JP2018530167A - Insulating layer manufacturing method and multilayer printed circuit board manufacturing method - Google Patents

Abstract

The present invention is obtained from a method for manufacturing an insulating layer capable of realizing a uniform and fine pattern and ensuring excellent mechanical properties while improving efficiency in terms of cost and productivity, and the method for manufacturing the insulating layer. The present invention relates to a method for manufacturing a multilayer printed circuit board using an insulating layer.

Description

[Cross-reference of related applications]
This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0101419 dated August 9, 2016 and Korean Patent Application No. 10-2017-0096355 dated July 28, 2017, and All the contents disclosed in the Korean patent application literature are included as part of this specification.

  The present invention relates to an insulating layer manufacturing method and a multilayer printed circuit board manufacturing method. In more detail, while improving efficiency in terms of cost and productivity, it is possible to realize a uniform and fine pattern and to ensure excellent mechanical properties, and an insulating layer obtained from the insulating layer manufacturing method The present invention relates to a method for manufacturing a multilayer printed circuit board using layers.

  Recent electronic devices are becoming smaller, lighter and more functional. For this reason, the use of multilayer printed circuit boards is rapidly increasing as the application field of build-up PCB (Build-up Printed Circuit Board) is rapidly expanding mainly in small devices.

  Multi-layer printed circuit boards can be used in three-dimensional wiring from planar wiring. Especially in the industrial electronics field, the integration of functional elements such as integrated circuits (ICs) and large scale integrations (LSIs) has been improved. This product is advantageous for downsizing, weight reduction, high functionality, structural electrical function integration, assembly time reduction and cost saving.

  The build-up PCB used in such an application area always forms a via hole for connection between the layers, and the via hole corresponds to an interlayer electrical connection path of the multilayer printed circuit board. In addition, existing machining is performed with a mechanical drill, but the hole diameter is reduced due to miniaturization of the circuit, while machining using a laser is increased due to the increase in machining cost due to mechanical drilling and the limitations of fine hole machining. A method has emerged as an alternative.

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

  Therefore, a method for forming a via hole having a fine diameter at low cost using a photosensitive insulating material instead of the laser processing technique described above has been proposed. Specifically, examples of the photosensitive insulating material include a photosensitive insulating film called a solder resist capable of forming a fine opening pattern using photosensitivity.

  Such photosensitive insulating materials and solder resists are divided into a case where a sodium carbonate developer is used for pattern formation and a case where a different developer is used. In the case of using different developing solutions, there is a limit that the photosensitive insulating material and the solder resist are difficult to apply in an actual process for environmental and cost reasons.

  On the other hand, the use of a sodium carbonate developer has the advantage of being environmentally friendly. In this case, an acid-modified acrylate resin containing a large number of carboxylic acids and acrylate groups is used to impart photosensitivity, but most of the acrylate groups and carboxy groups are linked by ester bonds, so that the desired shape is obtained. In order to polymerize, a polymerization inhibitor or the like is included, and in order to cause a radical reaction by ultraviolet irradiation, a photoinitiator or the like is also included.

  However, the polymerization inhibitor or the photoinitiator is diffused to the outside of the resin under a high temperature condition, and can cause interface desorption with the insulating layer or the conductive layer during or after the semiconductor package process. In addition, the ester bond in the resin causes a hydrolysis reaction at high humidity, causing a decrease in the crosslinking density of the resin and increasing the moisture absorption rate of the resin. Initiators and the like are diffused to the outside of the resin under high temperature conditions, so that interface desorption with the insulating layer and the conductive layer can occur during or after the semiconductor package process, and the HAST characteristics are also deteriorated.

  Therefore, development of a method for manufacturing an insulating layer capable of realizing a uniform and fine pattern at a low cost while preventing interface desorption with an insulating layer or a conductive layer is required.

  The present invention provides a method for manufacturing an insulating layer capable of realizing a uniform and fine pattern and ensuring excellent mechanical properties while improving efficiency in terms of cost and productivity.

  Moreover, this invention provides the manufacturing method of the multilayer printed circuit board using the insulating layer obtained from the manufacturing method of the said insulating layer.

In the present specification, a step of adhering an opposite surface of a metal layer having a carrier film bonded to one surface onto a polymer resin layer containing an alkali-soluble resin and a thermosetting binder; patterned photosensitivity on the carrier film Forming a resin layer; removing a carrier film and a metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer; and forming a carrier film from the patterned metal layer. Separating and removing;
There is provided a method for producing an insulating layer, comprising: alkali-developing the polymer resin layer exposed by the patterned metal layer; and thermally curing the polymer resin layer after the alkali development.

  The present specification also provides a method for manufacturing a multilayer printed circuit board, including a step of forming a metal substrate having a pattern formed on an insulating layer manufactured by the method for manufacturing an insulating layer.

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

  In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

  In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but 1 to 40 is preferable. 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, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl and pentyl. N-pentyl, isopentyl, neopentyl, tert-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, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl- Propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-and methyl hexyl and the like, but is not limited thereto.

  In the present 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 one embodiment, the aryl group has 6 to 20 carbon atoms. Examples of the monocyclic aryl group as the aryl group include, but are not limited to, a phenyl group, a biphenyl group, and a terphenyl group. Examples of the polycyclic aryl group include, but are not limited to, naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrycenyl group, and fluorenyl group.

  According to one embodiment of the invention, the opposite surface of the metal layer having the carrier film bonded on one side thereof is adhered on the polymer resin layer containing the alkali-soluble resin and the thermosetting binder; and patterned on the carrier film. Forming a patterned photosensitive resin layer; removing a carrier film and a metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer; and forming the patterned metal layer. Separating and removing the carrier film from the substrate; alkali-developing the polymer resin layer exposed by the patterned metal layer; and thermosetting the polymer resin layer after the alkali development; A method for manufacturing an insulating layer may be provided.

  According to the manufacturing method of the insulating layer of the one embodiment, the inventors of the present invention have a role of a mask when a metal layer having a pattern introduced on a polymer resin layer having alkali solubility is subjected to alkali development on the polymer resin layer. The portion of the polymer resin layer exposed by the metal layer pattern is removed through alkali development, and the portion of the polymer resin layer that is not exposed by the metal layer pattern is protected from the alkaline developer by a chemical method. It was confirmed that a fine pattern could be realized in the polymer resin layer.

  In addition, the insulating layer on which the fine pattern is formed by the above method can form a more uniform and fine pattern promptly at a low cost compared to the insulating layer manufactured through laser processing. The invention was completed by confirming through experiments that excellent physical properties could be realized in the insulating layer.

  Moreover, the final manufactured insulating layer contains a cured product of a thermosetting resin that is a non-photosensitive insulating material, so that a photoinitiator or The content of polymerization inhibitor was greatly reduced. This makes it possible to produce an insulating layer having excellent mechanical properties, such as an interface desorption property with an insulating layer or a conductive layer that can be generated by a photoinitiator or a polymerization inhibitor is reduced.

  In particular, in the method of manufacturing an insulating layer according to the embodiment, when a metal layer is introduced as a mask on the polymer resin layer, the carrier film is used by performing the process with the carrier film adhered to the metal layer. Not only can the metal layer be easily laminated, but also the carrier film is removed simultaneously with the same etching solution as the metal layer, so that the metal layer can be easily etched even when 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 on the carrier film can be easily removed through physical peeling between the carrier film and the metal layer. There is an advantage in terms of process efficiency that it is not necessary to process a separate stripping solution for the removal.

  The alkali-soluble resin used in the method for manufacturing an insulating layer according to the embodiment includes an acidic functional group in the molecular structure including a cyclic imide functional group substituted with a characteristic amino group together with the acidic functional group. Can achieve alkali solubility, and the cyclic imide functional group substituted with an amino group can increase the curing density upon reaction with a thermosetting binder to improve heat resistance reliability and mechanical properties. Adhesion can be increased.

  Therefore, the polymer resin layer containing the alkali-soluble resin can increase the interfacial adhesive force with the metal layer laminated on the upper part, specifically, the carrier film laminated on the metal layer upper part and Since it can have an adhesive force higher than the interfacial adhesive force between the metal layer, as described above, physical peeling between the carrier film and the metal layer becomes possible.

  Specifically, the method for producing the insulating layer includes the step of adhering the opposite surface of the metal layer having the carrier film adhered to one surface onto a polymer resin layer containing an alkali-soluble resin and a thermosetting binder; Forming a patterned photosensitive resin layer; removing a carrier film and a metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer; Separating and removing the carrier film from the metal layer; developing the polymer resin layer exposed by the patterned metal layer with an alkali; and thermosetting the polymer resin layer after the alkali development. Can be included.

