KR20210047650A - Method for manufacturing insulating film and multilayered printed circuit board - Google Patents

Abstract

The present invention relates to a method for manufacturing an insulating layer and a method for manufacturing a multilayer printed circuit board, and more specifically, to a method for manufacturing an insulating layer and a method for manufacturing a multilayer printed circuit board, which improves the adhesion between the insulating layer and a metal substrate by treating the surface of a cured polymer resin layer with a surface treatment solution, implements a uniform and fine pattern while improving efficiency in terms of cost and productivity, and secures excellent mechanical properties.

Description

Insulation layer manufacturing method and multilayer printed circuit board manufacturing method {METHOD FOR MANUFACTURING INSULATING FILM AND MULTILAYERED PRINTED CIRCUIT BOARD}

The present invention relates to a method for manufacturing an insulating layer and a method for manufacturing a multilayer printed circuit board. Specifically, the surface on which the polymer resin layer is cured is treated with a surface treatment solution to improve the adhesion between the insulating layer and the metal substrate, and in terms of cost and productivity. The present invention relates to a method for manufacturing an insulating layer and a method for manufacturing a multilayer printed circuit board, which can implement a uniform and fine pattern, and secure excellent mechanical properties while improving efficiency in

Recently, electronic devices are becoming more compact, lighter, and highly functional. To this end, as the application field of a build-up printed circuit board (PCB) is rapidly expanding centering on small devices, the use of multilayer printed circuit boards is rapidly increasing.

Multilayer printed circuit boards are capable of three-dimensional wiring from flat to three-dimensional, especially in the field of industrial electronics, with improved integration of functional devices such as IC (integrated circuit) and LSI (large scale integration), and miniaturization, weight reduction, high functionality, and structural This product is advantageous for electrical function integration, assembly time reduction, and cost reduction.

The build-up PCB used in this application area must form a via hole for connection between each layer, and the via hole corresponds to the electrical connection path between layers of a multilayer printed circuit board. Drill), but as the diameter of the hole became smaller due to the miniaturization of the circuit, the machining method using a laser appeared as an alternative due to the increase in machining cost and the limitation of fine hole machining due to mechanical drilling.

However, in the case of a processing method using a laser, a CO ₂ or YAG laser drill is used, but since the size of the 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 is used. There is a limit in which it is difficult to manufacture a via hole. In addition, when it is necessary to form a plurality of via holes, there is also a limitation in that the cost burden is large.

Accordingly, instead of the above-described laser processing technology, a method of forming a via hole having a fine diameter at low cost using a photosensitive insulating material has been proposed. Specifically, the photosensitive insulating material may be a photosensitive insulating film called a solder resist capable of forming a fine opening pattern using photosensitivity.

Such a photosensitive insulating material or solder resist can be divided into a case of using a sodium carbonate developer for pattern formation and a case of using a different developer. In the case of using a different developer, the photosensitive insulating material or solder resist has a limitation in being difficult to apply in an actual process due to environmental and cost reasons.

On the other hand, the use of sodium carbonate developer has the advantage of being environmentally friendly. In this case, an acid-modified acrylate resin including a number of carboxylic acids and acrylate groups is used to impart photosensitivity.Since most acrylate groups and carboxyl groups are linked by ester bonds, polymerization inhibitors, etc. It includes, and also includes a photoinitiator or the like to cause a radical reaction by irradiation with ultraviolet rays.

However, the polymerization inhibitor or the photoinitiator may be diffused out of the resin under high temperature conditions, and interfacial desorption with the insulating layer or the conductive layer may occur during or after completion of the semiconductor package process. In addition, ester bonds in the resin cause hydrolysis reaction at high humidity and reduce the crosslinking density of the resin to increase the moisture absorption rate of the resin.If the moisture absorption rate is high, polymerization inhibitors or photoinitiators are used under high temperature conditions. In terms of the outside of the resin, interfacial desorption with the insulating layer or the conductive layer may occur during or after the semiconductor package process is completed, and there is a limit in that the HAST characteristics are also deteriorated.

On the other hand, with the miniaturization of electronic devices, printed circuit boards are gradually becoming thinner due to miniaturization, and high rigidity is also required for insulating materials used for substrates to work with thin-walled boards.

In order to improve the rigidity of photosensitive insulating materials or solder resists, the ratio of inorganic fillers in the resin must be increased, but there is a problem that light does not pass through the opaque inorganic fillers, and even in the case of transparent inorganic fillers, light is scattered and photosensitive. There is a limit to making it difficult to form an opening pattern using

Accordingly, there is a need to develop a method for manufacturing an insulating layer having excellent rigidity, which can implement a uniform and fine pattern at low cost while preventing interfacial desorption with an insulating layer or a conductive layer, that is, a metal substrate.

The technical problem to be achieved by the present invention is to provide a method for manufacturing an insulating layer and a method for manufacturing a multilayer printed circuit board that improves adhesion between an insulating layer and a metal substrate.

However, the problem to be solved by the present invention is not limited to the above-mentioned problems, and other problems that are not mentioned will be clearly understood by those skilled in the art from the following description.

An embodiment of the present invention comprises the steps of providing a polymer resin layer including an alkali-soluble resin and a thermosetting binder on the conductor wiring; Providing a photosensitive resin layer on the polymer resin layer; Exposing and alkali developing the photosensitive resin layer to provide a photosensitive resin pattern and at the same time alkali developing the polymer resin layer exposed by the photosensitive resin pattern; After the alkali development, thermosetting the polymer resin layer; Peeling the photosensitive resin pattern; And surface-treating the heat-cured polymer resin layer with a surface treatment solution.

Another embodiment of the present invention provides a method for manufacturing a multilayer printed circuit board including the step of providing a metal substrate having a pattern on an insulating layer manufactured by a method for manufacturing an insulating layer.

In the method of manufacturing an insulating layer according to an exemplary embodiment of the present invention, while efficiency is improved in terms of cost and productivity, a uniform and fine pattern can be implemented, and excellent mechanical properties can be secured.

In the method of manufacturing a multilayer printed circuit board according to another exemplary embodiment of the present invention, the surface on which the polymer resin layer is cured is treated with a surface treatment solution to improve adhesion between the insulating layer and the metal substrate.

The effects of the present invention are not limited to the above-described effects, and effects that are not mentioned will be clearly understood by those skilled in the art from the present specification and the accompanying drawings.

1 schematically shows an insulating layer manufacturing process according to an exemplary embodiment of the present invention.
2 schematically shows a process of manufacturing a multilayer printed circuit board according to an exemplary embodiment of the present invention.
3 is a front photograph of a multilayer printed circuit board of Examples 1 and 2 and Comparative Examples 1 to 4;

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

In the present specification, when a member is said to be positioned "on" another member, this includes not only the case where the certain member is in contact with the other member, but also the case where another member exists between the two members.

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 is preferably 1 to 40. Specifically, the alkyl group has 1 to 20 carbon atoms. More specifically, the alkyl group has 1 to 10 carbon atoms or 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, 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, cycloheptylmethyl, 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-methylhexyl, and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. Specifically, the number of carbon atoms of the aryl group is 6 to 30 or 6 to 20. The aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

Hereinafter, the present invention will be described in more detail.

An exemplary embodiment of the present invention comprises the steps of providing a polymer resin layer including an alkali-soluble resin and a thermosetting binder on the conductor wiring; Providing a photosensitive resin layer on the polymer resin layer; Exposing and alkali developing the photosensitive resin layer to provide a photosensitive resin pattern and at the same time alkali developing the polymer resin layer exposed by the photosensitive resin pattern; After the alkali development, thermosetting the polymer resin layer; Peeling the photosensitive resin pattern; And surface-treating the heat-cured polymer resin layer with a surface treatment solution.

