like.

The amine compound may be a primary amine compound containing at least one amine group (—NH ₂ ) in the molecular structure. More preferably, an amine-substituted carboxylic acid compound, a polyfunctional amine compound containing at least two amine groups, or a mixture thereof can be used.

Among the carboxylic acid compounds substituted with an amine group, the carboxylic acid compound is a compound containing a carboxylic acid (-COOH) functional group in the molecule, and it depends on the kind of the hydrocarbon bonded to the carboxylic acid functional group, which may be Includes all aliphatic, alicyclic, and aromatic carboxylic acids. Since a large number of carboxylic acid functional groups, which are acid functional groups contained in an alkali-soluble resin via a carboxylic acid compound substituted with an amine group, the developability of the alkali-soluble resin can be improved.

The term "substituted" as used herein means that another functional group is bonded to replace a hydrogen atom in a compound, and the substitution position of the amine group in the carboxylic acid is not limited as long as it is a position where the hydrogen atom is substituted . The number of amine groups to be substituted may be 1 or more.

Specific examples of amine-substituted carboxylic acids include 20 of the following: α-amino acid, 4-aminobutyric acid, 5-aminovaleric acid, 6-aminohexanoic acid, 7-aminoheptanoic acid , 8-aminooctanoic acid, 4-aminobenzoic acid, 4-aminophenylacetic acid, 4-aminocyclohexanecarboxylic acid, etc., which are known as raw materials for proteins.

In addition, the polyfunctional amine compound containing two or more amine groups may be a compound containing at least two amine groups (-NH ₂ ) in the molecule, and it depends on the type of the hydrocarbon bonded to the amine group, which All aliphatic, alicyclic, and aromatic polyfunctional amines can be included. The flexibility, toughness, and adhesion of the copper foil of the alkali-soluble resin can be improved by the polyfunctional amine compound containing at least two amine groups.

Specific examples of the polyfunctional amine compound containing two or more amine groups include 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis (aminomethyl) -cyclohexane Alkane, 1,4-bis (aminomethyl) -cyclohexane, bis (aminomethyl) -norbornene, octahydro-4,7-methyleneindene-1 (2) (octahydro-4 , 7-methanoindene-1 (2)), 5 (6) -dimethanamine, 4,4'-methylenebis (cyclohexylamine), 4,4'-methylene Bis (2-methylcyclohexylamine), isophoronediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,3,5,6-methyl-1,4-phenylenediamine, 2,4,5,6-tetrafluoro-1,3-phenylenediamine, 2,3,5,6-tetrafluoro-1 4,4-phenylenediamine, 4,6-diaminoresorcinol, 2,5-diamino-1,4-benzenedithiol, 3-aminobenzylamine, 4-aminobenzyl Amine, diamine, p-diamine, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 2,6-diaminoanthraquinone, m-toluidine, o-toluidine, 3,3 ', 5,5'-tetramethylbenzidine (TMB), o-dimethoxyaniline, 4,4'-methylenebis (2-chloroaniline), 3,3'-diamine group Aniline, 2,2'-bis (trifluoromethyl) -benzidine, 4,4'-diamino octafluorobiphenyl, 4,4'-diamino-p-terphenyl, 3,3'- Amino diphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane , 4,4'-methylenebis (2-ethyl-6-methylaniline), 4,4'-methylenebis (2,6-diethylaniline), 3,3'-diamine Benzophenone, 4,4'-diaminobenzophenone, 4,4'-ethylenediphenylamine, 4,4'-diamino-2,2'-dimethylbibenzyl, 2, 2'-bis (3-amino-4-hydroxyphenyl) propane, 2,2'-bis (3-aminephenyl) -hexafluoropropane, 2,2'-bis (3-aminephenyl)- Hexafluoropropane, 2,2'-bis (3-amino-4-tolyl) -hexafluoropropane, 2,2'-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, α , α'-bis (4-aminophenyl) -1,4-dicumene, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,1'- Bis (4-aminophenyl) -cyclohexane, 9,9'-bis (4-aminephenyl) -fluorene, 9,9'-bis (4-amino-3-chlorophenyl) fluorene, 9 , 9'-bis (4-amino-3-fluorophenyl) fluorene, 9,9'-bis (4-amino-3-tolyl) fluorene, 3,4'-diaminodiphenyl ether 4,4'-diaminodiphenyl ether, 1,3-bis (3-aminophenoxy) -benzene, 1,3-bis (4-aminophenoxy) -benzene, 1, 4-bis (4-aminophenoxy) -benzene, 1,4-bis (4-amino-2-trifluoromethylphenoxy) -benzene, 4,4'-bis (4- Phenylphenoxy) -biphenyl, 2,2'-bis [4- (4-aminophenoxy) -phenyl] propane, 2,2'-bis [4- (4-aminophenoxy ) -Phenyl] hexafluoropropane, bis (2-aminephenyl) sulfide, bis (4-aminephenyl) sulfide, bis (3-aminephenyl) fluorene, bis (4-aminephenyl) fluorene , Bis (3-amino-4-hydroxy) fluorene, bis [4- (3-aminophenoxy) -phenyl] fluorene, bis [4- (4-aminophenoxy) -phenyl] Hydrazone, o-toluidine hydrazone, 3,6-diaminocarbazole, 1,3,5-gins (4-aminophenyl) -benzene, 1,3-bis (3-aminopropyl) -tetramethyl Disylsiloxane, 4,4'-diaminobenzylamine benzene, 2- (3-aminophenyl) -5-aminobenzimidazole, 2- (4-aminophenyl) -5- Aminobenzo Azole, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 4,6-diaminoresorcinol, 2 , 3,5,6-pyridine tetramine, including Shin-Etsu Silicone (PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B -3, X-22-9409) polyfunctional amines with a siloxane structure, polyfunctional amines with a siloxane structure including Dow Corning (Dow Corning 3055), polyether structures (Huntsman, BASF) Functional amines, etc.

In addition, the alkali-soluble resin may include at least one repeating unit represented by Chemical Formula 3 below and at least one repeating unit represented by Chemical Formula 4 below.

In Chemical Formula 3, R ₂ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and "* "Means a key node.