  Hereinafter, specific contents will be described for each stage.

  Adhering the opposite side of the metal layer with the carrier film on one side onto a polymer resin layer containing an alkali-soluble resin and a thermosetting binder

  In the step of adhering the opposite surface of the metal layer having the carrier film adhered to the one surface onto the polymer resin layer containing the alkali-soluble resin and the thermosetting binder, the polymer resin layer is made of the alkali-soluble resin and the thermosetting resin. It means a film formed through drying of a polymer resin composition containing a binder.

  The polymer resin layer can be present alone or in a state where it is formed on a base material containing a semiconductor material such as a circuit board, a sheet, or a multilayer printed wiring board. Examples of the method of forming the upper layer are not particularly limited. For example, the polymer resin composition is directly coated on a substrate, or the polymer resin composition is coated on a carrier film or a metal layer to which the carrier film is bonded. After the application, a method of laminating with a substrate can be used.

  In addition, as an example of a method for adhering the opposite surface of the metal layer having the carrier film adhered to the one surface onto the polymer resin layer containing the alkali-soluble resin and the thermosetting binder, the carrier film is adhered to the one surface. A method of applying a polymer resin composition containing an alkali-soluble resin and a thermosetting binder to the opposite surface of the metal layer and drying it can be used.

  The polymer resin layer may include an alkali-soluble resin and a thermosetting binder.

  The polymer resin layer may include 1 to 150 parts by weight, 10 to 100 parts by weight, or 20 to 50 parts by weight of a thermosetting binder with respect to 100 parts by weight of the alkali-soluble resin. When there is too much content of the said thermosetting binder, the developability of the said polymeric resin layer will fall, and intensity | strength can fall. On the other hand, when the content of the thermosetting binder is too small, not only the polymer resin layer is excessively developed but also the uniformity during coating can be lowered.

  The thermosetting binder includes at least one functional group selected from the group consisting of a thermosetting functional group, an oxetanyl group, a cyclic ether group, a cyclic thioether group, a cyano group, a maleimide group, and a benzoxazine group, and an epoxy group. Can be included. That is, the thermosetting binder necessarily includes an epoxy group, and besides the epoxy group, an oxetanyl group, a cyclic ether group, a cyclic thioether group, a cyanoide group, a maleimide group, a benzoxazine group, or Two or more of these may be mixed and included. Such a thermosetting binder can ensure the heat resistance or mechanical properties of the insulating layer by forming a cross-linking bond with an alkali-soluble resin or the like by thermosetting.

  More specifically, as the thermosetting binder, a multifunctional resin compound containing two or more functional groups described above in the molecule can be used.

  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 binder containing two or more cyclic (thio) ether groups in the molecule is either one or two of three, four or five-membered cyclic ether groups or cyclic thioether groups in the molecule. A compound having at least two groups may be included.

  Examples of the compound having two or more cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resins.

  The polyfunctional resin compound is a polyfunctional epoxy compound containing at least two or more epoxy groups in the molecule, a polyfunctional oxetane compound containing at least two oxetanyl groups in the molecule, or two in the molecule. Including an episulfide resin containing the above thioether group, a polyfunctional cyanate ester compound containing at least two cyano groups in the molecule, or a polyfunctional benzoxazine compound containing at least two benzoxazine groups in the molecule Good.

  Specific examples of the polyfunctional epoxy compound include, for example, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and novolak. Type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolac type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, chelate type epoxy resin, glyoxal type epoxy Resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenolic epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, Tiger glycidyl xylenoyl yl ethane resins, silicone-modified epoxy resins, such as ε- caprolactone-modified epoxy resin. Moreover, you may use what introduced atoms, such as phosphorus, in the structure for flame retardance provision. These epoxy resins are thermally cured to improve properties such as adhesion of the cured film, solder heat resistance, and electroless plating resistance.

  Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene), cardo bisphenol , Calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxy group such as silsesquioxane and the like. Other examples include a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

  Examples of the polyfunctional cyanate ester compound include bisphenol A type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol M type cyanate ester resin, and novolak type cyanate ester. Examples thereof include resins, phenol novolac-type cyanate ester resins, cresol novolac-type cyanate ester resins, bisphenol A novolac-type cyanate ester resins, biphenol-type cyanate ester resins and oligomers or copolymers thereof.

  Examples of the polyfunctional maleimide compound include 4,4'-diphenylmethane bismaleimide (4,4'-diphenylmethane bismaleimide), phenylmethane bismaleimide, m-phenylmethane bismaleimide, and m-phenylmethane bismaleimide. Bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide (3,3′-dimethyl-5,5′-diethyl-4) , 4'-diphenylmethane bismaleimide), 4 Methyl-1,3-phenylenebismaleimide (4-methyl-1,3-phenylene bismaleimide), 1,6′-bismaleimide- (2,2,4-trimethyl) hexane (1,6′-bismaleimide- (2 , 2,4-trimethyl) hexane) and the like.

  Examples of the polyfunctional benzoxazine compound include bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, phenolphthalein type benzoxazine resin, thiodiphenol type benzoxazine resin, dicyclopentadiene type benzoxazine resin, 3 , 3 ′-(methylene-1,4-diphenylene) bis (3,4-dihydro-2H-1,3-benzoxazine (3,3 ′-(methylene-1,4-diphenylene) bis (3,4) dihydro-2H-1,3-benzoxazine) resin and the like.

  More specific examples of the polyfunctional resin compound include YDCN-500-80P manufactured by Kokuto Chemical Co., Ltd., phenol novolak-type cyanate ester resin PT-30S manufactured by Lonza Japan Co., Ltd., Daiwa Kasei Kogyo Co., Ltd. And phenylmethane type maleimide resin BMI-2300 manufactured by Shikoku Kasei Kogyo Co., Ltd. and Pd type benzoxazine resin.

  Meanwhile, the alkali-soluble resin may include at least one or two or more cyclic imide functional groups each substituted with an amino group; and an amino group. Although the example of the said acidic functional group is not specifically limited, For example, a carboxy group or a phenol group can be included. The alkali-soluble resin contains at least one or two or more acidic functional groups so that the polymer resin layer exhibits higher alkali developability, and the development speed of the polymer resin layer can be adjusted.

  The cyclic imide functional group substituted with the amino group includes an amino group and a cyclic imide group in the functional group structure, and may be included in at least one or two or more. When the alkali-soluble resin contains at least one or two or more cyclic imide functional groups substituted with the amino group, the alkali-soluble resin has a large number of active hydrogens contained in the amino group. It has a structure and can improve the heat density and mechanical properties by increasing the curing density while improving the reactivity with the thermosetting binder during thermosetting.

  Further, since a large number of the cyclic imide functional groups are present in the alkali-soluble resin, the polarity is increased by the carbonyl group and the tertiary amine group contained in the cyclic imide functional group, and the interfacial adhesive force of the alkali-soluble resin is increased. Can be increased. As a result, the polymer resin layer containing the alkali-soluble resin can increase the interfacial adhesive force with the metal layer laminated on the upper part, specifically, the carrier film laminated on the metal layer upper part. As described later, physical peeling between the carrier film and the metal layer becomes possible.

  More specifically, the cyclic imide functional group substituted with the amino group may include a functional group represented by the following chemical formula 1.

In Chemical Formula 1, R ₁ is an alkylene group or alkenyl group having 1 to 10 carbon atoms, 1 to 5 carbon atoms, or 1 to 3 carbon atoms, and “ ^* ” means a point of attachment. The alkylene group is a divalent functional group derived from alkane, for example, a linear, branched or cyclic methylene group, ethylene group, propylene group, isobutylene group, sec-butylene group, Examples thereof include a tert-butylene group, a pentylene group, and a hexylene group. One or more hydrogen atoms contained in the alkylene group may be substituted with different substituents. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms. , Alkynyl group having 2 to 10 carbon atoms, aryl group having 6 to 12 carbon atoms, heteroaryl group having 2 to 12 carbon atoms, arylalkyl group having 6 to 12 carbon atoms, halogen atom, cyano group, amino group, amidino group , A nitro group, an amide group, a carbonyl group, a hydroxy group, a sulfonyl group, a carbamate group, an alkoxy group having 1 to 10 carbon atoms, and the like.

  The term “substituted” means that another functional group is bonded in place of a hydrogen atom in a compound, and the substituted position is a position where a hydrogen atom is substituted, that is, the substituent can be substituted. There is no limitation as long as it is a position, and when two or more substituents are substituted, the two or more substituents may be the same or different from each other.