In the method of manufacturing an insulating layer according to an exemplary embodiment of the present invention, while efficiency is improved in terms of cost and productivity, a uniform and fine pattern can be implemented, and excellent mechanical properties can be secured.

Specifically, the step of surface-treating the heat-cured polymer resin layer with a surface treatment solution may increase the surface roughness of the polymer resin layer, through which the surface roughness of the insulating layer including the surface-treated polymer resin layer is also Can increase.

Further, when a metal substrate is provided on the insulating layer by plating or sputtering, which will be described later, adhesion between the insulating layer and the metal substrate may be improved, and reliability of a multilayer printed circuit board implemented therefrom may be improved.

An exemplary embodiment of the present invention includes the step of providing a polymer resin layer including an alkali-soluble resin and a thermosetting binder on the conductor wiring.

According to an exemplary embodiment of the present invention, the polymer resin layer may be a film formed by drying a polymer resin composition including an alkali-soluble resin and a thermosetting binder.

In an exemplary embodiment of the present invention, the polymer resin layer may exist alone or may exist in a state formed on a substrate including a semiconductor material such as a circuit board, a sheet, and a multilayer printed wiring board, wherein the polymer resin layer is formed on the substrate. Although the example of the method is not largely limited, for example, a method of directly coating the polymer resin composition on a substrate or in a state in which the polymer resin composition is applied on a carrier film, and then removing the carrier film after coating. Can be used.

According to an exemplary embodiment of the present invention, the polymer resin layer includes an alkali-soluble resin and a thermosetting binder.

According to an exemplary embodiment of the present invention, the polymer resin layer comprises 1 part by weight to 150 parts by weight, or 10 parts by weight to 100 parts by weight, or 20 parts by weight to 50 parts by weight, based on 100 parts by weight of the alkali-soluble resin. Can include. If the content of the thermosetting binder is too high, developability of the polymer resin layer may decrease and strength may decrease. Conversely, if the content of the thermosetting binder is too low, not only the polymer resin layer is excessively developed, but also the uniformity during coating may be deteriorated.

According to an exemplary embodiment of the present invention, the thermosetting binder is at least one selected from the group consisting of a thermosetting functional group, an oxetanyl group, a cyclic ether group, a cyclic thioether group, a cyanide group, a maleimide group, and a benzoxazine group. It may contain functional groups and epoxy groups. That is, the thermosetting binder necessarily contains an epoxy group, and in addition to the epoxy group, an oxetanyl group, a cyclic ether group, a cyclic thioether group, a cyanide group, a maleimide group, a benzoxazine group, or Two or more of these may be mixed and included. Such a thermosetting binder can secure heat resistance or mechanical properties of the insulating layer by forming a crosslinking bond with an alkali-soluble resin or the like by heat curing. More specifically, as the thermosetting binder, a polyfunctional resin compound including two or more of the above-described functional groups in a molecule may be used.

According to an exemplary embodiment of the present invention, the multifunctional resin compound may include a resin including two or more cyclic ether groups and/or cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in a molecule. .

According to an exemplary embodiment of the present invention, the thermosetting binder including two or more cyclic (thio) ether groups in the molecule is a 3, 4 or 5 membered cyclic ether group, or any one or two of cyclic thioether groups in the molecule. It may include a compound having at least two or more groups.

According to an exemplary embodiment of the present invention, the compound having two or more cyclic thioether groups in the molecule may be a bisphenol A-type episulfide resin YL7000 manufactured by Japan Epoxy Resin Co., Ltd.

According to an exemplary embodiment of the present invention, the polyfunctional resin compound is a polyfunctional epoxy compound containing at least two or more epoxy groups in a molecule, a polyfunctional oxetane compound containing at least two or more oxetanyl groups in a molecule, or two in a molecule Episulfide resin containing the above thioether group, a polyfunctional cyanate ester compound containing at least two or more cyanide groups in the molecule, or a polyfunctional benzoxazine compound containing at least two or more benzoxazine groups in the molecule may be included. have.

According to an exemplary embodiment of the present invention, the multifunctional epoxy compound is a 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, novolac. Type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolak 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 type epoxy resin, diglycidylphthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoylethane resin, silicone It may be a modified epoxy resin or an ε-caprolactone modified epoxy resin. Further, in order to impart flame retardancy, one in which an atom such as phosphorus is introduced into the structure may be used. By thermosetting the epoxy resin, properties such as adhesion, solder heat resistance, and electroless plating resistance of the cured film are improved.

According to an exemplary embodiment of the present invention, the multifunctional oxetane compound is 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)methylacrylate, (3-ethyl-3-oxetanyl)methylacrylate, (3-methyl-3-oxetanyl)methylmethacrylate, (3-ethyl-3-oxe In addition to polyfunctional oxetanes such as cetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolac resin, poly(p-hydroxystyrene), cardo-type bisphenols, carix arenes, It may be an ether product of a resin having a hydroxy group such as carixresolecin arenes or silsesquioxane, and may be a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate.

According to an exemplary embodiment of the present invention, the polyfunctional cyanate ester compound is a bisphenol A type cyanate ester resin, a bisphenol E type cyanate ester resin, a bisphenol F type cyanate ester resin, a bisphenol S type cyanate ester resin, a bisphenol. M type cyanate ester resin, novolak type cyanate ester resin, phenol novolak type cyanate ester resin, cresol novolak type cyanate ester resin, novolac type cyanate ester resin of bisphenol A, biphenol type cyanate ester It may be a resin or an oligomer or copolymer thereof.

According to an exemplary embodiment of the present invention, examples of the multifunctional maleimide compound include 4,4'-diphenylmethane bismaleimide, phenylmethane bismaleimide, m -Phenylmethane bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenyl Methane bismaleimide (3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide), 4-methyl-1,3-phenylene bismaleimide (4-methyl-1,3- phenylene bismaleimide), 1,6'-bismaleimide-(2,2,4-trimethyl)hexane (1,6'-bismaleimide-(2,2,4-trimethyl)hexane).

According to an exemplary embodiment of the present invention, the multifunctional benzoxazine compound is a bisphenol A-type benzoxazine resin, a bisphenol F-type benzoxazine resin, a phenolphthalein-type benzoxazine resin, a thiodiphenol-type benzoxazine resin, a dicyclo pentadiene-type benzoxazine. Photo 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.

According to an exemplary embodiment of the present invention, the multifunctional resin compound is YDCN-500-80P from Kukdo Chemicals, phenol novolac-type cyanite Esner resin PT-30S from Ronza, and phenylmethane-type maleimide resin BMI- from Daiwa. 2300, it may be a Pd-type benzoxazine resin from Shikoku.

According to an exemplary embodiment of the present invention, the alkali-soluble resin is an acidic functional group; And at least one or two or more cyclic imide functional groups substituted with an amino group, respectively. The acidic functional group is not limited, but may include, for example, a carboxyl group or a phenol group. The alkali-soluble resin includes at least one or two or more acidic functional groups, so that the polymer resin layer has higher alkali developability, and the developing speed of the polymer resin layer can be controlled.

According to an exemplary embodiment of the present invention, 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 more or two or more. As 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 structure in which a large number of active hydrogens contained in the amino group are present. As the reactivity with the thermosetting binder is improved, the curing density can be increased, thereby increasing heat resistance reliability and mechanical properties. In addition, as a plurality of cyclic imide functional groups are present in the alkali-soluble resin, the polarity is increased by the carbonyl group and tertiary amine group included in the cyclic imide functional group, thereby increasing the interfacial adhesion of the alkali-soluble resin.

According to an exemplary embodiment of the present invention, the cyclic imide functional group substituted with the amino group may include a functional group represented by the following formula (2).