In Chemical Formula 4, R ₃ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms; R ₄ is -H, -OH, -NR ₅ R ₆ , halogen, or an alkyl group having 1 to 20 carbon atoms; R ₅ and R ₆ may each independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, or An aryl group having 6 to 20 carbon atoms, and "*" means a bond point.

Preferably, in Chemical Formula 3, R ₂ is a phenylene group, and in Chemical Formula 4, R ₃ is a phenylene group and R ₄ may be -OH.

Meanwhile, the alkali-soluble resin may further include a vinyl-based repeating unit in addition to the repeating unit represented by Chemical Formula 3 and the repeating unit represented by Chemical Formula 4. The vinyl-based repeating unit is a repeating unit contained in a homopolymer of a vinyl-based monomer containing at least one or more vinyls in a molecule, and examples of the vinyl-based monomer may include but are not limited to Ethylene, propylene, isobutylene, butadiene, styrene, acrylic acid, methacrylic acid, maleic anhydride, maleimide and the like.

The alkali-soluble resin containing at least one repeating unit represented by the above-mentioned chemical formula 3 and at least one repeating unit represented by the above-mentioned chemical formula 4 can be obtained by using a polymer containing a repeating unit represented by the following chemical formula 5 and represented by the following chemical formula 6 An amine is produced by reacting with an amine represented by Chemical Formula 7 shown below.

In Chemical Formulas 5 to 7, R ₂ to R ₄ are the same as the above Chemical Formulas 3 and 4, and "*" means a bond point.

Specific examples of the polymer containing a repeating unit represented by Chemical Formula 5 may include, but are not limited to, SMA (Cray Valley), Xiran (Polyscope), Scripset (Solenis), Isobam (Kuraray), Polyanhydride resin (Chevron Phillips Chemical Company), Maldene (Lindau Chemicals) and others.

In addition, the alkali-soluble resin containing at least one repeating unit represented by the above Chemical Formula 3 and at least one repeating unit represented by the aforementioned Chemical Formula 4 can be obtained by reacting a compound represented by the following Chemical Formula 8 with a compound represented by the following Chemical Formula 9 Manufacturing.

In Chemical Formulas 8 and 9, R ₂ to R ₄ are the same as the above Chemical Formulas 3 and 4.

In addition, the alkali-soluble resin may be a conventionally known carboxyl group-containing resin or a phenol group-containing resin including a carboxyl group or a phenol group in the molecule. Preferably, a carboxyl-containing resin or a mixture of the carboxyl-containing resin and the phenol-based resin can be used.

Examples of the carboxyl group-containing resin include resins listed in (1) to (7) below.

(1) a carboxyl-containing resin obtained by reacting a polyfunctional epoxy resin with a saturated or unsaturated monocarboxylic acid and then reacting with a polybasic acid anhydride; (2) by reacting a bifunctional epoxy resin with a bifunctional epoxy resin; Functional group phenol and / or dicarboxylic acid, and then a carboxyl group-containing resin obtained by reacting with a polybasic acid anhydride; (3) reacting a polyfunctional phenol-based resin with a compound having an epoxy group in the molecule; A carboxyl-containing resin obtained by reacting with a polybasic acid anhydride, (4) a carboxyl-containing resin obtained by reacting a compound having two or more alcoholic hydroxyl groups in a molecule with a polybasic acid anhydride, and (5) a diamine by reacting Polyamic acid resin or copolymer resin of the polyamic acid resin obtained by reaction with dianhydride, (6) polyacrylic resin or copolymer of the polyacrylic resin reacted with acrylic acid, and ( 7) Resin prepared by reacting maleic anhydride and anhydride of maleic anhydride copolymer with weak acid, diamine, imidazole, or dimethylarsine to perform ring opening on maleic anhydride resin, but Not limited to this.

More specific examples of the carboxyl-containing resin include CCR-1291H (Nippon Kayaku), SHA-1216CA60 (Shin-A T & C), Noverite K-700 (Lubrizol), or a mixture of two or more thereof.

Examples of the phenol-based resin are not particularly limited, but for example, novolac resins such as phenol-based novolac resins, cresol novolac resins, bisphenol F (BPF) novolac resins, or bisphenol A-based resins can be used alone or in combination Resins, such as 4,4 '-(1- (4- (2- (4-hydroxyphenyl) prop-2-yl) phenyl) ethyl-1,1-diyl) diphenol.

The polymer resin layer may further include at least one additive selected from the group consisting of a thermosetting catalyst, an inorganic filler, a leveling agent, a dispersant, a release agent, and a metal adhesion promoter.

The alkali-soluble resin may have an acid value determined by KOH titration of 50 mgKOH / g to 250 mgKOH / g, or 70 mgKOH / g to 200 mgKOH / g. Examples of the method for measuring the acid value of the alkali-soluble resin are not particularly limited, but, for example, the following methods can be used. A KOH solution (solvent: methanol) having a concentration of 0.1 N was prepared as an alkali solution, and α-naphthol benzyl alcohol (pH: 0.8 to 8.2 was yellow, and 10.0 was blue-green) were used as indicators. Subsequently, about 1 to 2 g of the alkali-soluble resin was collected as a sample and dissolved in 50 g of an indicator-added dimethylformamide (DMF) solvent, followed by titration with an alkali solvent. The acid value is measured in mgKOH / g using the amount of the alkali solvent used when properly completed.

When the acid value of the alkali-soluble resin is excessively lowered to less than 50 mgKOH / g, the developing properties of the alkali-soluble resin are reduced, thus making it difficult to perform the developing method. In addition, when the acid value of the alkali-soluble resin is excessively increased to more than 250 mgKOH / g, phase separation from another resin occurs due to an increase in polarity.