  The alkenyl group means that one or more carbon-carbon double bonds are contained in the middle or terminal of the above-described alkylene group, and examples thereof include ethylene, propylene, butylene, hexylene, and acetylene. One or more hydrogen atoms in the alkenyl group can be substituted with the same substituent as in the alkylene group.

  Preferably, the cyclic imide functional group substituted with the amino group may be a functional group represented by the following chemical formula 2.

In Chemical Formula 2, “ ^* ” means a point of attachment.

  As described above, the alkali-soluble resin includes a cyclic imide functional group substituted with an amino group together with an acidic functional group. Specifically, the alkali-soluble resin has an acidic function on at least one terminal of the cyclic imide functional group substituted with the amino group. Groups can be attached. At this time, the cyclic imide functional group substituted with the amino group and the acidic functional group can be bonded via a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, for example, a cyclic group substituted with the amino group. An acidic functional group can be bonded to the terminal of the amino group contained in the imide functional group via a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and the cyclic imide functional group substituted with the amino group An acidic functional group can be bonded to the terminal of the contained imide functional group via a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group.

  More specifically, the terminal of the amino group contained in the cyclic imide functional group substituted with the amino group means a nitrogen atom contained in the amino group in the chemical formula 1, and is substituted with the amino group. The term “end of the imide functional group contained in the cyclic imide functional group” means a nitrogen atom contained in the cyclic imide functional group in Chemical Formula 1.

  The alkylene group is a divalent functional group derived from alkane, for example, a linear, branched or cyclic methylene group, ethylene group, propylene group, isobutylene group, sec-butylene group, Examples thereof include a tert-butylene group, a pentylene group, and a hexylene group. One or more hydrogen atoms contained in the alkylene group may be substituted with different substituents. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms. , Alkynyl group having 2 to 10 carbon atoms, aryl group having 6 to 12 carbon atoms, heteroaryl group having 2 to 12 carbon atoms, arylalkyl group having 6 to 12 carbon atoms, halogen atom, cyano group, amino group, amidino group , A nitro group, an amide group, a carbonyl group, a hydroxy group, a sulfonyl group, a carbamate group, an alkoxy group having 1 to 10 carbon atoms, and the like.

  The arylene group is a divalent functional group derived from arene, and examples thereof include a cyclic phenyl group and a naphthyl group. One or more hydrogen atoms contained in the arylene group may be substituted with different substituents. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms. , Alkynyl group having 2 to 10 carbon atoms, aryl group having 6 to 12 carbon atoms, heteroaryl group having 2 to 12 carbon atoms, arylalkyl group having 6 to 12 carbon atoms, halogen atom, cyano group, amino group, amidino group , A nitro group, an amide group, a carbonyl group, a hydroxy group, a sulfonyl group, a carbamate group, an alkoxy group having 1 to 10 carbon atoms, and the like.

  Although the example of the method of manufacturing the said alkali-soluble resin is not specifically limited, For example, it can manufacture through reaction of a cyclic unsaturated imide compound; and an amine compound. At this time, at least one of the cyclic unsaturated imide compound and the amine compound may include an acidic functional group substituted at a terminal. That is, the cyclic unsaturated imide compound, the amine compound, or any of these two compounds can be substituted with an acidic functional group at the terminal. The contents for the acidic functional group are as described above.

  The cyclic imide compound is a compound containing the above-mentioned cyclic imide functional group, and the cyclic unsaturated imide compound is a compound containing at least one unsaturated bond, that is, at least one double bond or triple bond in the cyclic imide compound. Means.

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

  Although the example of the weight ratio with which the said cyclic unsaturated imide compound and an amine compound are made to react is not specifically limited, For example, the said amine compound is 10-80 weight part with respect to 100 weight part of the said cyclic unsaturated imide compound, or 30- It can be made to react by mixing at 60 parts by weight.

  Examples of the cyclic unsaturated imide compound include N-substituted maleimide compounds. N-substituted means that a functional group is bonded instead of a hydrogen atom bonded to a nitrogen atom contained in the maleimide compound, and the N-substituted maleimide compound is an N-substituted maleimide compound. According to the number, it is classified into a monofunctional N-substituted maleimide compound and a polyfunctional N-substituted maleimide compound.

  The monofunctional N-substituted maleimide compound is a compound in which an active group is substituted on a nitrogen atom contained in one maleimide compound, and the polyfunctional N-substituted maleimide compound is added to each of two or more maleimide compounds. It is a compound in which the contained nitrogen atom is bonded through a functional group.

  In the monofunctional N-substituted maleimide compound, the functional group substituted by the nitrogen atom contained in the maleimide compound can include various known aliphatic, alicyclic or aromatic functional groups without limitation. The functional group substituted by the nitrogen atom may also include a functional group in which an acidic functional group is substituted for an aliphatic, alicyclic or aromatic functional group. The contents for the acidic functional group are as described above.

  Specific examples of the monofunctional N-substituted maleimide compound include o-methylphenylmaleimide, p-hydroxyphenylmaleimide, p-carboxyphenylmaleimide, and dodecylmaleimide.

  In the polyfunctional N-substituted maleimide compound, the functional group that mediates the bond between nitrogen atoms contained in each of the two or more maleimide compounds may be a variety of known aliphatic, alicyclic, or aromatic functional groups. As a specific example, a 4,4′-diphenylmethane functional group or the like can be used. The functional group substituted with the nitrogen atom may include a functional group in which an acidic functional group is substituted for an aliphatic, alicyclic or aromatic functional group. The contents for the acidic functional group are as described above.

  Specific examples of the polyfunctional N-substituted maleimide compound include 4,4′-diphenylmethane bismaleimide (BMI-1000, BMI-1100, etc. manufactured by Daiwa Kasei Kogyo Co., Ltd.), phenylmethane bismaleimide, m- Phenylenemethane bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6 ′ -Bismaleimide- (2,2,4-trimethyl) hexane and the like.

As the amine compound, a primary amine compound having at least one amino group (—NH ₂ ) in the molecular structure can be used, and more preferably, a carboxylic acid compound substituted with an amino group, two or more. A polyfunctional amine compound containing any amino group or a mixture thereof can be used.

  In the carboxylic acid compound substituted with the amino group, the carboxylic acid compound is a compound containing a carboxylic acid (—COOH) functional group in the molecule, and is aliphatic depending on the type of hydrocarbon bonded to the carboxylic acid functional group. All of the alicyclic or aromatic carboxylic acids can be included. The development property of the alkali-soluble resin can be improved while a large number of carboxylic acid functional groups of the acidic functional group are contained in the alkali-soluble resin through the carboxylic acid compound substituted with the amino group.

  The term “substituted” means that another functional group is bonded instead of a hydrogen atom in the compound, and the position where the amino group is substituted in the carboxylic acid compound is the position where the hydrogen atom is substituted. As long as it is not limited, the number of substituted amino groups may be one or more.

  Specific examples of the carboxylic acid compound substituted with the amino group include about 20 kinds of α-amino acids, 4-aminobutanoic acid, 5-aminopentanoic acid, 6-aminohexanoic acid known as protein raw materials, Examples include 7-aminoheptanoic acid, 8-aminooctanoic acid, 4-aminobenzoic acid, 4-aminophenylacetic acid, and 4-aminocyclohexanecarboxylic acid.

In addition, the polyfunctional amine compound containing two or more amino groups is a compound containing two or more amino groups (—NH ₂ ) in the molecule, and depending on the type of hydrocarbon bonded to the amino group, All aromatic, alicyclic or aromatic polyfunctional amines can be included. The flexibility, toughness, copper foil adhesion, etc. of the alkali-soluble resin can be improved through the polyfunctional amine compound containing two or more amino groups.