[Formula 2]

In Formula 2, R ₁ is an alkylene group or alkenyl group having 1 to 10 carbon atoms, or 1 to 5, or 1 to 3, and "*" means a bonding point. The alkylene group is a divalent functional group derived from alkane, for example, as a straight chain, branched or cyclic, methylene group, ethylene group, propylene group, isobutylene group, sec-butylene group, It may be a tert-butylene group, a pentylene group, a hexylene group, and the like. One or more hydrogen atoms included in the alkylene group may be substituted with other substituents, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and 6 Aryl group of to 12, heteroaryl group of 2 to 12 carbon atoms, arylalkyl group of 6 to 12 carbon atoms, halogen atom, cyano group, amino group, amidino group, nitro group, amide group, carbonyl group, hydroxy group, sulfonyl group, carba A mate group, a C1-C10 alkoxy group, etc. are mentioned.

In the present invention, the term "substitution" means that other functional groups are bonded instead of a hydrogen atom in the compound, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and two or more substitutions If so, two or more substituents may be the same or different from each other.

In the present invention, the alkenyl group means containing one or more carbon-carbon double bonds in the middle or terminal of the alkylene group described above, for example, ethylene, propylene, butylene, hexylene, acetylene. And the like. At least one hydrogen atom in the alkenyl group may be substituted with the same substituent as in the case of the alkylene group.

According to an exemplary embodiment of the present invention, the cyclic imide functional group substituted with the amino group may be a functional group represented by the following formula (3).

[Formula 3]

In Formula 3, "*" means a bonding point.

As described above, the alkali-soluble resin includes a cyclic imide functional group substituted with an amino group together with an acidic functional group, and specifically, an acidic functional group is bonded to at least one end of the cyclic imide functional group substituted with the amino group can do. At this time, the cyclic imide functional group substituted with the amino group and the acidic functional group may be bonded via a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, for example, a cyclic type substituted with the amino group An acidic functional group may be bonded to the terminal of the amino group included in the imide functional group via a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and already included in the cyclic imide functional group substituted with the amino group. The acidic functional group may be bonded to the terminal of the de functional group via a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group.

According to an exemplary embodiment of the present invention, the terminal of the amino group included in the cyclic imide functional group substituted with the amino group means a nitrogen atom included in the amino group in Formula 2, and a cyclic imide substituted with the amino group The terminal of the imide functional group included in the functional group may mean a nitrogen atom included in the cyclic imide functional group in Formula 2.

According to an exemplary embodiment of the present invention, the alkylene group is a divalent functional group derived from alkane, a straight chain, branched or cyclic, methylene group, ethylene group, propylene group, isobutylene group, It may be a sec-butylene group, a tert-butylene group, a pentylene group, a hexylene group, and the like. One or more hydrogen atoms included in the alkylene group may be substituted with other substituents, and the substituent is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and 6 to 12 carbon atoms. Aryl group, C2-C12 heteroaryl group, C6-C12 arylalkyl group, halogen atom, cyano group, amino group, amidino group, nitro group, amide group, carbonyl group, hydroxy group, sulfonyl group, carbamate group , It may be an alkoxy group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present invention, the arylene group is a divalent functional group derived from arene, and may be a cyclic group, such as a phenyl group or a naphthyl group. One or more hydrogen atoms included in the arylene group may be substituted with other substituents, and the substituent is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and 6 to 12 carbon atoms. Aryl group, C2-C12 heteroaryl group, C6-C12 arylalkyl group, halogen atom, cyano group, amino group, amidino group, nitro group, amide group, carbonyl group, hydroxy group, sulfonyl group, carbamate group , It may be an alkoxy group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present invention, a method of preparing the alkali-soluble resin is not limited, but a cyclic unsaturated imide compound; And it can be prepared through the reaction of an amine compound. At this time, the cyclic unsaturated imide compound; And amine compounds; At least one of them may include an acidic functional group substituted at the terminal. That is, an acidic functional group may be substituted at the terminal of the cyclic unsaturated imide compound, the amine compound, or both of these compounds. The contents of the acidic functional group are as described above.

According to an exemplary embodiment of the present invention, the cyclic imide compound is a compound containing the aforementioned cyclic imide functional group, and the cyclic unsaturated imide compound is an unsaturated bond, that is, a double bond or a triple bond in the cyclic imide compound. It means a compound containing at least one bond.

According to an exemplary embodiment of the present invention, the alkali-soluble resin may be prepared through a reaction of an amino group included in the amine compound and a double bond or a triple bond included in the cyclic unsaturated imide compound.

According to an exemplary embodiment of the present invention, the weight ratio of reacting the cyclic unsaturated imide compound and the amine compound is not largely limited, but based on 100 parts by weight of the cyclic unsaturated imide compound, the amine compound is 10 to It may be reacted by mixing in an amount of 80 parts by weight, or 30 to 60 parts by weight.

According to an exemplary embodiment of the present invention, the cyclic unsaturated imide compound may be an N-substituted maleimide compound. N-substituted means that a functional group is bonded instead of a hydrogen atom bonded to a nitrogen atom contained in a maleimide compound, and the N-substituted maleimide compound is a monofunctional N-substituted maleimide depending on the number of N-substituted maleimide compounds. Compounds and polyfunctional N-substituted maleimide compounds can be classified.

In the present invention, the monofunctional N-substituted maleimide compound is a compound in which a functional group is substituted with a nitrogen atom included in one maleimide compound, and the polyfunctional N-substituted maleimide compound is in each of two or more maleimide compounds. It refers to a compound in which the nitrogen atom contained is bonded through a functional group.

According to an exemplary embodiment of the present invention, in the monofunctional N-substituted maleimide compound, the functional group substituted for the nitrogen atom included in the maleimide compound may include, without limitation, various known aliphatic, alicyclic or aromatic functional groups. In addition, the functional group substituted with the nitrogen atom may include a functional group in which an acidic functional group is substituted with an aliphatic, alicyclic or aromatic functional group. The contents of the acidic functional group are as described above.

According to an exemplary embodiment of the present invention, the monofunctional N-substituted maleimide compound may be o-methylphenylmaleimide, p-hydroxyphenylmaleimide, p-carboxyphenylmaleimide, or dodecylmaleimide.

According to an exemplary embodiment of the present invention, in the multifunctional N-substituted maleimide compound, the functional group that mediates the bond between nitrogen atoms contained in each of the two or more maleimide compounds is not limited to various known aliphatic, alicyclic, or aromatic functional groups. It may include, and specifically, a 4,4'-diphenylmethane functional group may be used. The functional group substituted with the nitrogen atom may include a functional group in which an acidic functional group is substituted with an aliphatic, alicyclic or aromatic functional group. The contents of the acidic functional group are as described above.

According to an exemplary embodiment of the present invention, the polyfunctional N-substituted maleimide compound is 4,4'-diphenylmethane bismaleimide (Daiwakasei's BMI-1000, BMI-1100, etc.), phenylmethane bismaleimide, m -Phenylenemethane bismaleimide, bisphenol A diphenylether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane.

According to an exemplary embodiment of the present invention, the amine compound _{may be a primary amine compound containing at least one amino group (-NH 2} ) in the molecular structure, and more preferably a carboxylic acid compound substituted with an amino group, 2 Polyfunctional amine compounds containing the above amino groups or mixtures thereof can be used.

According to an exemplary embodiment of the present invention, 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 depending on the type of hydrocarbon bonded to the carboxylic acid functional group, aliphatic, alicyclic or It may contain all aromatic carboxylic acids. Through the carboxylic acid compound substituted with the amino group, a plurality of carboxylic acid functional groups, which are acidic functional groups, are included in the alkali-soluble resin, so that the developability of the alkali-soluble resin may be improved.

In the present invention, the position at which the amino group is substituted in the carboxylic acid compound is not limited as long as the position at which a hydrogen atom is substituted, and the number of substituted amino groups may be 1 or more.