Thermal curing catalysts are used to promote thermal curing of thermally curable adhesives. Examples of heat curing catalysts include imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1 -Cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; amine compounds such as dicyandiamine, benzyldimethylamine, 4 -(Dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, and 4-methyl-N, N-dimethyl Benzylamine; hydrazine compounds such as dihydrazine adipate and dihydrazine sebacate; phosphorus compounds such as triphenylphosphine; and the like. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (product names of imidazole compounds) manufactured by Shikoku Chemicals Corporation; U-CAT3503N and UCAT3502T (Dimethyl A) manufactured by San-Apro Ltd. Product names of amine block isocyanate compounds), and DBU, DBN, U-CATS A102, U-CAT5002 (bicyclic fluorene compounds and their salts). However, the thermal curing catalyst is not limited to these, and may be a thermal curing catalyst for epoxy resin or oxocyclobutane compound, or a catalyst that accelerates the reaction of epoxy group and / or oxocyclobutane group with carboxyl group. Compound. These catalysts can be used alone or as a mixture of two or more. In addition, S-Three can be used Derivatives such as guanamine, eguanidamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-tri , 2-vinyl-4,6-diamino-S-tri , 2-vinyl-4,6-diamino-S-tri , 2-vinyl-4,6-diamino-S-tri -Trimeric isocyanate adduct, 2,4-diamino-6-methacryloxyethyl-S-tri -Trimeric isocyanate adducts, etc. Preferably, the compound that can be used as an adhesion-imparting agent can also be used in combination with a thermosetting catalyst.

Examples of the inorganic filler include silica, barium sulfate, barium titanate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, or a mixture of two or more thereof.

The content of the inorganic filler is not particularly limited. However, in order to obtain high rigidity of the polymer resin layer, the inorganic filler may be added in an amount of 100 parts by weight or more based on 100 parts by weight of all the resin components contained in the polymer resin layer. 600 parts by weight, 150 parts by weight to 500 parts by weight, or 200 parts by weight to 500 parts by weight.

Examples of the release agent include polyalkylene waxes such as low molecular weight polypropylene and low molecular weight polyethylene, ester wax, carnauba wax, paraffin wax, and the like.

The metal adhesion promoter may be a material that does not cause surface deterioration or transparency problems of metal materials, such as a silane coupling agent, an organic metal coupling agent, and the like.

Leveling agents are used to remove protrusions or pits on the surface during film coating, and for example, BYK-380N, BYK-307, BYK-378, and BYK-350 available from BYK-Chemie GmbH can be used.

In addition, the polymer resin layer may further include a resin or an elastomer having a molecular weight of 5000 or more that can cause phase separation. Therefore, the cured product of the polymer resin layer can be roughened. Examples of the method for measuring the molecular weight of a resin or an elastomer having a molecular weight of 5000 or more are not particularly limited, and for example, it means that the weight average molecular weight with respect to polystyrene is measured by GPC (gel permeation chromatography). In the method for determining the weight-average molecular weight of polystyrene by GPC, a generally known analysis device, a detector such as a differential refractive index detector, and an analytical column can be used. Can be used for general application conditions of temperature, solvent, and flow rate. Specific examples of the measurement conditions include a temperature of 30 ° C, tetrahydrofuran (THF), and a flow rate of 1 mL / min.

In addition, in order to make the polymer resin layer have photo-curable properties, the polymer resin layer may further include a heat-curable adhesive containing a photoreactive unsaturated group, or a photoreactive unsaturated group and a photoinitiator. Agent of alkali-soluble resin. Specific examples of the heat-curable adhesive containing a photo-reactive unsaturated group or the alkali-soluble resin containing a photo-reactive unsaturated group and a photoinitiator are not particularly limited, and a photo-curable resin composition may be used. Various compounds are used in the technical field without limitation.

On the other hand, the opposite surface of the metal layer to which one surface of the carrier film is adhered may be adhered to the polymer resin layer. Examples of the metal described in the metal layer include metals such as gold, silver, copper, tin, nickel, aluminum, and titanium, and mixtures of two or more of these metals. The thickness of the metal layer may be 10 nm to 10 μm. If the thickness of the metal layer is excessively increased to more than 10 μm, excess metal is required to form the metal layer, thereby increasing raw material costs and reducing economic efficiency.

The carrier film may be adhered to a surface of the metal layer. The carrier film can be adhered to a surface of the metal layer to prevent direct contact with the surface of the metal layer during a process such as moving or adhering the metal layer, and the carrier film can be physically peeled after being adhered to the metal layer. Can be easily removed. Specific examples of the carrier film are not particularly limited, and, for example, organic and inorganic materials such as polymers, metals, and rubbers can be variously applied. In one embodiment, the same material as that of the metal layer is preferably used as the material of the carrier film. As such, as described below, the carrier film and the metal layer can be simultaneously etched by the same etchant to form a pattern.

On the other hand, the surface opposite to the surface of the metal layer to which the carrier film is adhered may be adhered to the polymer resin layer. The opposite surface of one surface of the metal layer means a surface parallel to and facing the one surface of the metal layer. When the opposite surface of the metal layer to which one surface of the carrier film is adhered is adhered to the polymer resin layer, a structure in which a metal layer system is laminated on the polymer resin layer, and then a carrier film is laminated on the metal layer may be formed. .

In this case, as described below, since the adhesive force between the carrier film and the metal layer can be smaller than the adhesive force between the polymer resin layer and the metal layer, physical properties between the carrier film and the metal layer can be prevented. The polymer resin layer is peeled from the metal layer during peeling. When the adhesive force between the polymer resin layer and the metal layer is smaller than the adhesive force between the carrier film and the metal layer, during the physical peeling of the carrier film from the metal layer, the polymer resin layer and the metal layer Since the metal layer is peeled, it may be difficult to form a fine pattern on the polymer resin layer.

Step of forming a patterned photosensitive resin layer on a carrier film

The photosensitive resin layer may be laminated on the carrier film in a state where a pattern is formed, or may be patterned after being laminated, but more preferably, the pattern may be formed after being laminated on the carrier film.

Examples of the photosensitive resin layer may include a photosensitive dry film resist (DFR, etc.) that is alkali-soluble or non-thermosetting.

The step of forming a patterned photosensitive resin layer on the carrier film may include exposing and subjecting the photosensitive resin layer formed on the carrier film to alkaline development. In this case, the photosensitive resin layer can be used as a protective layer of the carrier film or as a patterned mask.

In the step of forming a patterned photosensitive resin layer on a carrier film, the thickness of the photosensitive resin layer formed on the carrier film may be 1 μm to 500 μm, 3 μm to 500 μm, 3 μm to 200 μm, 1 μm to 60 μm, Or 5 μm to 30 μm. When the thickness of the photosensitive resin layer is excessively increased, the resolution of the polymer resin layer is reduced.