  Specific examples of the polyfunctional amine compound containing two or more amino groups include 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis (aminomethyl) -cyclohexane, 1,4 -Bis (aminomethyl) -cyclohexane, bis (aminomethyl) -norbornene, octahydro-4,7-methanoindene-1 (2), 5 (6) -dimethanamine, 4,4'-methylenebis (cyclohexylamine), 4, 4'-methylenebis (2-methylcyclohexylamine), isophoronediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,3,5,6- Tetramethyl-1,4-phenylenediamine, 2,4,5,6-tetrafluoro-1,3-pheny Diamine, 2,3,5,6-tetrafluoro-1,4-phenylenediamine, 4,6-diaminoresinol, 2,5-diamino-1,4-benzenedithiol, 3-aminobenzylamine, 4- Aminobenzylamine, m-xylenediamine, p-xylenediamine, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 2,6-diaminoanthraquinone, m-tolidine, o-tolidine, 3,3 ', 5 5'-tetramethylbenzidine (TMB), o-dianisidine, 4,4'-methylenebis (2-chloroaniline), 3,3'-diaminobenzidine, 2,2'-bis (trifluoromethyl) -benzidine, 4 , 4′-diaminooctafluorobiphenyl, 4,4′-diamino-p-terphenyl, 3,3′-diaminodiphe Rumethane, 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′-diaminobenzophenone, 4,4′-diaminobenzophenone, 4,4′-ethylenedianiline, 4,4′-diamino-2,2 '-Dimethylbibenzyl, 2,2'-bis (3-amino-4-hydroxyphenyl) propane, 2,2'-bis (3-aminophenyl) -hexafluoropropane, 2,2'-bis (4- Aminophenyl) -hexafluoropropane, 2,2′-bis (3-amino-4-methylphenyl) -hexafluoropropane, 2,2′- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,1′-bis (4-aminophenyl) -cyclohexane, 9,9′-bis (4-aminophenyl) -fluorene, 9,9′-bis (4-amino-3- Chlorophenyl) fluorene, 9,9′-bis (4-amino-3-fluorophenyl) fluorene, 9,9′-bis (4-amino-3-methylphenyl) fluorene, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 1,3-bis (3-aminophenoxy) -benzene, 1,3-bis (4-aminophenoxy) -benzene, 1,4- (4-aminophenoxy) -benzene, 1,4-bis (4-amino-2-trifluoromethylphenoxy) -benzene, 4,4′-bis (4-aminophenoxy) -biphenyl, 2,2′- Bis [4- (4-aminophenoxy) -phenyl] propane, 2,2′-bis [4- (4-aminophenoxy) -phenyl] hexafluoropropane, bis (2-aminophenyl) sulfide, bis (4- Aminophenyl) sulfide, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, bis (3-amino-4-hydroxy) sulfone, bis [4- (3-aminophenoxy) -phenyl] sulfone, Bis [4- (4-aminophenoxy) -phenyl] sulfone, o-tolidinesulfone, 3,6-diaminocarbazole, 1,3,5- Tris (4-aminophenyl) -benzene, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, 4,4′-diaminobenzanilide, 2- (3-aminophenyl) -5-aminobenzimidazole 2- (4-aminophenyl) -5-aminobenzoxazole, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, 4,6 -Diaminoresorcinol, 2,3,5,6-pyridinetetraamine, polyfunctional amine containing siloxane structure of Shin-Etsu silicone (PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012) , KF-8008, X-22-1660B-3, X-22-9409), a polyfunctional amine containing Dow Corning siloxane structure Dow Corning3055), polyfunctional amine containing polyether structure (Huntsman Corporation, BASF Corporation).

  The alkali-soluble resin may include at least one repeating unit represented by the following chemical formula 3; and at least one repeating unit represented by the following chemical formula 4.

In 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 bonding point. ,

In 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, and R ₄ is —H, —OH, -NR ₅ R _6, halogen, or an alkyl group having 1 to 20 carbon atoms, wherein _{R 5} and _{R 6} are each independently hydrogen, alkyl group having 1 to 20 carbon atoms or 6 to 20 carbon atoms, It may be an aryl group, and “ ^* ” means a point of attachment.

Preferably, in Chemical Formula 3, R ₂ may be phenylene, and in Chemical Formula 4, R ₃ may be phenylene 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 repeating unit is a repeating unit contained in a homopolymer of a vinyl monomer containing at least one vinyl group in the molecule, and examples of the vinyl monomer are particularly limited. Examples thereof include ethylene, propylene, isobutylene, butadiene, styrene, acrylic acid, methacrylic acid, maleic anhydride, and maleimide.

  The alkali-soluble resin containing at least one repeating unit represented by Chemical Formula 3 and at least one repeating unit represented by Chemical Formula 3 is a polymer containing a repeating unit represented by Chemical Formula 5 below, It can be produced by the reaction of an amine represented by Chemical Formula 6 and an amine represented by Chemical Formula 7 below.

In the chemical formulas 5 to 7, R _{2 to} R ₄ are the same as those described above in the chemical formulas 3 and 4, and “ ^* ” means a bonding point.

  Specific examples of the polymer including the repeating unit represented by Formula 5 are not particularly limited. For example, SMA from Cray valley, Xiran from Polyscope, Scripes from Solenis, Isobam from Kuraray, and Chevron Phillips Chemical Polyhydride resin of the company, Maldene of Lindau Chemicals, and the like.

  Further, the alkali-soluble resin containing at least one repeating unit represented by Chemical Formula 3; and at least one repeating unit represented by Chemical Formula 3 is represented by the following compound represented by Chemical Formula 8 and Chemical Formula 9 below. It can be produced by the reaction of the compound represented.

In the chemical formulas 8 to 9, R _{2 to} R ₄ are the same as those described above in the chemical formulas 3 and 4.

  The alkali-soluble resin may be a known and commonly used carboxy group-containing resin or phenol group-containing resin containing a carboxy group or a phenol group in the molecule. Preferably, a phenol group-containing resin can be mixed with the carboxy group-containing resin or the carboxy group-containing resin.

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

(1) A carboxy group-containing resin obtained by reacting a polyfunctional epoxy resin with a saturated or unsaturated monocarboxy group and then reacting with a polybasic acid anhydride,
(2) a carboxy group-containing resin obtained by reacting a bifunctional epoxy resin with a bifunctional phenol and / or a dicarboxy group and then reacting with a polybasic acid anhydride,
(3) A carboxy group-containing resin obtained by reacting a polyfunctional phenol resin with a compound having one epoxy group in the molecule and then reacting with a polybasic acid anhydride,
(4) a carboxy group-containing resin obtained by reacting a polybasic acid anhydride with a compound having two or more alcoholic hydroxyl groups in the molecule;
(5) A polyamic acid resin obtained by reacting diamine and dianhydride or a copolymer resin of polyamic acid resin,
(6) A polyacrylic acid resin reacted with acrylic acid or a copolymer of polyacrylic acid resin,
(7) Manufactured by ring-opening polymaleic anhydride resin and maleic anhydride resin copolymer anhydride reacted with maleic anhydride with weak acid, diamine, imidazole, dimethyl sulfoxide However, it is not limited to these.

  More specific examples of the carboxy group-containing resin include CCR-1291H manufactured by Nippon Kayaku Co., Ltd., SHA-1216CA60 manufactured by SHIN-A T & C, Novelite K-700 manufactured by Lubrizol, or two of these. The above mixture etc. are mentioned.

  Examples of the phenol group-containing resin are not particularly limited. For example, a phenolic novolac resin, a cresol novolac resin, a borac resin such as bisphenol F (BPF) novolac resin, or 4,4 ′-(1- (4- (2- (4-Hydroxyphenyl) propan-2-yl) phenyl) ethane-1,1-diyl) diphenol [4,4 ′-(1- (4- (2- (4-hydroxyphenyl) propan-2-yl) Bisphenol A resins such as phenyl) ether-1,1-diyl) diphenol] can be used alone or in combination.

  The polymer resin layer may further include one or more additives 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 mg KOH / g to 250 mg KOH / g, or 70 mg KOH / g to 200 mg KOH / g. Although the example of the method of measuring the acid value of the said alkali-soluble resin is not specifically limited, For example, the following methods can be used. A 0.1N concentration KOH solution (solvent: methanol) was prepared as a base solution, and alpha-naphtholbenzene (pH: 0.8-8) was used as an indicator. .2 yellow, 10.0 blue green). Next, about 1 to 2 g of an alkali-soluble resin as a sample was collected and dissolved in 50 g of a dimethylformaldehyde (DMF) solvent, and after adding a label, it was titrated with a base solvent. The acid value was determined in units of mg KOH / g by the amount of base solvent used at the completion of the titration.

  If the acid value of the alkali-soluble resin is too low to be less than 50 mg KOH / g, the developability of the alkali-soluble resin may be lowered and the development process may be difficult to proceed. If the acid value of the alkali-soluble resin exceeds 250 mg KOH / g and increases too much, phase separation from other resins may occur due to the increase in polarity.