According to an exemplary embodiment of the present invention, the amino group-substituted carboxylic acid compound is 20 kinds of α-amino acids, 4-aminobutanoic acid, 5-aminopentanoic acid, 6-aminohexanoic acid, and 7-amino, which are known as raw materials for proteins. Heptanoic acid, 8-aminooctanoic acid, 4-aminobenzoic acid, 4-aminophenylacetic acid, 4-amino cyclohexane carboxylic acid.

According to an exemplary embodiment of the present invention, the polyfunctional amine compound containing two or more amino groups is a compound containing two or more amino groups (-NH ₂ ) in a molecule, and is aliphatic, alicyclic or aromatic depending on the type of hydrocarbon bonded to the amino group. It may contain all functional amines. Flexibility, toughness, copper foil adhesion, and the like of the alkali-soluble resin may be improved through the polyfunctional amine compound including two or more amino groups.

According to an exemplary embodiment of the present invention, the polyfunctional amine compound including two or more amino groups is 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-phenylenediamine, 2 ,3,5,6-tetrafluoro-1,4-phenylenediamine, 4,6-diaminoresorcinol, 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'-diaminodiphenylmethane , 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 Si)-benzene, 1,4-bis(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]hexa Fluoropropane, bis(2-aminophenyl)sulfide, bis(4-aminophenyl)sulfide, bis(3-aminophenyl)sulfone, bis(4-aminophenyl)sulfone, bis(3-amino-4-hydroxyl) )Sulfone, bis[4-(3-aminophenoxy)-phenyl]sulfone, bis[4-(4-aminophenoxy)-phenyl]sulfone, o-tolidine sulfone, 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- Polyfunctional amines including inden-5-amine, 4,6-diaminoresorcinol, 2,3,5,6-pyridine tetraamine, and the 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), polyfunctional amines containing Dow Corning's siloxane structure (Dow Corning 3055), polyethers It may be a polyfunctional amine containing a structure (Huntsman, BASF).

According to an exemplary embodiment of the present invention, the alkali-soluble resin is a repeating unit represented by the following formula (4); And at least one or more repeating units represented by the following Chemical Formula 5, respectively.

[Formula 4]

In Formula 4, 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,

[Formula 5]

In Formula 5, 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, and R ₅ and R ₆ may each independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and "*" indicates a bonding point it means. Preferably, in Formula 4, R ₂ may be phenylene, in Formula 5, R ₃ may be phenylene, and R ₄ may be -OH.

On the other hand, the alkali-soluble resin is a repeating unit represented by the formula (4); And it may further include a vinyl-based repeating unit in addition to the repeating unit represented by the formula (5). The vinyl-based repeating unit is a repeating unit contained in a homopolymer of a vinyl-based monomer containing at least one vinyl group in a molecule, and examples of the vinyl-based monomer are not limited, for example, ethylene, propylene, isobutylene. , Butadiene, styrene, acrylic acid, methacrylic acid, maleic anhydride, or maleimide.

A repeating unit represented by Formula 4 above; And the alkali-soluble resin each containing at least one or more repeating units represented by Formula 4 is a reaction of a polymer including a repeating unit represented by Formula 6 below, an amine represented by Formula 7 below, and an amine represented by Formula 8 below. Can be manufactured.

[Formula 6]

[Formula 7]

[Formula 8]

In Formulas 6 to 8, R ₂ to R ₄ are the same as those described above in Formulas 4 and 5, and "*" means a bonding point.

The polymer including the repeating unit represented by Formula 6 is not limited, but may be SMA of Cray valley, Xiran of Polyscope, Scripset of Solenis, Isobam of Kuraray, Polyanhydride resin of Chevron Phillips Chemical, Maldene of Lindau Chemicals.

In addition, the repeating unit represented by the above-described formula 4; And the alkali-soluble resin each including at least one or more repeating units represented by Formula 4 may be prepared by a reaction of a compound represented by Formula 9 below and a compound represented by Formula 10 below.

[Formula 9]

[Formula 10]

In Formulas 8 to 9, R ₂ to R ₄ are the same as those described above in Formulas 4 and 5.

According to an exemplary embodiment of the present invention, the alkali-soluble resin may be a conventionally known carboxy group-containing resin or phenol group-containing resin containing a carboxyl group or a phenol group in the molecule. Preferably, a phenol group-containing resin may be mixed with the carboxy group-containing resin or the carboxy group-containing resin.

According to an exemplary embodiment of the present invention, the carboxy group-containing resin includes the resins (1) to (7) listed below. (1) After reacting a polyfunctional epoxy resin with a saturated or unsaturated monocarboxy group, a resin containing a carboxyl group obtained by reacting a polybasic acid anhydride, (2) after reacting a bifunctional epoxy resin with a difunctional phenol and/or a dicarboxy group Carboxy group-containing resin obtained by reacting a polybasic acid anhydride, (3) a carboxy group-containing resin obtained by reacting a polyfunctional phenolic resin with a compound having one epoxy group in the molecule and then reacting a polybasic acid anhydride, (4) two or more alcoholic hydroxyl groups in the molecule Carboxy group-containing resin obtained by reacting a polybasic acid anhydride with a compound having (5) a polyamic acid resin obtained by reacting diamine and dianhydride or a copolymer resin of a polyamic acid resin, (6) acrylic acid Polyacrylic acid resin or copolymer of polyacrylic acid resin or (7) polymaleic anhydride resin reacted with maleic anhydride and anhydride of polymaleic anhydride resin copolymer are weak acid, diamine, imidazole, dimethyl sulfoxide ( dimethyl sulfoxide) may be a resin prepared by ring opening, but is not limited thereto.

According to an exemplary embodiment of the present invention, the carboxy group-containing resin may be CCR-1291H of Japanese Explosives, SHA-1216CA60 of Shina T&C, Noverite K-700 of Lubrizol, or a mixture of two or more thereof.

According to an exemplary embodiment of the present invention, the phenol group-containing resin is not limited, but a phenol novolak resin, a cresol novolac resin, a bisphenol F (BPF) novolak resin of a novolak resin, or 4,4'-(1 -(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl)ethane-1,1-diyl)diphenol [4,4'-(1-(4-(2-(4) Bisphenol A resin of -Hydroxyphenyl)propan-2-yl)phenyl)ethane-1,1-diyl)diphenol] may be used alone or in combination.

According to an exemplary embodiment of the present invention, the alkali-soluble resin may have an acid value calculated by KOH titration of 50 mgKOH/g to 250 mgKOH/g, or 70 mgKOH/g to 200 mgKOH/g. Although an example of a method of measuring the acid value of the alkali-soluble resin is not largely limited, for example, the following method may be used. A 0.1 N KOH solution (solvent: methanol) was prepared as a base solution, and alpha-naphtholbenzein (pH: 0.8 ~ 8.2 yellow, 10.0 blue green) was prepared as an indicator. I did. Then, about 1 to 2 g of an alkali-soluble resin as a sample was taken and dissolved in 50 g of a dimethylformaldehyde (DMF) solvent, and then a marker was added, followed by titration with a base solvent. The acid value was calculated in units of mg KOH/g as the amount of the base solvent used at the time of completion of the titration.

When the acid value of the alkali-soluble resin is excessively reduced to less than 50 mgKOH/g, the developability of the alkali-soluble resin is lowered, and it may be difficult to proceed with the developing process. In addition, when the acid value of the alkali-soluble resin is excessively increased to more than 250 mgKOH/g, phase separation with other resins may occur due to increased polarity.

According to an exemplary embodiment of the present invention, 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.