In the steps of exposing and subjecting the photosensitive resin layer formed on the carrier film to alkaline development, an example of a method for forming the photosensitive resin layer on the carrier film is not particularly limited, and for example, it can be used on a carrier film A method of laminating a film-like photosensitive resin such as a photosensitive dry film, or a method of coating a photosensitive resin composition by spraying or dipping on the carrier film and pressing the coated film, and the like.

In the steps of exposing and subjecting the photosensitive resin layer formed on the carrier film to alkaline development, examples of the method of exposing and subjecting the photosensitive resin layer to alkaline development are not particularly limited, but for example, the exposure may be performed via A method in which a photomask formed with a predetermined pattern is brought into contact with the photosensitive resin layer and then irradiated with ultraviolet rays, a method of imaging a predetermined pattern included in the mask through a projection objective, and then irradiated with ultraviolet rays, using a laser diode as The light source selectively performs a method of directly imaging a predetermined pattern included in the mask and then irradiating it with ultraviolet rays. In this case, examples of the ultraviolet irradiation conditions may include irradiation with a light amount of ⁵ mJ / cm ² to 600 mJ / cm ² .

In addition, in the steps of exposing and subjecting the photosensitive resin layer formed on the carrier film to alkaline development, examples of a method of developing the photosensitive resin layer may include a method of treating with an alkaline developer. Examples of the alkaline developer are not particularly limited, but, for example, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, amine can be used Etc., and preferably, a 1% sodium carbonate developer at 30 ° C can be used. The specific amount of the alkaline developer is not particularly limited.

In the case of processing an alkaline developer, only a part of the photosensitive resin layer is removed by development, and a polymer resin layer containing an alkali-soluble resin and a heat-curable adhesive at the lower part can be protected by a carrier film. This prevents the layer from being developed. Therefore, there is no need for a separate step for preventing the development of the polymer resin layer, such as a step of curing the polymer resin layer in advance, or introducing two or more different metal layers for sequentially patterning with different etchant. Step; The resolution of the via hole can be improved by reducing the aspect ratio by forming a fine metal layer on the polymer layer as a resist mask.

Step of removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer

In the step of removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer, the photosensitive resin pattern is used as a resist for forming a pattern on the carrier film and the metal layer. Therefore, the carrier film and the metal layer exposed by the pattern of the photosensitive resin layer mean a portion of the surface of the carrier film and the metal layer that is not in contact with the photosensitive resin layer.

Specifically, the step of removing the carrier film and the metal layer exposed by the pattern of the photosensitive resin layer may include a step of an etchant passing through the patterned photosensitive resin layer and contacting the carrier film and the metal layer.

The etchant can be selected according to the type of the carrier film and the metal layer, and if possible, it is preferable to use a substance that has less influence on the underlying copper wire and does not affect the photosensitive resin layer.

However, as mentioned above, in this embodiment, it is preferable to use the same material as the metal layer as the material of the carrier film, so that the carrier film and the metal layer can be simultaneously or sequentially moved by the same etchant. Can be easily formed.

On the other hand, in the step of removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form the patterned metal layer, the removal rate of the polymer resin layer is based on the polymer resin layer. The total weight may be 0.01% by weight or less. The word "the removal rate of the polymer resin layer is 0.01% by weight or less based on the total weight of the polymer resin layer" may mean that the degree of removal of the polymer resin layer is very insignificant, or the polymer resin layer Not removed.

That is, the etchant used in the step of removing the exposed carrier film and the metal layer of the patterned photosensitive resin layer to form the patterned metal layer has no physical or chemical influence on the polymer resin layer. Therefore, the polymer resin layer can be stably maintained until the fine metal pattern layer is formed, and the resolution of the via hole can be improved by reducing the aspect ratio by using the fine metal pattern layer as a resist mask.

Steps to separate and remove carrier film from patterned metal layer

After the steps of removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer as described above, the patterned metal layer, the patterned carrier film, and the pattern The converted photosensitive resin layer may be sequentially laminated.

At this time, in order to form the insulating layer, it is necessary to remove all the remaining layers except the polymer resin layer and the patterned metal layer formed on the polymer resin layer. For this reason, it is customary to use an alkaline developer to remove the photosensitive resin layer for patterning. In this case, there is a problem that the alkaline developer allows the polymer resin layer to be developed simultaneously or sequentially. In addition, in the case where a metal layer for forming a pattern is used, since an etchant is used to remove the metal layer, problems such as corrosion of a copper wire below may occur.

On the other hand, in one embodiment, the remaining layers other than the patterned metal layer formed on the polymer resin layer can be easily separated and removed by a simple method of separating and removing the carrier film from the metal layer. Removed.

In the above embodiment, since the adhesive force between the carrier film and the metal layer is smaller than the adhesive force between the polymer resin layer and the metal layer, it can be prevented during the physical peeling of the carrier film and the metal layer. The polymer resin layer is separated from the metal layer.

In addition, in the process of separating the carrier film from the metal layer, the carrier film is removed together with the photosensitive resin layer formed on the carrier film in a state of adhesion or peeling, even without using an etchant. Only a fine metal pattern mask can be easily left on the polymer resin layer, so the resolution of the via hole can be improved by reducing the aspect ratio through a patterning process described below.

Step of subjecting the polymer resin layer exposed to the patterned metal layer to alkaline development

In addition, the method of manufacturing the insulating layer may include performing alkaline development on the polymer resin layer exposed by the patterned metal layer. When replacing the conventional laser etching process, through the process of selectively contacting only the surface portion of the polymer resin layer exposed through the pattern formed on the metal layer with the alkaline developer as described above, it can ensure the same level of accuracy and high Process economy.

In the step of performing alkaline development on the polymer resin layer exposed by the patterned metal layer, a metal layer pattern is used as a resist for forming a pattern on the polymer resin layer. Therefore, the polymer resin layer exposed by the metal layer pattern means a portion where the surface of the polymer resin layer is not in contact with the metal layer.

Specifically, the step of performing alkaline development on the polymer resin layer exposed by the patterned metal layer may include a step of passing an alkaline developer through the patterned metal layer and contacting the polymer resin layer.