  The thermosetting catalyst plays a role of promoting thermosetting of the thermosetting binder. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1 Imidazole derivatives such as-(2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethyl Examples include amine compounds such as benzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N and UCAT3502T manufactured by San Apro. (All are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATS A102, U-CAT5002 (all bicyclic amidine compounds and salts thereof), and the like. It is not particularly limited to these, and may be a thermosetting catalyst for an epoxy resin or an oxetane compound, or a catalyst that promotes a reaction between an epoxy group and / or an oxetanyl group and a carboxy group. It can also be used by mixing. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl-4,6 S-triazine derivatives such as -diamino-S-triazine-isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct can also be used. A compound that also functions as an imparting agent can be used in combination with the 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.

  An example of the content of the inorganic filler is not particularly limited, but in order to achieve high rigidity of the polymer resin layer, with respect to 100 parts by weight of all the resin components contained in the polymer resin layer, The inorganic filler can be added at 100 parts by weight or more, or 100 to 600 parts by weight, or 100 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 waxes, carnauba waxes, and paraffin waxes.

  As the metal adhesion promoter, a substance that does not cause a problem in surface modification or transparency of a metal material, for example, a silane coupling agent or an organometallic coupling agent can be used.

  The leveling agent serves to remove surface popping and craters during film coating. For example, BYK-Chemie GmbH's BYK-380N, BYK-307, BYK-378, and BYK-350 can be used.

  The polymer resin layer may further include a resin or elastomer having a molecular weight of 5000 or more that can induce phase separation. This makes it possible to roughen the cured product of the polymer resin layer.

  The example of the molecular weight measuring method of the resin or elastomer having a molecular weight of 5000 or more is not particularly limited, and means, for example, a polystyrene-equivalent weight average molecular weight measured by GPC method. In the process of measuring the polystyrene-equivalent weight average molecular weight measured by the GPC method, a commonly known analyzer and a detector such as a differential refractive index detector (Refractive Index Detector) and an analytical column can be used. Temperature conditions, solvent, flow rate can be applied. Specific examples of the measurement conditions include a temperature of 30 ° C., a chloroform solvent (Chloroform), and a flow rate of 1 mL / min.

  The polymer resin layer includes a thermosetting binder containing a photoreactive unsaturated group or an alkali-soluble resin containing a photoreactive unsaturated group in order to impart photocurable properties to the polymer resin layer. A photoinitiator can further be included. Specific examples of the thermosetting binder containing the photoreactive unsaturated group, the alkali-soluble resin containing the photoreactive unsaturated group, and the photoinitiator are not particularly limited, and the related technical field of the photocurable resin composition The various compounds used in can be used without limitation.

  On the other hand, on the polymer resin layer, the opposite surface of the metal layer having a carrier film adhered on one surface can be adhered. Examples of the metal contained in the metal layer include metals such as gold, silver, copper, tin, nickel aluminum, and titanium, or alloys containing a mixture of two or more of these, and the thickness of the metal layer. May be 10 nm to 10 μm. If the thickness of the metal layer exceeds 10 μm and increases too much, raw material costs increase and economical efficiency decreases as excess metal is required to form the metal layer. be able to.

  A carrier film is bonded to one surface of the metal layer. The carrier film is bonded to one surface of the metal layer to prevent direct contact with the surface of the metal layer in a process such as moving or bonding the metal layer. After the metal layer is bonded, the carrier film is physically peeled off. Can be easily removed. Specific examples of the carrier film are not particularly limited, and various organic and inorganic materials such as polymers, metals, and rubbers can be applied. In the said one Embodiment, Preferably the same raw material as the said metal layer can be used as a raw material of a carrier film. Therefore, as will be described later, the carrier film and the metal layer can be simultaneously etched with the same etchant to form a pattern.

  Meanwhile, the opposite surface of the metal layer to which the carrier film is bonded can be bonded to the polymer resin layer. The opposite surface of one surface of the metal layer means a surface parallel to the one surface of the metal layer and facing each other, and the opposite surface of the one surface of the metal layer to which the carrier film is bonded is bonded to the polymer resin layer. A structure in which a metal layer on a polymer resin layer and a carrier film on the metal layer are sequentially laminated can be formed.

  At this time, the adhesive force between the carrier film and the metal layer may be smaller than the adhesive force between the polymer resin layer and the metal layer. Therefore, as will be described later, it is possible to prevent peeling between the polymer resin layer and the metal layer during physical peeling between the carrier film and the metal layer. If 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, the polymer resin layer and the metal layer are peeled off when the carrier film and the metal layer are physically peeled off. Thus, it is difficult to form a fine pattern on the polymer resin layer.

  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 a pattern may be formed after being laminated, more preferably, the layer is formed on the carrier film. A pattern can be formed after being applied.

  Examples of the photosensitive resin layer include alkali-soluble and non-thermosetting photosensitive dry film resist (DFR).

  The step of forming a protective layer having a pattern formed on the carrier film may include a step of exposing and alkali developing the photosensitive resin layer formed on the carrier film. In this case, the photosensitive resin layer is used as a protective layer for the carrier film or a patterning mask.

  In the step of exposing and alkali developing the photosensitive resin layer formed on the carrier film, the thickness of the photosensitive resin layer formed on the carrier film is 1 μm to 500 μm, or 3 μm to 500 μm, or 3 μm to It can be 200 μm, or 1 μm to 60 μm, or 5 μm to 30 μm. If the thickness of the photosensitive resin layer increases too much, the resolution of the polymer resin layer can be reduced.

  The method of forming the photosensitive resin layer on the carrier film in the step of exposing and alkali developing the photosensitive resin layer formed on the carrier film is not particularly limited. For example, a photosensitive dry film resist is used. A method of laminating a photosensitive resin in the form of a film on a carrier film, a method of coating a photosensitive resin composition on a carrier film by a spraying or dipping method, and press-bonding can be used.

An example of a method of exposing the photosensitive resin layer in the stage of exposing and alkali developing the photosensitive resin layer formed on the carrier film is not particularly limited. For example, a predetermined pattern is formed on the photosensitive resin layer. The formed photomask is contacted and irradiated with ultraviolet rays, or a predetermined pattern included in the mask is imaged through a projection objective lens, and then irradiated with ultraviolet rays, or a laser diode (Laser Diode) is used as a light source. After direct imaging, it can be selectively exposed through a method such as irradiation with ultraviolet rays. In this case, examples of ultraviolet irradiation conditions include irradiating light quantity of 5 mJ / cm ² to 600 mJ / cm ^2.

  An example of a method of developing the photosensitive resin layer at the stage of exposing and alkali developing the photosensitive resin layer formed on the carrier film is a method of treating an alkaline developer. Examples of the alkaline developer are not particularly limited. For example, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, amines may be used. Preferably, a 30 ° C., 1% sodium carbonate developer can be used. The specific usage amount of the alkali developer is not particularly limited.

  When processing the alkali developer, only a part of the photosensitive resin layer is removed by development, the polymer resin layer containing the alkali-soluble resin and the thermosetting binder located at the bottom is protected by the carrier film, Development can be prevented. Therefore, a separate process for preventing the development of the polymer resin layer, for example, the polymer resin layer is cured in advance, or two or more different metal layers are introduced and sequentially patterned with different etchants. By using a fine metal layer formed on the polymer resin layer as a resist mask without using a process, the aspect ratio can be lowered to increase the resolution of the via hole.

  Removing the exposed carrier film and metal layer 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 photosensitive resin layer pattern, 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 photosensitive resin layer pattern mean a carrier film and a metal layer portion that do not come into contact with the photosensitive resin layer on the surface.

  Specifically, the step of removing the carrier film and the metal layer exposed by the photosensitive resin layer pattern includes the step of contacting the carrier film and the metal layer with the etching solution passing through the photosensitive resin layer on which the pattern is formed. Can be included.

  The etchant is selected according to the type of the carrier film and the metal layer, and it is preferable to use a substance that has as little influence on the lower copper line as possible and does not affect the photosensitive resin layer.

  However, as described above, in the embodiment, the carrier film and the metal layer are preferably removed simultaneously or sequentially with the same etching solution by using the same material as the metal layer as the material of the carrier film. A pattern can be easily formed.

  Meanwhile, in the step of forming the patterned metal layer by removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer, the ratio of the polymer resin layer to be removed is the entire polymer resin layer It may be 0.01% by weight or less with respect to the weight of. When the ratio of the polymer resin layer to be removed is 0.01% by weight or less with respect to the weight of the entire polymer resin layer, the degree to which the polymer resin layer is removed is very small, Means not removed.