According to an exemplary embodiment of the present invention, as the thermosetting catalyst, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4 Imidazole derivatives such as phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine compound; Hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; It may be a phosphorus compound of triphenylphosphine. Specifically, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ manufactured by Shikoku Kasei Kogyo Co., Ltd. (Trade name of), DBU, DBN, U-CATS A102, U-CAT5002 (all bicyclic amidine compounds and salts thereof). It is not particularly limited to these, and may be a thermosetting catalyst of an epoxy resin or an oxetane compound, or a reaction between an epoxy group and/or an oxetanyl group and a carboxyl group, and may be used alone or in combination of two or more. . In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine-isosaanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isosaanuric acid S-triazine derivatives such as adducts can also be used, and preferably, compounds that also function as adhesion-imparting agents can be used in combination with the thermosetting catalyst. By using the above-described thermosetting catalyst, it is possible to accelerate the thermosetting of the thermosetting binder.

According to an exemplary embodiment of the present invention, the inorganic filler may be silica, barium sulfate, barium titanate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, or a mixture of two or more thereof.

According to an exemplary embodiment of the present invention, examples of the content of the inorganic filler are not largely limited, but in order to achieve high rigidity of the polymer resin layer, based on 100 parts by weight of all resin components contained in the polymer resin layer, the The inorganic filler may be added in an amount of 100 parts by weight or more, or 100 parts by weight to 600 parts by weight, or 150 parts by weight to 500 parts by weight, or 200 parts by weight to 500 parts by weight.

According to an exemplary embodiment of the present invention, the release agent may be a low molecular weight polypropylene, a low molecular weight polyethylene polyalkylene wax, an ester wax, a carnauba wax, or a paraffin wax.

According to an exemplary embodiment of the present invention, the metal adhesion promoter may be a material that does not cause a problem in surface deterioration or transparency of the metal material. Specifically, a silane coupling agent or an organometallic coupling agent may be used.

According to an exemplary embodiment of the present invention, the leveling agent may be BYK-380N, BYK-307, BYK-378, BYK-350 of BYK-Chemie GmbH. By using the leveling agent, the surface is popped during film coating. Or craters can be removed.

According to an exemplary embodiment of the present invention, the polymer resin layer may further include a resin or elastomer having a weight average molecular weight of 5000 or more capable of causing phase separation. Accordingly, a roughening treatment of the cured product of the polymer resin layer may be possible. The example of the method for measuring the molecular weight of the resin or elastomer having a weight average molecular weight of 5000 or more is not limited, for example, it refers to a weight average molecular weight in terms of polystyrene measured by the GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a commonly known analysis device, a detector such as a Refractive Index Detector, and a column for analysis can be used, and the temperature normally applied Conditions, solvents, and flow rates can be applied. Specific examples of the measurement conditions include a temperature of 30, a chloroform solvent, and a flow rate of 1 mL/min.

According to an exemplary embodiment of the present invention, the polymer resin layer further comprises a thermosetting binder comprising a photoreactive unsaturated group or an alkali-soluble resin comprising a photoreactive unsaturated group and a photoinitiator in order to impart photocurable properties to the polymer resin layer. can do. Specific examples of the thermosetting binder including the photoreactive unsaturated group, the alkali-soluble resin including the photoreactive unsaturated group, and the photoinitiator are not limited thereto, and various compounds used in the technical field related to the photocurable resin composition may be used without limitation.

According to an exemplary embodiment of the present invention, the content of the photoinitiator contained in the polymer resin layer may be 0.01% by weight or less based on the total weight of the polymer resin layer. When the content of the photoinitiator contained in the polymer resin layer is 0.01% by weight or less based on the total weight of the polymer resin layer, it may mean that the content of the photoinitiator contained in the polymer resin layer is very insignificant or no photoinitiator is included. . Accordingly, the interfacial desorption property with the insulating layer or the conductive layer that may be generated by the photoinitiator may be reduced, and thus the adhesion and durability of the insulating layer may be improved.

According to an exemplary embodiment of the present invention, comprising the step of providing a photosensitive resin layer on the polymer resin layer.

The photosensitive resin layer includes a polymer in which a molecular structure is changed and physical properties are changed by the action of light, and may be a photosensitive dry film resist (DFR) or a liquid resist.

According to an exemplary embodiment of the present invention, the photosensitive resin layer may exhibit photosensitivity and alkali solubility. Accordingly, the molecular structure may be modified by an exposure process of irradiating light onto the photosensitive resin layer, and the resin layer may be etched or removed by a developing process of contacting an alkaline developer.

According to an exemplary embodiment of the present invention, an example of a method of forming the photosensitive resin layer on the polymer resin layer is not largely limited, but a method of laminating a film-type photosensitive resin such as a photosensitive dry film resist on the polymer resin layer, or A method of coating the photosensitive resin composition on the polymer resin layer by spraying or dipping and compressing it may be used.

According to an exemplary embodiment of the present invention, the thickness of the polymer resin layer is 1 μm to 500 μm, or 3 μm to 500 μm, or 3 μm to 200 μm, or 1 μm to 60 μm, or 5 μm to 30 μm. And the thickness of the photosensitive resin layer formed on the polymer resin layer is 1 µm to 500 µm, or 3 µm to 500 µm, or 3 µm to 200 µm, or 1 µm to 60 µm, or 5 µm to 30 µm I can. When the thickness of the photosensitive resin layer is excessively increased, the resolution of the polymer resin layer may decrease.

According to an exemplary embodiment of the present invention, the photosensitive resin layer is exposed to light and alkali developed to provide a photosensitive resin pattern, and at the same time, the polymer resin layer exposed by the photosensitive resin pattern is also alkali developed.

According to an exemplary embodiment of the present invention, the photosensitive resin layer may exhibit photosensitivity and alkali solubility. Accordingly, the molecular structure may be modified by an exposure process of irradiating light onto the photosensitive resin layer, and the resin layer may be etched or removed by a developing process of contacting an alkaline developer.

Accordingly, when a portion of the photosensitive resin layer is selectively exposed and then alkali developed, the exposed portion is not developed, and only the unexposed portion may be selectively etched and removed. In this way, a part of the photosensitive resin layer that is not alkali developed by exposure and remains as it is is referred to as a photosensitive resin pattern.

According to an exemplary embodiment of the present invention, the method of exposing the photosensitive resin layer includes contacting a photomask having a predetermined pattern on the photosensitive resin layer and irradiating ultraviolet rays, or using a projection objective lens to apply a predetermined pattern included in the mask. After imaging through, ultraviolet rays may be irradiated, or a laser diode may be used as a light source to directly image and then ultraviolet rays may be irradiated. At this time, as an example of the ultraviolet irradiation conditions, irradiation with a light amount of 5 mJ/cm 2 to 600 mJ/cm 2 is mentioned.

According to an exemplary embodiment of the present invention, the method of developing alkali after exposure to the photosensitive resin layer may be a method of treating an alkali developer. Examples of the alkali developer are not largely limited, but the concentration and temperature of an alkali aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, amines, etc. It can be used, and alkaline developer sold as a product can also be used. The specific amount of the alkali developer is not limited, but it needs to be adjusted to a concentration and temperature that does not damage the photosensitive resin pattern. For example, a 0.5 to 3% aqueous solution of sodium carbonate of 25 to 35 may be used.

According to an exemplary embodiment of the present invention, the ratio at which the photosensitive resin pattern is removed may be 0.01% by weight or less based on the total weight of the photosensitive resin pattern. When the ratio at which the photosensitive resin pattern is removed is 0.01% by weight or less based on the total weight of the photosensitive resin pattern, it may mean that the ratio at which the photosensitive resin pattern is removed is very insignificant or the photosensitive resin pattern is not removed at all.