Since the polymer resin layer includes an alkali-soluble resin, which has alkali solubility to dissolve it in an alkaline developer, a portion of the polymer resin layer that is in contact with the alkaline developer can be dissolved and removed.

On the other hand, after the step of alkaline developing the polymer resin layer exposed by the patterned metal layer, it will remain based on the total weight of the polymer resin layer exposed by the patterned metal layer It is 0.1 to 85% by weight, 0.1 to 50% by weight, or 0.1 to 10% by weight. This is considered to be because the alkali-soluble resin contained in the polymer resin layer has been removed by the alkaline developer, but the heat-curable adhesive or inorganic filler having low alkaline development properties has not been removed. Caused by.

Therefore, when the patterned metal layer is removed by an etchant treatment as needed, the underlying copper foil exposed by the pattern can be etched together with it, thereby minimizing deep etching.

Meanwhile, the polymer resin layer remaining after the step of subjecting the polymer resin layer exposed to the patterned metal layer to alkaline development can be removed by treatment with a peeling liquid or the like. That is, after the step of performing alkaline development on the polymer resin layer exposed by the patterned metal layer, the method may further include a step of processing a peeling liquid, and the kind and processing method of the peeling liquid are not particularly limited.

In particular, in order to control the extent to which the inorganic filler and the heat-curable adhesive remain, the weight ratio of the heat-curable adhesive and the inorganic filler to the alkali-soluble resin, the ratio of the acid functional groups on the surface of the inorganic filler, and the like control. Preferably, based on 100 parts by weight of the alkali-soluble resin, 20 to 100 parts by weight of a heat-curable adhesive and 100 to 600 parts by weight of an inorganic filler may be added. The acid value on the surface of the inorganic filler may be in a range of 0 mgKOH / g to 5 mgKOH / g, or 0.01 mgKOH / g to 5 mgKOH / g. The details of the acid value are the same as those in the method of measuring the acid value of the alkali-soluble resin.

Examples of the alkaline developer are not particularly limited, but, for example, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, amine can be used Etc., and preferably, a 1% sodium carbonate developer at 30 ° C can be used. The specific amount of the alkaline developer is not particularly limited.

Step of thermally curing a polymer resin layer after alkaline development

In addition, the method of manufacturing the insulating layer may include thermally curing the polymer resin layer after alkaline development. The step of curing the polymer resin layer may be performed at a temperature of 100 to 250 ° C.

Meanwhile, after the step of thermally curing the polymer resin layer, the method may further include removing a metal layer on the polymer resin layer. The method of removing the metal layer includes a method of removing the metal layer without removing the copper wire under the polymer resin layer or removing only a part thereof.

As a specific example, by making the thickness of the copper foil of the metal layer to an extremely thin thickness of 3 μm or less, the metal layer is removed but the underlying copper wires are partially removed, or the metal layer is removed but can be used without Etchant that affects the underlying copper wires.

On the other hand, according to another aspect of the present invention, a method for manufacturing a multilayer printed circuit board is provided. The method includes the step of forming a patterned metal substrate on the insulating layer manufactured in the aspect.

The inventor has found that, since the insulating layer manufactured in the above embodiment includes a specific opening pattern, in the process of newly laminating a metal substrate on the insulating layer, the inside of the opening pattern is filled with metal, so that it is located in the upper part The metal substrates below and below are connected based on this insulating layer to make a multilayer printed circuit board. The present invention has been completed based on this finding.

The insulating layer may be used as an interlayer insulating material of a multilayer printed circuit board, and may include a cured product of an alkali-soluble resin and a heat-curable adhesive. The details of the alkali-soluble resin and the heat-curable adhesive include those described in the above embodiments. If necessary, a copper foil having a thickness of 5 μm or less may be formed on the surface of the insulating layer.

The step of forming a patterned metal substrate on the insulating layer is a fine circuit pattern forming process known as a semi-additive process (SAP) or a modified semi-additive process (MSAP). SAP means a process of forming a fine circuit pattern in a state where nothing is present on the insulating layer, and MSAP means a process of forming a fine circuit pattern in a state where a copper foil of 5 m or less is formed on the insulating layer.

More specific examples of the step of forming a patterned metal substrate on an insulating layer include the following steps: forming a metal thin film on the insulating layer; forming a photosensitive resin layer having a pattern formed thereon on the metal thin film; Metal is deposited on the metal film exposed by the photosensitive resin layer pattern; removing the photosensitive resin layer; and removing the exposed metal film.

In the step of forming the metal thin film on the insulating layer, examples of the method for forming the metal thin film include a dry deposition method or a wet deposition method, and specific examples of the dry deposition method include vacuum deposition, ion plating, sputtering, and the like. On the other hand, as a specific example of the wet deposition method, electroless plating of various metals may be mentioned, and more specifically, electroless copper plating may be used. In addition, a roughening treatment step may be additionally included before or after vapor deposition.

In addition, as for the method of forming a metal thin film on an insulating layer, when a metal layer is used as a protective layer in the manufacturing method of the insulating layer in this embodiment, when the step of removing the metal layer is not performed, The manufactured insulating layer can be used as it is.

The roughening method can be a dry method or a wet method, depending on the method conditions. Examples of the dry method include vacuum processing, atmospheric pressure processing, gas plasma processing, gas excimer UV processing, and the like. Examples of the wet method include desmear treatment. By such a roughening treatment method, the surface roughness of the metal thin film can be improved and the adhesion to the metal deposited on the metal thin film can be improved.

The step of forming a metal thin film on the insulating layer may further include a step of forming a surface treatment layer on the insulating layer before depositing the metal thin film. Therefore, the adhesion between the metal thin film and the insulating layer can be improved.

Specifically, as an example of a method of forming a surface treatment layer on the insulating layer, any one selected from an ion-assisted reaction method, an ion beam treatment method, and a plasma treatment method can be used. The plasma treatment method may include any one of an atmospheric plasma treatment method, a DC plasma treatment method, and an RF plasma treatment method. Due to the surface treatment process, a surface treatment layer containing a reactive functional group can be formed on the surface of the insulating layer. As another example of a method of forming a surface treatment layer on an insulating layer, a method of depositing chromium (Cr) and titanium (Ti) metals with a thickness of 50 nm to 300 nm on the surface of the insulating layer may be mentioned.