  That is, the etchant used 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 is physically applied to the polymer resin layer. The polymer resin layer can be stably maintained until the fine metal pattern layer is formed, and the aspect ratio is reduced by using the fine metal pattern layer as a resist mask. As a result, the resolution of the via hole can be increased.

  Separating and removing the carrier film from the patterned metal layer;

  As described above, after the step of forming the patterned metal layer by removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer, it is patterned on the polymer resin layer. A metal layer, a patterned carrier film, and a patterned photosensitive resin layer can be sequentially laminated.

  At this time, in order to form the insulating layer, all of the remaining layers except the polymer resin layer and the patterned metal layer formed on the polymer resin layer must be removed. For this reason, conventionally, an alkaline developer is used to remove the photosensitive resin layer used for pattern formation. At this time, the alkaline developer develops the polymer resin layer simultaneously or sequentially. There was a problem. Further, when the metal layer used for pattern formation is used, problems such as corrosion of the lower copper line can be caused by using an etching solution to remove the metal layer.

  On the other hand, in the case of the one embodiment, the remaining portions except for the polymer resin layer and the patterned metal layer formed on the polymer resin layer through a simple method of separating and removing the carrier film and the metal layer are removed. The layer can be easily removed.

  In the 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, the polymer is physically separated from the carrier film and the metal layer. Peeling between the resin layer and the metal layer can be prevented.

  Further, in the process of separating the carrier film and the metal layer, the carrier film and the photosensitive resin layer formed on the carrier film are removed together in an adhered or peeled state. Even without using a liquid, it is possible to easily increase the resolution of the via hole by leaving only the fine metal pattern mask on the polymer resin layer and reducing the aspect ratio through a patterning process described later.

  A step of alkali developing the polymer resin layer exposed by the patterned metal layer

  The method for manufacturing the insulating layer may include a step of alkali developing the polymer resin layer exposed by the metal layer pattern. As described above, through the process of selectively contacting the surface of a part of the polymer resin layer exposed through the fine pattern formed on the metal layer with an alkaline developer, the conventional laser etching process may be substituted. Therefore, it is possible to ensure a precision equal to or higher than this level and a higher process economy.

  In the step of alkali developing the polymer resin layer exposed by the metal layer pattern, the 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 polymer resin layer portion whose surface does not contact the metal layer.

  Specifically, the step of alkali developing the polymer resin layer exposed by the metal layer pattern may include a step in which an alkali developer passes through the metal layer having the pattern and contacts the polymer resin layer. .

  Since the polymer resin layer contains an alkali-soluble resin, the polymer resin layer has an alkali-solubility that is dissolved by an alkali developer. Therefore, a portion of the polymer resin layer in contact with the alkali developer is dissolved and removed. be able to.

  On the other hand, after the step of alkali developing the polymer resin layer exposed by the patterned metal layer, 0.1 wt% or more based on the total weight of the polymer resin layer exposed by the patterned metal layer. 85% by weight, or 0.1% to 50% by weight, or 0.1% to 10% by weight can remain. This is because the alkali-soluble resin contained in the polymer resin layer is removed by the alkali developer, but the thermosetting binder or the inorganic filler having almost no alkali developability remains without being removed.

  As a result, when the patterned metal layer is removed by an etchant treatment as necessary, it is possible to minimize the occurrence of etch back due to the etching of the lower copper foil exposed by the pattern together. .

  Meanwhile, the polymer resin layer remaining after the step of alkali developing the polymer resin layer exposed by the patterned metal layer can be removed by treating with a stripping solution or the like. In other words, after the step of alkali developing the polymer resin layer exposed by the patterned metal layer, a step of treating the stripping solution can be further included, and the type and processing method of the stripping solution are not particularly limited.

  In particular, in order to adjust the degree to which the inorganic filler and the thermosetting binder remain, the weight ratio of the alkali-soluble resin to the thermosetting binder and the inorganic filler, the acidic functional group ratio on the surface of the inorganic filler, and the like can be adjusted. Preferably, 100 to 100 parts by weight of the alkali-soluble resin and 20 to 100 parts by weight of the thermosetting binder and 100 to 600 parts by weight of the inorganic filler can be added, and the acid value on the surface of the inorganic filler is 0 mgKOH. / G to 5 mg KOH / g, or 0.01 mg KOH / g to 5 mg KOH / g. The contents relating to the acid value are the same as the method for measuring the acid value of the alkali-soluble resin.

  Examples of the alkaline developer are not particularly limited. For example, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, amines may be used. Preferably, a 30 ° C., 1% sodium carbonate developer can be used. The specific usage amount of the alkali developer is not particularly limited.

  Step of thermosetting the polymer resin layer after alkali development

  The method for manufacturing the insulating layer may include a step of thermosetting the polymer resin layer after the alkali development. The step of thermosetting the polymer resin layer may be performed at a temperature of 100 ° C. to 250 ° C.

  Meanwhile, the method may further include the step of removing the metal layer on the polymer resin layer after the step of thermosetting the polymer resin layer. As the method for removing the metal layer, a method in which the metal layer can be removed while removing the copper line below the polymer resin layer or removing only a part thereof can be used.

  As a concrete example, the copper foil thickness of the metal layer is made very thin as 3 μm or less, and the metal layer is removed while removing a part of the lower copper line, or the metal layer is removed, An etchant that does not affect the copper line can be used.

  Meanwhile, according to another embodiment of the invention, there is provided a method of manufacturing a multilayer printed circuit board, including a step of forming a metal substrate having a pattern formed on the insulating layer manufactured in the one embodiment. Can do.

  The inventors of the present invention include that the insulating layer manufactured in the embodiment includes a certain opening pattern, so that the inside of the opening pattern is filled with metal in the process of further laminating a metal substrate on the insulating layer. As a result, it was confirmed that the metal substrates positioned at the upper part and the lower part with respect to the insulating layer were connected to each other to manufacture a multilayer printed circuit board, and the invention was completed.

  The insulating layer can be used as an interlayer insulating material for a multilayer printed circuit board, and can include an alkali-soluble resin and a thermoset of a thermosetting binder. The content regarding the alkali-soluble resin and the thermosetting binder includes the content described above in the embodiment. If necessary, a copper foil layer having a thickness of 5 μm or less may be formed on the surface of the insulating layer.

  The step of forming a metal substrate having a pattern formed on the insulating layer is a fine circuit pattern forming process known in the art as Semi-Additive Process (SAP) or Modified Semi-Additive Process (MSAP). The SAP process means forming a fine circuit pattern with nothing on the insulating layer, and the MSAP process forms a fine circuit pattern with a copper foil of 5 μm or less formed on the insulating layer. It means to form.

  More specifically, the step of forming a metal substrate having a pattern formed on the insulating layer includes, for example, a step of forming a metal thin film on the insulating layer; and a photosensitivity having a pattern formed on the metal thin film. Forming a resin layer; depositing a metal on the metal thin film exposed by the photosensitive resin layer pattern; and removing the photosensitive resin layer and removing the exposed metal thin film.

  In the step of forming the metal thin film on the insulating layer, examples of the method of forming the metal thin film include a dry deposition process or a wet deposition process. Specific examples of the dry deposition process include vacuum deposition and ion deposition. Examples thereof include plating and sputtering methods. Meanwhile, specific examples of the wet deposition process include electroless plating of various metals, and more specifically, electroless copper plating can be used. In addition, a roughening process may be further included before or after the vapor deposition.

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

  Also in the roughening treatment step, there are dry and wet methods depending on conditions. Examples of the dry method include vacuum, normal pressure, plasma treatment by gas, and excimer UV treatment by gas. As an example of the method, desmear treatment can be used. Through such a roughening treatment step, the surface roughness of the metal thin film can be increased to improve the adhesion with the metal deposited on the metal thin film.

  In addition, forming the metal thin film on the insulating layer may further include forming a surface treatment layer on the insulating layer before depositing the metal thin film. Thereby, the adhesive force between the metal thin film and the insulating layer can be improved.

  Specifically, as an example of a method for forming a surface treatment layer on the insulating layer, at least one of an ion-assisted reaction method, an ion beam treatment method, and a plasma treatment method can be used. The plasma processing method may include any one of a normal pressure plasma processing method, a DC plasma processing method, and an RF plasma processing method. As a result of the surface treatment step, a surface treatment layer containing a reactive functional group can be formed on the surface of the insulating layer. As another example of the method of forming the surface treatment layer on the insulating layer, a method of vapor-depositing chromium (Cr) or titanium (Ti) metal having a thickness of 50 nm to 300 nm on the surface of the insulating layer can be given.