Accordingly, in the method of manufacturing the insulating layer, the photosensitive resin layer may be exposed and alkali developed to form a photosensitive resin pattern, and the polymer resin layer exposed by the photosensitive resin pattern may be alkali developed. As described above, the photosensitive resin layer may have a fine and uniform pattern using photosensitivity, and only a portion of the surface of the polymer resin layer exposed through the pattern formed on the photosensitive resin layer is selectively contacted with the alkali developer. Through this process, while replacing the conventional etching process using a laser, it is possible to secure an equal or higher level of precision and higher process economy.

That is, in the step of alkali developing the polymer resin layer exposed by the photosensitive resin pattern, the photosensitive resin pattern remains as it is and is used as a resist mask due to the nature of not being removed by an alkali developer, and alkali through the opening of the photosensitive resin pattern. The developer may contact the polymer resin layer located under the photosensitive resin layer. In this case, since the polymer resin layer contains an alkali-soluble resin, it has alkali solubility that is dissolved by an alkali developer, and thus a portion of the polymer resin layer in contact with the alkali developer may be dissolved and removed.

Therefore, the polymer resin layer exposed by the photosensitive resin pattern means a portion of the polymer resin layer whose surface is not in contact with the photosensitive resin pattern, and the step of alkali developing the polymer resin layer exposed by the photosensitive resin pattern The alkali developer used to form the photosensitive resin pattern may include the step of passing through the photosensitive resin pattern and contacting the lower polymer resin layer.

By alkali developing the polymer resin layer exposed by the photosensitive resin pattern, a polymer resin pattern having the same shape as the photosensitive resin pattern may be formed on the polymer resin layer as shown in FIG. 1 below. 1 schematically shows an insulating layer manufacturing process according to an exemplary embodiment of the present invention. Like the photosensitive resin pattern, a part of the polymer resin layer that is not alkali developed and remains as it is may be referred to as a polymer resin pattern.

In this way, as the pattern formation through the development of the photosensitive resin layer and the pattern formation through the development of the polymer resin layer are simultaneously carried out in one alkali developer, mass production is possible quickly, so that the efficiency of the process can be improved. , A fine pattern having the same shape as the fine pattern formed on the photosensitive resin layer can be easily introduced into the polymer resin layer by a chemical method.

According to an exemplary embodiment of the present invention, after the step of forming a photosensitive resin pattern by exposing the photosensitive resin layer to light and developing alkali and developing an alkali developing the polymer resin layer exposed by the photosensitive resin pattern at the same time, the photosensitive resin pattern 0.1 wt% to 85 wt%, or 0.1 wt% to 50 wt%, or 0.1 wt% to 10 wt% based on the total weight of the polymer resin layer exposed by the resin layer may remain. This seems to be because the alkali-soluble resin contained in the polymer resin layer was removed by an alkali developer, but a thermosetting binder or inorganic filler having little alkali developability was not removed and remained.

According to an exemplary embodiment of the present invention, in order to control the degree to which the inorganic filler and the thermosetting binder remain, the weight ratio of the thermosetting binder and the inorganic filler to the alkali-soluble resin, the acidic functional group ratio on the surface of the inorganic filler, etc. can be adjusted, Preferably, 20 to 100 parts by weight of a thermosetting binder and 100 to 600 parts by weight of an inorganic filler may be added relative to 100 parts by weight of the alkali-soluble resin, and the acid value of the surface of the inorganic filler is 0 mgKOH/g To 5 mgKOH/g, or 0.01 mgKOH/g to 5 mgKOH/g. The content of the acid value is the same as the method of measuring the acid value of the alkali-soluble resin.

In this way, in the process of alkali developing the polymer resin layer exposed by the photosensitive resin pattern, some of the polymer resin layers remain undeveloped, and thus, in the subsequent removal process of the photosensitive resin pattern, the target polymer resin pattern is removed. Instead, while the remaining polymer resin layer is removed, expansion of via holes due to removal of the polymer resin pattern can be prevented.

According to an exemplary embodiment of the present invention, after the alkali development, it includes the step of thermally curing the polymer resin layer.

According to an exemplary embodiment of the present invention, the method of manufacturing the insulating layer may include the step of thermally curing the polymer resin layer after the alkali development. By including the step of thermally curing the polymer resin layer, damage to the polymer resin layer may be minimized during the subsequent photosensitive resin pattern peeling process.

At this time, the specific thermosetting conditions are not limited, and preferable conditions may be adjusted according to the peeling method of the photosensitive resin pattern. For example, when the photoresist stripper is treated to peel the photosensitive resin pattern, the step of thermally curing the polymer resin layer may be performed at a temperature of 60 to 150° C. for 5 minutes to 2 hours. If the heat curing temperature of the polymer resin layer is too low or the heat curing time is short, the polymer resin pattern may be damaged by the stripper, and the heat curing temperature of the polymer resin layer is high, or the heat curing time is prolonged. If so, it may be difficult to remove the photosensitive resin pattern by the stripper.

According to an exemplary embodiment of the present invention, when the resist mask is peeled through a desmear process, the step of thermally curing the polymer resin layer may be performed at a temperature of 150 to 230° C. for 1 to 4 hours. .

According to an exemplary embodiment of the present invention, it includes the step of peeling the photosensitive resin pattern.

According to an exemplary embodiment of the present invention, the method of manufacturing the insulating layer may include peeling the photosensitive resin pattern after the thermosetting. When removing the photosensitive resin pattern, it is preferable to use a method capable of removing only the photosensitive resin layer while not removing the lower polymer resin layer as much as possible. In addition, a part of the polymer resin layer may be removed to adjust the shape of the opening pattern or to remove residues of the polymer resin layer that may remain on the bottom surface of the opening pattern.

According to an exemplary embodiment of the present invention, a ratio of removing the polymer resin layer in the step of peeling the photosensitive resin pattern may be 10% by weight or less, or 1% by weight or less, or 0.01% by weight or less based on the total weight of the polymer resin layer. . When the ratio at which the polymer resin layer is removed is 0.01% by weight or less based on the total weight of the polymer resin layer, it may mean that the ratio at which the polymer resin layer is removed is very insignificant or that the polymer resin layer is not removed at all.

According to an exemplary embodiment of the present invention, a specific example of a method of removing the photosensitive resin pattern, a photoresist stripper, may be treated, a desmear process or plasma etching may be performed, and the above methods may be used in combination. You may.

According to an exemplary embodiment of the present invention, a peeling method using a photoresist stripper is not limited, but the concentration and temperature of an alkaline aqueous solution such as potassium hydroxide and sodium hydroxide can be adjusted to be used. Commercially available products such as ORC-731, ORC-723K, ORC-740, and SLF-6000 can also be used. The specific amount of the photoresist stripper is not limited, but it needs to be adjusted to a concentration and temperature that does not damage the lower polymer resin layer pattern, and an aqueous solution of 1 to 5% sodium hydroxide at 25°C to 60°C may be used. .

According to an exemplary embodiment of the present invention, the peeling method using the desmear process is not limited, and a sweller chemical of Securiganth E, Securiganth HP, Securiganth BLG, Securiganth MV SWELLER, Securiganth SAP SWELLER as Atotech's desmear process chemicals, Securiganth P 500, Securiganth MV ETCH P, Securiganth SAP ETCH P permanganate, Securiganth E Reduction Cleaner, Securiganth HP Reduction Cleaner, Securiganth BLG Reduction Cleaner, Securiganth MV Reduction Cleaner, Securiganth SAP Reduction Cleaner As process chemicals, commercially available products such as ORC-310A, ORC-315A, ORC-315H, Sweller chemicals of ORC-312, permanganate chemicals such as ORC-340B, and reducing agents of ORC-370 and ORC-372 are used in each process condition You can use it accordingly.

According to an exemplary embodiment of the present invention, it includes the step of surface-treating the heat-cured polymer resin layer with a surface treatment solution.