Meanwhile, the step of forming the photosensitive resin layer in which the pattern is formed on the metal thin film may include the steps of exposing and developing the photosensitive resin layer formed on the metal thin film. Details of the photosensitive resin layer and exposure and development may include those in the one embodiment described above.

In the step of depositing a metal on the metal thin film exposed by the photosensitive resin layer pattern, the metal thin film exposed by the photosensitive resin layer pattern means a portion of the metal thin film whose surface is not in contact with the photosensitive resin layer. The metal to be deposited may be copper. Examples of the deposition method are not particularly limited, and various well-known physical or chemical vapor deposition methods can be used without limitation. As a general example, an electrolytic copper plating method can be used.

In the steps of removing the photosensitive resin layer and removing the exposed metal film, a photoresist peeling liquid may be used in an example of a method for removing the photosensitive resin layer, and an etchant may be used due to the removal of the photosensitive resin layer. An example of a method for removing an exposed metal film.

The multilayer printed circuit board manufactured by the manufacturing method of the multilayer printed circuit board can be used again as a buildup material. For example, according to the first step of forming an insulating layer on a multilayer printed circuit board according to the manufacturing method of the insulating layer in this embodiment, and forming the metal substrate on the insulating layer according to the manufacturing method of the multilayer printed circuit board in another embodiment. The second step can be repeated.

Therefore, the number of laminated layers included in the multilayer printed circuit board manufactured by the manufacturing method of the multilayer printed circuit board is not particularly limited, and may have, for example, one to twenty layers depending on the purpose and application of the application.

According to the present invention, a method for manufacturing an insulating layer can be proposed, which can achieve a uniform and fine pattern while improving efficiency in terms of cost and productivity and ensuring excellent mechanical properties; and a multilayer using the insulating layer obtained from the method for manufacturing the insulating layer Manufacturing method of printed circuit board.

Hereinafter, the present invention is described in more detail by way of examples. However, these examples are for illustrative purposes only and should not be considered as limiting the scope of the invention.

     <Preparation example: Preparation of alkali-soluble resin>     

Preparation Example 1

632 g of dimethylformamide (DMF) as a solvent, 358 g of BMI-1100 (product name, manufactured by Daiwakasei) as an N-substituted maleimide compound, and 151 g of 4- Aminophenylacetic acid was placed in a 2 liter reaction vessel with heating and cooling capabilities and equipped with a thermometer, a stirrer, a reflux condenser, and a quantitative moisture analyzer and mixed, and stirred at 85 ° C for 24 hours to prepare Alkali-soluble resin solution with a solids content of 50%.

Preparation Example 2

632 g as a solvent of dimethylformamide (DMF), 434 g as an N-substituted maleimide compound, p-carboxyphenyl maleimide, and 198 g as a compound of amine 4, 4-Diaminodiphenylmethane was placed in a 2 liter reaction vessel with heating and cooling capabilities and equipped with a thermometer, a stirrer, a reflux condenser, and a quantitative moisture analyzer, and mixed, and stirred at 85 ° C for 24 hours. Hours to prepare an alkali-soluble resin solution with a solid content of 50%.

Preparation Example 3

543 g of dimethylacetamide (DMAc) as a solvent was placed in a 2 liter reaction vessel having heating and cooling capabilities and equipped with a thermometer, a stirrer, a reflux condenser, and a quantitative moisture analyzer, and mixed. Among them, 350 g of SMA1000 (Cray Valley), 144 g of 4-aminobenzoic acid (PABA), and 49 g of 4-aminophenol (PAP) were mixed and mixed. After the temperature of the reactor was fixed at 80 ° C under a nitrogen atmosphere, the acid anhydride and the aniline were reacted for 24 hours to form amidine. Then, after the reactor temperature was fixed at 150C, the imidization reaction was continued for 24 hours to prepare an alkali-soluble resin solution having a solid content of 50%.

Preparation Example 4

516 g of methyl ethyl ketone (MEK) as a solvent was placed in a 2 liter reaction vessel equipped with a heating and cooling capacity and equipped with a thermometer, a stirrer, a reflux condenser, and a quantitative moisture analyzer, and mixed, and 228 g was added P-carboxyphenyl maleimide diimide, 85 g of p-hydroxyphenyl maleimide diimide, 203 g of styrene, and 0.12 g of azobisisobutyronitrile (AIBN) and mix them. After the temperature of the reaction was gradually increased to 70 ° C. under a nitrogen atmosphere, the reaction was continued for 24 hours to prepare an alkali-soluble resin solution having a solid content of 50%.

     <Example>           <Example 1: Production of insulation layer>     

Referring to FIG. 1, by mixing 16 g of an alkali-soluble resin synthesized in Preparation Example 1, 5 g of MY-510 (manufactured by Huntsman) as a heat-curable adhesive, and 35 g of SC2050 MTO (manufactured by Adamatech) as an inorganic filler The obtained polymer resin composition was applied to an ultra-thin copper foil 4 MT18SD-H (manufactured by Mitsui Kinzoku) having a thickness of 3 μm and a carrier copper foil 5 adhered thereto, and dried to prepare a polymer having a thickness of 15 μm Resin layer 1. Then, the polymer resin layer 1 was vacuum-laminated on a circuit board at 85 ° C, and the copper wire 2 on the circuit board was formed on the copper foil laminate 3, and a photosensitive dry film having a thickness of 15 m was resisted at 110 ° C Agent KL 1015 (manufactured by Kolon Industries) 6 was laminated on the carrier copper foil 5.

A circular negative mask having a diameter of 30 μm was brought into contact with the photosensitive drying film resist 6 and irradiated with ultraviolet rays (a light amount of 25 mJ / cm ² ). Then, the dried film resist 6 is developed through a 1% sodium carbonate developer at 30 ° C. to form a specific pattern.

Subsequently, the carrier copper foil 5 and the ultra-thin copper foil 4 are etched by treatment with an etchant. At this time, the patterned photosensitive drying film resist 6 is used as a protective layer for the carrier copper foil 5 and the ultra-thin copper foil 4 so that the same pattern as the photosensitive drying film resist 6 is formed on the carrier equally. Copper foil 5 and ultra-thin copper foil 4.