  Meanwhile, forming the photosensitive resin layer having the pattern formed on the metal thin film may include exposing and developing the photosensitive resin layer formed on the metal thin film. The contents for the photosensitive resin layer and exposure and development may include the contents described above in the embodiment.

  The metal thin film exposed by the photosensitive resin layer pattern in the step of depositing a metal on the metal thin film exposed by the photosensitive resin layer pattern means a metal thin film portion that does not contact the photosensitive resin layer on the surface. The metal to be vapor-deposited can use copper, examples of the vapor deposition method are not particularly limited, and various known physical or chemical vapor deposition methods can be used without limitation. A plating method can be used.

  In the step of removing the photosensitive resin layer and removing the exposed metal thin film, as an example of the method for removing the photosensitive resin layer, a photoresist stripping solution can be used, and by removing the photosensitive resin layer, As an example of the method for removing the exposed metal thin film, an etching solution can be used.

  The multilayer printed circuit board manufactured by the multilayer printed circuit board manufacturing method can be used again as a build-up material. For example, the insulating layer is formed on the multilayer printed circuit board by the insulating layer manufacturing method of the embodiment. The first step of forming the metal substrate and the second step of forming the metal substrate on the insulating layer by the multilayer printed circuit board manufacturing method of the other embodiment can be performed repeatedly.

  Therefore, the number of stacked layers included in the multilayer printed circuit board manufactured by the multilayer printed circuit board manufacturing method is not particularly limited, and may include, for example, 1 to 20 layers depending on the purpose of use and application. .

  According to the present invention, while improving efficiency in terms of cost and productivity, a uniform and fine pattern can be realized, and excellent mechanical properties can be secured, and the insulating layer manufacturing method and the insulating layer manufacturing method can be obtained. A method for manufacturing a multilayer printed circuit board using an insulating layer may be provided.

FIG. 3 is a diagram schematically showing a manufacturing process of an insulating layer of Example 1. FIG. 10 is a diagram schematically illustrating a manufacturing process of a multilayer printed circuit board according to Example 2.

  The invention is explained in more detail in the following examples. However, the following examples are merely illustrative of the present invention, and the content of the present invention is not limited by these examples.

<Production example: Production of alkali-soluble resin>
Production Example 1
In a reaction vessel having a volume of 2 liters that can be heated and cooled, equipped with a production thermometer, a stirrer, a reflux condenser, and a moisture meter, 632 g of dimethylformamide (DMF) as a solvent, BMI as an N-substituted maleimide compound -1100 (manufactured by Daiwa Kasei Kogyo Co., Ltd.), 151 g of 4-aminophenylacetic acid as an amine compound were mixed and stirred at 85 ° C. for 24 hours to produce an alkali-soluble resin solution having a solid content of 50%. .

Production Example 2
In a reaction vessel having a volume of 2 liters that can be heated and cooled, equipped with a production thermometer, a stirrer, a reflux condenser, and a moisture meter, 632 g of dimethylformamide (DMF) as a solvent, p as an N-substituted maleimide compound -Carboxyphenylmaleimide (434 g) and 4,4′-diaminodiphenylmethane (198 g) as an amine compound were mixed and stirred at 85 ° C. for 24 hours to prepare an alkali-soluble resin solution having a solid content of 50%.

Production Example 3
543 g of dimethylacetamide (DMAc) as a solvent was placed in a reaction vessel having a volume of 2 liters that can be heated and cooled, equipped with a production thermometer, a stirrer, a reflux condenser, and a moisture meter, and manufactured by Cray Valley. 350 g of SMA1000, 144 g of 4-aminobenzoic acid (PABA) and 49 g of 4-aminophenol (4-aminophenol, PAP) were added and mixed. Under a nitrogen atmosphere, the temperature of the reactor was set at 80 ° C., and the acid anhydride and the aniline derivative reacted to form an amic acid for 24 hours. After that, the temperature of the reactor was set at 150 ° C. and the temperature was maintained for 24 hours. The alkali-soluble resin solution having a solid content of 50% was produced by proceeding with the conversion reaction.

Production Example 4
Methylethylketone (MEK) 516 g was placed in a 2 liter reaction vessel equipped with a production thermometer, a stirrer, a reflux condenser, and a moisture meter and capable of heating and cooling, and p-carboxyphenylmaleimide (MEK) was added. 228 g of p-carbophenylmaleimide), 85 g of p-hydroxyphenylmaleimide (p-hydroxyphenylmaleimide), 203 g of styrene, and 0.12 g of azobisisobutyronitrile (AIBN) were added and mixed. After gradually raising the temperature of the reactor to 70 ° C. under a nitrogen atmosphere, an alkali-soluble resin solution having a solid content of 50% was produced for 24 hours.

<Example 1: Production of insulating layer>
Referring to the contents of FIG. 1 below, 16 g of the alkali-soluble resin synthesized in Production Example 1, 5 g of MY-510 (manufactured by Huntsman) as a thermosetting binder, and 35 g of SC2050 MTO (manufactured by Adamatech) as an inorganic filler are mixed. The polymer resin composition was applied to a 3 μm-thick ultrathin copper foil 4 (MT18SD-H; manufactured by Mitsui Mining Co., Ltd.) to which a carrier copper foil 5 was adhered and dried, and a polymer resin layer having a thickness of 15 μm was dried. 1 was produced. Then, the polymer resin layer 1 is vacuum laminated at 85 ° C. on a circuit board on which copper lines 2 are formed on the copper foil laminate 3, and a photosensitive dry film resist having a thickness of 15 μm is formed on the carrier copper foil 5. (KL1015; manufactured by Kolon Industry Co., Ltd.) 6 was laminated at 110 ° C.

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

  Thereafter, the carrier copper foil 5 and the ultrathin copper foil 4 were etched by treating the etching solution. At this time, the photosensitive dry film resist 6 on which the pattern is formed functions as a protective layer for the carrier copper foil 5 and the ultrathin copper foil 4, and the photosensitive dry film is also applied to the carrier copper foil 5 and the ultrathin copper foil 4. The same pattern as the resist 6 was formed.

  Thereafter, the ultrathin copper foil 4 and the carrier copper foil 5 were separated, and the photosensitive copper film 5 and the photosensitive dry film resist 6 laminated on the carrier copper foil 5 were removed.

  Thereafter, the polymer resin layer 1 was developed through a 1% sodium carbonate developer at 30 ° C. At this time, the ultrathin copper foil 4 on which the pattern is formed acts as a protective layer for the polymer resin layer 1, and the same pattern as the ultrathin copper foil 4 is formed on the polymer resin layer 1 to form a via hole 7. did.

  Thereafter, after thermosetting at a temperature of 100 ° C. for 1 hour, the etching solution was processed to remove the ultrathin copper foil 4 and further a process of thermosetting at a temperature of 200 ° C. for 1 hour to produce an insulating layer. .

<Example 2: Production of multilayer printed circuit board>
Referring to the contents of FIG. 2 below, titanium (Ti) is formed through a sputtering method while supplying a mixed gas of argon and oxygen to the top surface of the insulating layer 1 and the side surface of the via hole 7 manufactured in Example 1 by vapor deposition equipment. A seed layer 8 was formed by evaporating metal to a thickness of 50 nm and copper (Cu) metal to a thickness of 0.5 μm.

  Thereafter, the photosensitive resin layer was exposed and developed on the seed layer 8 to form a photosensitive resin pattern 9. Then, a metal substrate 10 made of copper was formed on the seed layer 8 through electrolytic plating. Subsequently, the photosensitive resin pattern 9 was removed using a photosensitive resin stripping solution, and the exposed seed layer 8 was removed by etching, thereby manufacturing a multilayer printed circuit board.

<Example 3: Production of insulating layer>
Except that the alkali-soluble resin synthesized in Production Example 2 was used in place of the alkali-soluble resin synthesized in Production Example 1 at the production stage of the insulating layer of Example 1, the same as in Example 1 above. The insulating layer was manufactured by the method.

<Example 4: Production of insulating layer>
The same procedure as in Example 1 except that the alkali-soluble resin synthesized in Production Example 3 was used in place of the alkali-soluble resin synthesized in Production Example 1 at the production stage of the insulating layer of Example 1. The insulating layer was manufactured by the method.

<Example 5: Production of insulating layer>
The same procedure as in Example 1 except that the alkali-soluble resin synthesized in Production Example 4 was used instead of the alkali-soluble resin synthesized in Production Example 1 at the production stage of the insulating layer in Example 1. The insulating layer was manufactured by the method.