As described above, by treating the surface of the thermosetting polymer resin layer with a surface treatment solution, it is possible to improve the surface roughness of the thermosetting polymer resin layer. Further, it is possible to improve the surface roughness of the insulating layer provided by the thermosetting polymer resin layer. Furthermore, adhesion to the electric substrate provided on the insulating layer may be improved.

According to an exemplary embodiment of the present invention, the surface treatment solution may be an amine-based basic solution. When the surface treatment solution is selected as an amine-based basic solution, it is possible to improve the surface treatment efficiency of the heat-cured polymer resin layer, thereby improving the surface roughness within a short time.

According to an exemplary embodiment of the present invention, the surface treatment solution may be a solution containing the following formula (1).

[Formula 1]

In Formula 1, X ₁ and X ₂ are each independently an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or an aminoalkyl group having 1 to 3 carbon atoms, and X ₁ and X ₂ are additionally N or O It may form a ring that may contain.

By selecting the surface treatment solution of Formula 1, surface treatment efficiency may be improved, and roughness on the surface of the cured polymer resin layer may be improved.

According to an exemplary embodiment of the present invention, the surface treatment may be immersed in the surface treatment solution for more than 0 minutes and less than 3 minutes. Specifically, the surface treatment may be 0.5 minutes or more and 2.5 minutes or less, 1 minute or more and 2 minutes or less, or 1.5 minutes or more and 2.0 minutes or less.

Furthermore, according to an exemplary embodiment of the present invention, the surface treatment may be performed at 25° C. or more and 90° C. or less. Specifically, the temperature of the surface treatment step may be 30° C. or more and 85° C. or less, 35° C. or more and 80° C. or less, and 40° C. or more and 75° C. or less.

By controlling the temperature and time of the surface treatment step within the above-described range, it is possible to improve the surface treatment speed and implement an appropriate surface roughness to the cured polymer resin layer.

Another exemplary embodiment of the present invention provides a method for manufacturing a multilayer printed circuit board including the step of providing a metal substrate having a pattern on an insulating layer manufactured by the method for manufacturing an insulating layer.

According to another exemplary embodiment of the present invention, the method of manufacturing a multilayer printed circuit board may improve adhesion between the insulating layer and the metal substrate by treating the surface on which the polymer resin layer is cured with a surface treatment solution.

Specifically, the insulating layer manufactured by the method of manufacturing the insulating layer has improved surface roughness, and since a metal substrate is provided on the insulating layer, the metal substrate is positioned between the insulating layers with improved roughness to increase contact force, As the contact area between the insulating layer and the metal substrate increases, adhesive strength may be improved due to attractive force between the surfaces.

According to an exemplary embodiment of the present invention, the insulating layer may be used as an interlayer insulating material of a multilayer printed circuit board, and may include a thermosetting product of an alkali-soluble resin and a thermosetting binder. The contents of the alkali-soluble resin and the thermosetting binder are as described above.

According to an exemplary embodiment of the present invention, the step of providing a metal substrate on which a pattern is formed on the insulating layer is a microcircuit pattern forming process known as a Semi Additive Process (SAP) in the art, and the SAP process is performed on the insulating layer. It may mean a case in which a microcircuit pattern is provided in a state where there is nothing in the device.

2 schematically shows a process of manufacturing a multilayer printed circuit board according to an exemplary embodiment of the present invention. According to an exemplary embodiment of the present invention, the step of providing a metal substrate having a pattern on the insulating layer as shown in FIG. 2 includes: providing a metal thin film on the insulating layer; Providing a photosensitive resin layer provided with a pattern on the metal thin film; 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.

According to an exemplary embodiment of the present invention, 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, and specifically, the dry deposition process is vacuum It may be a vapor deposition, ion plating, sputtering method, or the like.

According to an exemplary embodiment of the present invention, the wet deposition process includes electroless plating of various metals, etc., electroless copper plating is generally used, and a roughening process may be further included before or after deposition.

According to an exemplary embodiment of the present invention, there are dry and wet methods according to conditions in the roughening treatment process, and examples of the dry method include vacuum, atmospheric pressure, plasma treatment for each gas, and Excimer UV treatment for each gas, As an example of the wet method, a desmear treatment may be used. Through this roughening process, it is possible to increase the surface roughness of the metal thin film to improve adhesion to the metal deposited on the metal thin film.

According to an exemplary embodiment of the present invention, the forming of the photosensitive resin layer on which the pattern is formed on the metal thin film may include exposing and developing the photosensitive resin layer formed on the metal thin film. The content of the photosensitive resin layer, exposure, and development may include the content described above in the embodiment.

According to an exemplary embodiment of the present invention, in the step of depositing a metal on the metal thin film exposed by the photosensitive resin layer pattern, the metal thin film exposed by the photosensitive resin layer pattern means that the surface does not contact the photosensitive resin layer. It refers to the part of the metal thin film that is not present. Copper may be used as the deposited metal, and the deposition method is not limited, and various known physical or chemical deposition methods may be used without limitation, and it is particularly preferable to use an electrolytic copper plating method.

According to an exemplary embodiment of the present invention, in the step of removing the photosensitive resin layer and removing the exposed metal thin film, a photoresist stripper may be used as an example of a method of removing the photosensitive resin layer, and the photosensitive resin layer An etchant may be used as an example of a method of removing the metal thin film exposed due to the removal of.

According to an exemplary embodiment of the present invention, the multilayer printed circuit board manufactured by the multilayer printed circuit board manufacturing method may be used again as a build-up material, for example, on the multilayer printed circuit board, A first process of forming an insulating layer according to the method of manufacturing an insulating layer and a second process of forming a metal substrate on the insulating layer according to the method of manufacturing a multilayer printed circuit board of another exemplary embodiment may be repeated. Accordingly, the number of laminated layers included in the multilayer printed circuit board manufactured by the multilayer printed circuit board manufacturing method is not limited also, and depending on the purpose and purpose of use, for example, one or more layers, or 1 to 20 layers Can have.

Hereinafter, examples will be described in detail in order to describe the present invention in detail. However, the embodiments according to the present invention may be modified in various forms, and the scope of the present invention is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely describe the present invention to those of ordinary skill in the art.

Example One

< Alkali Soluble Resin Manufacturing>

632 g of dimethylformamide (DMF) as a solvent and BMI-1100 (Daiwakasei) as a solvent in a reaction vessel with a volume of 2 liters capable of heating and cooling equipped with a manufacturing thermometer, agitating device, reflux cooling tube, and a moisture meter. Co., Ltd.) 358 g and 151 g of 4-aminophenylacetic acid 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%.

< Insulating layer Manufacturing>

1, a polymer resin composition in which 16 g of the synthesized alkali-soluble resin, 5 g of MY-510 (manufactured by Huntsman) as a thermosetting binder, and 35 g of SC2050 MTO (solid content 70%, manufactured by Adamatech) were mixed as an inorganic filler. It was applied to a PET film and dried to prepare a 15 µm-thick polymer resin layer (1). And. The polymer resin layer (1) was vacuum-laminated at 85° C. on a circuit board in which the copper wire (2) was formed on the copper clad laminate (3), and the PET film was removed. A 15 μm-thick photosensitive dry film resist KL1015 (manufactured by Kolon Industries) 4 was laminated on the polymer resin layer 1 at 110°C.

A circular negative photomask having a diameter of 30 µm is contacted on the photosensitive dry film resist 4, irradiated with ultraviolet rays (amount of light of 25 mJ/cm 2 ), and then the dry film resist through a 1% sodium carbonate developer at 30° C. (4) and the polymer resin layer (1) were sequentially developed.

At this time, the photosensitive dry film resist 4 on which the pattern is formed acts as a protective layer of the polymer resin layer 1, so that the same pattern as the photosensitive dry film resist 4 is formed in the polymer resin layer 1, A via hole 5 was formed. At this time, a white residue derived from the polymer resin layer 1 remained inside the via hole 5.