Subsequently, the ultra-thin copper foil 4 and the carrier copper foil 5 are separated, so that the carrier copper foil 5 and the photosensitive dry film resist 6 laminated on the carrier copper foil 5 are removed.

Next, the polymer resin layer 1 was developed through a 1% sodium carbonate developer at 30 ° C. At this time, the ultra-thin copper foil 4 on which the pattern is formed serves as a protective layer of the polymer resin layer 1. Therefore, when the same pattern as the ultra-thin copper foil 4 is formed, the via holes 7 are uniformly formed in the polymer resin layer 1. .

Subsequently, thermal curing was performed at a temperature of 110 ° C. for 1 hour, and then treated with an etchant to remove the ultra-thin copper foil 4, and an additional thermal curing process was performed at a temperature of 200 ° C. for 1 hour to manufacture an insulating layer.

     <Example 2: Manufacturing of multilayer printed circuit board>     

Referring to FIG. 2, when a mixed gas of argon and oxygen is supplied to the upper surface of the insulating layer and the side surface of the via hole 7 manufactured in Example 1 by a vapor deposition method through a sputtering method, titanium (Ti) The metal was deposited to a thickness of 50 nm and the copper (Cu) metal was deposited to a thickness of 0.5 μm to form the seed layer 8.

Subsequently, the photosensitive resin layer is exposed and developed on the seed layer 8 to form a photosensitive resin pattern 9. Then, a metal substrate 10 made of copper is formed on the seed layer 8 by electrolytic plating. Next, the photosensitive resin pattern 9 is removed using a photosensitive resin peeling liquid to remove the exposed seed layer 8 via etching, thereby manufacturing a multilayer printed circuit board.

     <Example 3: Production of insulation layer>     

The insulating layer was manufactured in the same manner as in Example 1, except that the alkali-soluble resin synthesized in Preparation Example 2 was used instead of the alkali-soluble resin synthesized in Preparation Example 1 in the manufacturing method of the insulating layer in Example 1.

     <Example 4: Production of insulation layer>     

The insulating layer was produced in the same manner as in Example 1, except that the alkali-soluble resin synthesized in 3 in Preparation Example was used instead of the alkali-soluble resin synthesized in Preparation Example 1 in the method of manufacturing the insulating layer in Example 1.

     <Example 5: Production of insulation layer>     

The insulating layer was produced in the same manner as in Example 1, except that the alkali-soluble resin synthesized in Preparation Example 4 was used instead of the alkali-soluble resin synthesized in Preparation Example 1 in the manufacturing method of the insulating layer in Example 1.

     <Comparative example 1: manufacture of insulating layer>     

By mixing 16 g of the alkali-soluble resin synthesized in Preparation Example 1, 5 g of MY-510 (manufactured by Huntsman) as a heat-curable adhesive, and 35 g of SC 2050 MTO (manufactured by Adamatech) as an inorganic filler. The obtained polymer resin composition was applied onto a PET film (25 μm) and dried to prepare a polymer resin layer 1 having a thickness of 15 μm. Then, the polymer resin layer 1 is laminated on a circuit board on which a copper wire 2 is formed on a copper foil laminate 3 at 85 ° C., and the PET film is removed.

A photosensitive dry film resist KL 1015 (manufactured by Kolon Industries) having a thickness of 15 μm was laminated on a polymer resin layer at 110 ° C. A circular negative mask having a diameter of 30 μm was brought into contact with a photosensitive dry film resist, and irradiated with ultraviolet rays (a light amount of 25 mJ / cm ² ). Then, the photosensitive dry film resist and the polymer resin layer are sequentially developed through a 1% sodium carbonate developer at 30 ° C.

At this time, the photosensitive dry film resist acts as a protective layer of the polymer resin layer, and when the same pattern as the photosensitive dry film resist is formed, via holes are uniformly formed in the polymer resin layer.

Subsequently, heat curing was performed at a temperature of 100 ° C for 1 hour, and then the liquid was stripped with a 3% sodium hydroxide resist to remove the photosensitive dry film resist, and further heat cured at 200 ° C for 1 hour. To make an insulating layer.

     <Comparative Example 2: Manufacturing of multilayer printed wiring board>     

The multilayer printed circuit board was manufactured in the same manner as in Example 2, except that the insulating layer manufactured in Comparative Example 1 was used instead of the insulating layer manufactured in Example 1.

     <Experimental Example: Measurement of Physical Properties of Insulation Layers Obtained in Examples and Comparative Examples>     

The physical properties of the insulating layers obtained in the above examples and comparative examples were measured by the following methods, and the results are shown in Table 1 below.

Diameter of via hole

The diameter of the upper opening (via hole) of the insulating layer obtained in Examples 1 and 3 to 7 and Comparative Example 1 was measured using an optical microscope.

2. Metal adhesion caused by hygroscopicity

The multilayer printed circuit boards obtained in Example 2 and Comparative Example 2 were kept at 135 ° C and 85% moisture absorption for 48 hours, and then the peel strength of the metal was measured according to the standard of IPC-TM-650. As a result, metal adhesion is obtained.

3. Highly accelerated temperature and humidity stress test (HAST) resistance

The HAST resistance of the multilayer printed circuit boards obtained in Example 2 and Comparative Example 2 was confirmed according to the JESD 22-A101 standard. Specifically, a voltage of 3 V was applied to the circuit board of the test piece having a width of 50 μm, an interval of 50 μm, and a thickness of 12 μm, and then the voltage was maintained for 168 hours. Then, the appearance of the circuit board of the test piece was confirmed according to the following criteria.

OK: No abnormality was observed in the appearance of the film

NG: Blistering and peeling were observed in the film

As shown in Table 1, in the case of the insulating layer of Comparative Example 1 in which the via hole was formed using only a photosensitive dry film as a protective layer, the diameter of the via hole was 45 μm. However, in Examples 1 and 3 to 5, The diameter of the via hole included in the manufactured insulating layer was reduced to 32 μm or 33 μm. Therefore, it was confirmed that in the case of the embodiment, a finer pattern can be obtained.