<Comparative Example 1: Production of insulating layer>
A polymer resin composition obtained by mixing 16 g of the alkali-soluble resin synthesized in Production Example 1, 5 g of MY-510 (manufactured by Huntsman) as a thermosetting binder, and 35 g of SC2050 MTO (manufactured by Adamatech) as an inorganic filler is 25 μm PET. The film was applied to a film and dried to produce a polymer resin layer having a thickness of 15 μm. Then, the polymer resin layer 1 was vacuum laminated at 85 ° C. on the circuit board on which the copper line 2 was formed on the copper foil laminate 3 to remove the PET film.

A photosensitive dry film resist (KL1015; manufactured by Kolon Industry Co., Ltd.) having a thickness of 15 μm was laminated on the polymer resin layer at 110 ° C. A circular negative photomask having a diameter of 30 μm is brought into contact with the photosensitive dry film resist, irradiated with ultraviolet rays (light amount of 25 mJ / cm ² ), and then the photosensitive dry film is passed through a 1% sodium carbonate developer at 30 ° C. The film resist and the polymer resin layer were successively developed.

  At this time, the photosensitive dry film resist acted as a protective layer for the polymer resin layer, and via holes were formed in the polymer resin layer while forming the same pattern as the photosensitive dry film resist.

  Thereafter, after thermosetting at a temperature of 100 ° C. for 1 hour, the photosensitive dry film resist is removed by treating a 3% sodium hydroxide resist stripping solution at 50 ° C., and thermosetting at a temperature of 200 ° C. for 1 hour. An insulating layer was manufactured.

<Comparative Example 2: Production of multilayer printed circuit board>
A 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 Insulating Layer and Multilayer Printed Circuit Board Obtained in Examples and Comparative Examples>
The physical properties of the insulating layers obtained in the examples and comparative examples were measured by the following methods, and the results are shown in Table 1.

1. Via Hole Diameter The diameter of the upper opening surface (via hole) was measured through an optical microscope for the insulating layers obtained in Examples 1, 3 to 7 and Comparative Example 1.

2. Metal adhesion due to moisture absorption After leaving the multilayer printed circuit board obtained in Example 2 and Comparative Example 2 to stand at 135 ° C. and 85% moisture absorption for 48 hours, metal peeling according to the IPC-TM-650 standard The strength was measured, and the metal adhesion was determined from this.

3. HAST (Highly Accelerated Temp & Humidity Stress Test) Characteristics HAST characteristics of the multilayer printed circuit boards obtained in Example 2 and Comparative Example 2 were confirmed according to JESD22-A101 standards. Specifically, a voltage of 3 V is applied to a specimen circuit board having a width, interval, and thickness of 50 μm, 50 μm, and 12 μm, respectively, and the specimen circuit board is allowed to stand for 168 hours, and then the appearance of the specimen circuit board is as follows. The above abnormality was confirmed.
OK: No abnormality is observed in the coating appearance NG: Water bubbles or peeling is observed in the coating

  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 the photosensitive rye film as the protective layer, the diameter of the via hole was 45 μm, whereas Examples 1 and 3 The diameters of the via holes included in the insulating layers manufactured in the first to fifth methods are reduced to 32 μm or 33 μm, and it has been confirmed that a finer pattern can be realized in the case of the above example.

  Further, in the case of the multilayer printed circuit board of Comparative Example 2 obtained from the insulating layer of Comparative Example 1, the metal adhesion was measured to 0.3 kgf / cm, while in the case of the multilayer printed circuit board of Example 2 above. The metal adhesion strength was measured as high as 0.4 kgf / cm, and it was confirmed that the interfacial bonding force between the insulating layer and the conductive layer was improved and excellent HAST characteristics were exhibited.

1: Polymer resin layer 2: Copper line 3: Copper foil laminate 4: Ultra-thin copper foil 5: Carrier copper foil 6: Photosensitive dry film resist (DFR)
7: Via hole 8: Seed layer 9: Photosensitive resin pattern 10: Metal substrate
<1> to <8>: Order of process progress

Claims (20)

Adhering the opposite side of the metal layer having the carrier film bonded on one side onto a polymer resin layer comprising an alkali-soluble resin and a thermosetting binder;
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;
Separating and removing the carrier film from the patterned metal layer;
A method for producing an insulating layer, comprising: alkali-developing the polymer resin layer exposed by the patterned metal layer; and thermally curing the polymer resin layer after the alkali development. In the step of adhering the opposite surface of the metal layer to which the carrier film is bonded to the one surface onto the polymer resin layer containing the alkali-soluble resin and the thermosetting binder,
The method for manufacturing an insulating layer according to claim 1, wherein an adhesive force between the carrier film and the metal layer is smaller than an adhesive force between the polymer resin layer and the metal layer. Separating and removing the carrier film from the patterned metal layer;
The method for producing an insulating layer according to claim 1, wherein both the carrier film and the photosensitive resin layer formed on the carrier film are removed. Removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer;
The method for manufacturing an insulating layer according to claim 1, wherein the carrier film and the metal layer exposed by the patterned photosensitive resin layer are removed simultaneously or sequentially with the same etching solution. Removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer;
The method for producing an insulating layer according to claim 1, wherein a ratio of removing the polymer resin layer is 0.01% by weight or less with respect to the weight of the whole polymer resin layer. The step of forming a patterned photosensitive resin layer on the carrier film,
The manufacturing method of the insulating layer of Claim 1 including the step which exposes and alkali develops the photosensitive resin layer formed on the said carrier film. In the step of exposing and alkali developing the photosensitive resin layer formed on the carrier film,
The method for producing an insulating layer according to claim 6, wherein the polymer resin layer is protected by the carrier film. After the step of thermosetting the polymer resin layer,
The method of manufacturing an insulating layer according to claim 1, further comprising removing a metal layer on the polymer resin layer.   The method for producing an insulating layer according to claim 1, wherein the alkali-soluble resin includes at least one acidic functional group; and at least one cyclic imide functional group substituted with an amino group. The method for producing an insulating layer according to claim 9, wherein the cyclic imide functional group substituted with the amino group includes a functional group represented by the following chemical formula 1:

In the chemical formula 1, R ₁ is an alkylene group or alkenyl group having 1 to 10 carbon atoms, and “ ^* ” means a point of attachment.   The alkali-soluble resin is produced through a reaction of a cyclic unsaturated imide compound; and an amine compound, and at least one of the cyclic unsaturated imide compound and the amine compound includes an acidic functional group substituted at a terminal. Item 10. A method for producing an insulating layer according to Item 9.   12. The insulating layer according to claim 11, wherein the amine compound includes one or more selected from the group consisting of a carboxylic acid compound substituted with an amino group and a polyfunctional amine compound containing two or more amino groups. Production method. The method for producing an insulating layer according to claim 1, wherein the alkali-soluble resin includes at least one repeating unit represented by the following chemical formula 3; and at least one repeating unit represented by the following chemical formula 4:

In 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 bonding point. ,

In 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 be independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
“ ^* ” Means a point of attachment. The alkali-soluble resin is produced by a reaction of a polymer containing a repeating unit represented by the following chemical formula 5, an amine represented by the following chemical formula 6, and an amine represented by the following chemical formula 7. The manufacturing method of the insulating layer as described in 13:

In the chemical formulas 5 to 7, R _{2 to} R ₄ are as defined in claim 13 and “ ^* ” means a point of attachment. The method for producing an insulating layer according to claim 13, wherein the alkali-soluble resin is produced by a reaction of a compound represented by the following chemical formula 8 and a compound represented by the following chemical formula 9:

In the chemical formulas 8 to 9, R _{2 to} R ₄ are as defined in claim 13.   2. The method for manufacturing an insulating layer according to claim 1, wherein the alkali-soluble resin has an acid value determined by KOH titration of 50 mgKOH / g to 250 mgKOH / g.   The said polymeric resin layer is a manufacturing method of the insulating layer of Claim 1 containing 1-150 weight part of thermosetting binders with respect to 100 weight part of alkali-soluble resin.   The thermosetting binder comprises at least one functional group selected from the group consisting of an oxetanyl group, a cyclic ether group, a cyclic thioether group, a cyano group, a maleimide group, and a benzoxazine group, and an epoxy group. The manufacturing method of the insulating layer of description.   2. The insulation according to claim 1, wherein the polymer resin layer further includes at least one 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. Layer manufacturing method.   A method for manufacturing a multilayer printed circuit board, comprising: forming a metal substrate having a pattern formed on an insulating layer manufactured by the method according to any one of claims 1 to 19.

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