Thereafter, after heat curing at a temperature of 100 for 1 hour, the residue and the photosensitive dry film resist 4 were removed using a 3% sodium hydroxide resist stripper at a temperature of 50° C., and then thermoset at a temperature of 200° C. for 1 hour. The process of making it more advanced.

After the peeling, the surface of the heat-cured polymer resin layer was immersed in an amine-based basic solution, Amine Alkali (YMT, DR58), at 50° C. for 1 minute to perform surface treatment.

<Manufacturing of multilayer printed circuit boards>

Referring to FIG. 2, a mixed gas of argon and oxygen is supplied to the deposition equipment on the upper surface of the insulating layer 7 and the side of the via hole 5, while the copper (Cu) metal is converted to 300 nm through a sputtering method. Deposited to form a seed layer (8).

Thereafter, the photosensitive resin pattern 9 was formed by exposing and developing the photosensitive resin layer on the seed layer 8. Then, a metal substrate 10 made of copper was formed on the seed layer 8 through electroplating to a thickness of 20 μm. Next, the photosensitive resin pattern 9 was removed using a photosensitive resin stripper, and the seed layer 8 exposed thereto was removed through etching to prepare a multilayer printed circuit board.

Example 2

A multilayer printed circuit board was manufactured in the same manner as in Example 1, except that the surface treatment was performed for 2 minutes in Example 1.

Comparative example One

In Example 1, a multilayer printed circuit board was manufactured in the same manner as in Example 1, except that the surface treatment was performed for 2 minutes with a sodium hydroxide solution having a concentration of 5%.

Comparative example 2

A multilayer printed circuit board was manufactured in the same manner as in Example 1, except that the surface treatment was performed for 3 minutes in Example 1.

Comparative example 3

A multilayer printed circuit board was manufactured in the same manner as in Example 1, except that the surface treatment was performed for 4 minutes in Example 1.

Comparative example 4

A multilayer printed circuit board was manufactured in the same manner as in Example 1, except that the surface treatment was performed for 5 minutes in Example 1.

Experimental example One

The peel strength of the metal was measured for the multilayer printed circuit boards of Examples 1 and 2 and Comparative Examples 1 to 4 according to the IPC-TM-650 standard, and metal adhesion was obtained therefrom.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Metal adhesion
(kgf/cm) 0.28 0.31 0.17 0.16 0.16 0.18

In Example 1, the surface treatment was performed for 1 minute using an amine-based basic solution, and Example 2 was performed for 2 minutes. As shown in Table 1, in Examples 1 and 2, it was confirmed that the adhesion between the insulating layer and the metal substrate was improved.

In contrast, referring to Table 1, it was confirmed that in Comparative Example 1, by using sodium hydroxide solution as the surface treatment solution, the adhesion to the metal substrate was rapidly decreased. 3 is a front photograph of a multilayer printed circuit board of Examples 1 and 2 and Comparative Examples 1 to 4; Referring to FIG. 3, it was confirmed that in Comparative Example 1, as the sodium hydroxide solution was used as the surface treatment solution, the surface treatment did not proceed efficiently, and the surface color of the metal substrate was changed.

In addition, in Comparative Example 2, by performing the surface treatment for 3 minutes, it was confirmed that the surface treatment time was excessive and the adhesion to the metal substrate was rapidly decreased.

Further, in Comparative Examples 3 and 4, it was confirmed that the adhesion to the metal substrate was rapidly decreased by performing the surface treatment for 4 minutes or more, and the surface was excessively roughened due to a long surface treatment time, as shown in FIG. It was confirmed that the surface color of the substrate was changed.

1: polymer resin layer
2: copper line
3: Copper clad laminate
4: Photosensitive dry film resist (DFR)
5: Via hole
6: metal layer
7: insulating layer
8: seed layer
9: photosensitive resin pattern
10: metal substrate
a: surface treatment solution
<1> to <6>: procedure of the process

Claims (15)

Providing a polymer resin layer including an alkali-soluble resin and a thermosetting binder on the conductor wiring;
Providing a photosensitive resin layer on the polymer resin layer;
Exposing and alkali developing the photosensitive resin layer to provide a photosensitive resin pattern and at the same time alkali developing the polymer resin layer exposed by the photosensitive resin pattern;
After the alkali development, thermosetting the polymer resin layer;
Peeling the photosensitive resin pattern; And
Insulating layer manufacturing method comprising; surface-treating the heat-cured polymer resin layer with a surface treatment solution. The method according to claim 1,
The method of manufacturing an insulating layer, wherein the surface treatment solution is an amine-based basic solution. The method according to claim 1,
The surface treatment solution is an insulating layer manufacturing method that is a solution containing the following formula (1);
[Formula 1]

In Formula 1, X ₁ and X ₂ are each independently an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or an aminoalkyl group having 1 to 3 carbon atoms, and X ₁ and X ₂ are N or O added. It can form a ring that can be included with. The method according to claim 1,
The step of surface treatment,
An insulating layer manufacturing method that is immersed in the surface treatment solution for more than 0 minutes and less than 3 minutes. The method according to claim 1,
The step of surface treatment,
An insulating layer manufacturing method that is treated at 25° C. or more and 90° C. or less. The method according to claim 1,
The alkali-soluble resin is an acidic functional group; And a cyclic imide functional group substituted with an amino group; The method of claim 6,
The method of manufacturing an insulating layer containing a functional group represented by the following formula (2):
[Formula 2]

In Formula 2, R ₁ is an alkylene group or alkenyl group having 1 to 10 carbon atoms, and "*" means a bonding point. The method of claim 6,
The alkali-soluble resin is a cyclic unsaturated imide compound; And an amine compound; wherein at least one of the cyclic unsaturated imide compound and the amine compound includes an acidic functional group substituted at the terminal. The method of claim 8,
The amine compound is an insulating layer manufacturing method comprising at least one selected from the group consisting of a carboxylic acid compound substituted with an amino group and a polyfunctional amine compound including two or more amino groups. The method according to claim 1,
The alkali-soluble resin is a repeating unit represented by the following formula (4); And a repeating unit represented by the following formula (5); an insulating layer manufacturing method comprising at least one each:
[Formula 4]

In Formula 4, 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,
[Formula 5]

In Formula 5, 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,
The R ₅ and R ₆ may each independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
"*" means the point of attachment. The method of claim 10,
The alkali-soluble resin is a method for producing an insulating layer prepared by reaction of a polymer including a repeating unit represented by the following formula 6, an amine represented by the following formula 7, and an amine represented by the following formula 8
[Formula 6]

[Formula 7]

[Formula 8]

In Formulas 6 to 8, R ₂ to R ₄ are as defined in claim 10, and "*" means a bonding point.
The method of claim 10,
The alkali-soluble resin is an insulating layer manufacturing method prepared by reaction of a compound represented by the following formula (9) and a compound represented by the following formula (10):
[Formula 9]

[Formula 10]

In Formulas 9 and 10, R ₂ to R ₄ are as defined in claim 10. The method according to claim 1,
The polymer resin layer is an insulating layer manufacturing method comprising 1 part by weight to 150 parts by weight of a thermosetting binder based on 100 parts by weight of an alkali-soluble resin. A method of manufacturing a multilayer printed circuit board comprising the step of providing a metal substrate with a pattern on the insulating layer manufactured according to any one of claims 1 to 13. The method of claim 14,
The step of providing a metal substrate with a pattern on the insulating layer,
Providing a metal thin film on the insulating layer;
Providing a photosensitive resin layer in which a pattern is formed on the metal thin film; And
Depositing a metal on the metal thin film exposed by the photosensitive resin layer pattern; And
A method of manufacturing a multilayer printed circuit board comprising removing the photosensitive resin layer and removing the exposed metal thin film.

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