In addition, it was confirmed that in the case of the multilayer printed wiring board of Comparative Example 2 obtained from the insulating layer of Comparative Example 1, the metal adhesion was measured to be 0.3 kgf / cm. However, in the case of the multilayer printed wiring board of Example 2, The measured metal adhesion is as high as 0.4 kgf / cm, thereby improving the interface adhesion between the insulating layer and the conductive layer, and exhibiting excellent HAST resistance.

Claims (20)

    A method for manufacturing an insulating layer, comprising the steps of: adhering an opposite surface of a metal layer to a surface of a carrier film adhered to a polymer resin layer containing an alkali-soluble resin and a heat-curable adhesive; and forming on the carrier film A patterned photosensitive resin layer; removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer; separation and removal from the patterned metal layer Removing the carrier film; performing alkaline development on the polymer resin layer exposed by the patterned metal layer; and thermally curing the polymer resin layer after the alkaline development.         For example, the method for manufacturing an insulating layer according to the scope of patent application, wherein the opposite surface of the surface of the metal layer to which one of the carrier films is adhered is adhered to a polymer resin layer containing an alkali-soluble resin and a heat-curable adhesive. In the step, the adhesive force between the carrier film and the metal layer is smaller than the adhesive force between the polymer resin layer and the metal layer.         For example, in the method for manufacturing an insulating layer of the scope of patent application, in the step of separating and removing the carrier film from the patterned metal layer, the carrier film and the photosensitivity formed on the carrier film The resin layer is removed together.         For example, in the method for manufacturing an insulating layer according to claim 1, wherein in the step of removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer, The carrier film and the metal layer are removed simultaneously or sequentially by the same etchant.         For example, in the method for manufacturing an insulating layer according to claim 1, wherein in the step of removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer, The removal rate of the polymer resin layer is 0.01% by weight or less based on the total weight of the polymer resin layer.         For example, the method for manufacturing an insulating layer according to the scope of patent application, wherein the step of forming a patterned photosensitive resin layer on the carrier film includes exposing and alkaline-working the photosensitive resin layer formed on the carrier film. Sexual development steps.         For example, the method for manufacturing an insulating layer according to item 6 of the patent application, wherein in the steps of exposing and performing alkaline development on the photosensitive resin layer formed on the carrier film, the polymer resin layer is subjected to the carrier film protection.         For example, the method for manufacturing an insulating layer according to claim 1, wherein after the step of thermally curing the polymer resin layer, the method may further include removing the metal layer on the polymer resin layer.         For example, the method for manufacturing an insulating layer according to claim 1 of the application, wherein the alkali-soluble resin includes at least one acid functional group and at least one cyclic amidine imine functional group substituted with an amine group.     For example, the method for manufacturing an insulating layer according to item 9 of the scope of patent application, wherein the amine substituted fluorene imine functional group includes a functional group represented by the following Chemical Formula 1: Among them, in Chemical Formula 1, R ₁ is an alkylene or alkenyl group having 1 to 10 carbon atoms, and “*” means a bonding point.     For example, the method for manufacturing an insulating layer according to item 9 of the application, wherein the alkali-soluble resin is produced through a reaction between a cyclic unsaturated sulfonium imine compound and an amine compound, and the cyclic unsaturated sulfonium imine compound and the amine At least one of the compounds contains an acid functional group substituted at its terminal.         For example, the method for manufacturing an insulating layer according to item 11 of the application, wherein the amine compound includes at least one selected from the group consisting of an amine-substituted carboxylic acid compound and two or more amines. Polyfunctional amine compound.     For example, the method for manufacturing an insulating layer of the scope of application for a patent, wherein the alkali-soluble resin includes at least one repeating unit represented by Chemical Formula 3 below and at least one repeating unit represented by Chemical Formula 4 below: Wherein, in Chemical Formula 3, R ₂ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and "*" Means a key node, Among them, in Chemical Formula 4, R ₃ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, R ₄ is -H, -OH, -NR ₅ R ₆ , halogen, or an alkyl group having 1 to 20 carbon atoms, and R ₅ and R ₆ may each independently be hydrogen and an alkyl group having 1 to 20 carbon atoms , Or an aryl group having 6 to 20 carbon atoms, and "*" means a bond point. For example, the method for manufacturing an insulating layer according to item 13 of the application, wherein the alkali-soluble resin is a polymer containing a repeating unit represented by Chemical Formula 5 below, an amine represented by Chemical Formula 6 below, and Chemical Formula 7 below. Represents the amine reaction to make: Among them, in Chemical Formulas 5 to 7, R ₂ to R ₄ are the same as those defined in item 13 of the scope of patent application, and "*" means a bond node. For example, the method for manufacturing an insulating layer according to item 13 of the application, wherein the alkali-soluble resin is produced by reacting a compound represented by the following Chemical Formula 8 with a compound represented by the following Chemical Formula 9: Among them, in Chemical Formulas 8 and 9, R ₂ to R ₄ are the same as those defined in item 13 of the scope of patent application.     For example, the method for manufacturing an insulating layer of the scope of application for a patent, wherein the alkali-soluble resin has an acid value of 50 mgKOH / g to 250 mgKOH / g as measured by KOH titration.         For example, the method for manufacturing an insulating layer according to claim 1, wherein the polymer resin layer includes a heat-curable adhesive in an amount of 1 to 150 parts by weight based on 100 parts by weight of the alkali-soluble resin.     For example, the method for manufacturing an insulating layer of the scope of patent application, wherein the heat-curable adhesive includes at least one functional group selected from the group consisting of: a heat-curable functional group, oxetanyl (oxetanyl ), Cyclic ether group, cyclic thioether group, cyanide group, maleimide group, and benzo And epoxy.     For example, the method for manufacturing an insulating layer according to the scope of patent application, wherein the polymer resin layer further includes at least one additive selected from the group consisting of a thermosetting catalyst, an inorganic filler, a leveling agent, and a dispersant. , Release agent, and metal adhesion promoter.         A method for manufacturing a multilayer printed circuit board, comprising the steps of forming a metal substrate having a pattern formed thereon on the insulating layer prepared as a method according to any one of claims 1 to 19.