JP6732047B2 - Method for manufacturing insulating layer and method for manufacturing multilayer printed circuit board - Google Patents

Description

Cross-reference with Related Applications This application has priority based on Korean Patent Application No. 10-2016-0138673 of October 24, 2016 and Korean Patent Application No. 10-2017-0136513 of October 20, 2017. All contents disclosed in the literature of the Korean patent application claiming benefit are included as part of this specification.

The present invention relates to a method of manufacturing an insulating layer and a method of manufacturing a multilayer printed circuit board. More specifically, it can be manufactured by a quicker and simpler method, the efficiency of the process can be improved, physical damage to the insulating layer can be prevented, and the thickness of the insulating layer can be easily adjusted. The present invention relates to a method for manufacturing a multilayer printed circuit board using an insulating layer obtained by the method.

Recent electronic devices are becoming smaller, lighter and more sophisticated. For this reason, as the application field of build-up printed circuit boards (PCBs) is rapidly expanding, centering on small devices, the use of multilayer printed circuit boards is rapidly increasing.

The multi-layer printed circuit board is capable of three-dimensional wiring from planar wiring. Particularly, in the field of industrial electronics, the integration of functional elements such as ICs (integrated circuits) and LSIs (large scale integration) is improved, and This product is advantageous for downsizing, weight reduction, high functionality, structural electrical function integration, shortening of assembly time and cost reduction.

In the build-up PCB used in such an application area, connection between layers is always required, and thus a via hole corresponding to an electrical connection path between layers of a multilayer printed circuit board is formed. Although the method has been used, there is a limit in reducing the diameter of the via hole, and there is a limit in achieving high density.

Therefore, a method has been proposed in which fine protrusions having a diameter smaller than that of a via hole are used as an electrical connection path between layers of a multilayer printed circuit board. However, the conventional method is to form fine protrusions of a metal component on a single circuit, cover the fine protrusions with an insulating layer, and physically remove the insulating layer until the fine protrusions are exposed on the surface. In most cases, the insulating layer is liable to crack during the physical removal process, and it is difficult to adjust the desired thickness easily.

The present invention provides a method for manufacturing an insulating layer, which can be manufactured by a quicker and simpler method, can improve process efficiency, prevent physical damage to the insulating layer, and can easily adjust the thickness.

The present invention also provides a method for manufacturing a multilayer printed circuit board using an insulating layer obtained from the method for manufacturing an insulating layer.

In the present specification, a step of sealing a conductor wiring having a metal protrusion formed on a surface thereof with a polymer resin layer containing an alkali-soluble resin and a thermosetting binder, and a step of primary curing the polymer resin layer, The insulating layer of the insulating layer includes the steps of etching the surface of the cured polymer resin layer with an alkaline aqueous solution to expose the metal protrusions, and secondly curing the polymer resin layer with the metal protrusions exposed. A manufacturing method is provided.

The present specification also provides a method of manufacturing a multilayer printed circuit board, which includes the step of forming a metal pattern layer on the insulating layer manufactured by the method of manufacturing an insulating layer.

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

According to one embodiment of the present invention, a step of sealing a conductor wiring having a metal protrusion formed on a surface thereof with a polymer resin layer containing an alkali-soluble resin and a thermosetting binder, and first curing the polymer resin layer. A step of etching the surface of the cured polymer resin layer with an alkaline aqueous solution to expose the metal protrusions, and a step of secondarily curing the polymer resin layer with the metal protrusions exposed. A method of manufacturing an insulating layer is provided.

According to the method of manufacturing an insulating layer of the embodiment, the present inventors expose the metal protrusions sealed by the polymer resin layer by chemical etching with an alkaline aqueous solution to thereby physically damage the insulating layer. It was confirmed through experiments that not only can the insulation layer be prevented and the thickness of the insulation layer can be easily adjusted to a desired range, but also that the insulation layer can be manufactured by an easier process in a shorter time and the process efficiency can be improved. And completed the invention.

Particularly, in the method for manufacturing an insulating layer of the one embodiment, a polymer resin of a novel component capable of advancing stable etching at a proper level by a specific alkaline aqueous solution is applied to easily expose metal projections on the surface of the insulating layer. Therefore, there is an advantage that the multilayer circuit board can be easily manufactured through the exposed metal protrusion.

More specifically, the method for producing an insulating layer according to the one embodiment includes a step of sealing a conductor wiring having a metal protrusion formed on a surface thereof with a polymer resin layer containing an alkali-soluble resin and a thermosetting binder, A step of first curing the polymer resin layer; a step of etching the surface of the cured polymer resin layer with an alkaline aqueous solution to expose the metal protrusions; and a step of exposing the metal protrusions to the polymer resin layer. Secondary curing.

First, at the stage of sealing the conductor wiring having the metal protrusion formed on the surface with the polymer resin layer containing the alkali-soluble resin and the thermosetting binder, the conductor wiring has the metal protrusion formed on the surface. The example of the method of forming the metal protrusion on the surface of the conductor wiring is not particularly limited, and, for example, a plating process for the opening of the photosensitive resin layer pattern or a bonding process using an adhesive agent may be used. You can

Specific examples of the plating process for the openings of the photosensitive resin layer pattern include a step of laminating a photosensitive resin layer on a conductor wiring, a step of forming a pattern on the photosensitive resin layer, and a step of electroplating. Any method of forming metal protrusions including and can be used.

More specifically, the photosensitive resin layer can exhibit photosensitivity and alkali solubility. Accordingly, the deformation of the molecular structure can be promoted by the exposure step of irradiating the photosensitive resin layer with light, and the resin layer can be etched or removed by the developing step of contacting with an alkaline developing solution.

Therefore, if the photosensitive resin layer is selectively exposed to light and then alkali-developed, the exposed portion is not developed and only the unexposed portion can be selectively etched and removed. Thus, a part of the photosensitive resin layer which is left as it is without being alkali-developed by exposure is called a photosensitive resin pattern.

That is, to give an example of a method of exposing the photosensitive resin layer, a photomask having a predetermined pattern formed on the photosensitive resin layer is brought into contact with the photomask to irradiate ultraviolet rays, or a predetermined pattern contained in the mask. The pattern can be selectively exposed by, for example, irradiating with ultraviolet rays after imaging through a projection objective lens, or directly irradiating with ultraviolet rays after directly imaging using a laser diode as a light source. At this time, examples of the ultraviolet irradiation conditions include irradiation with a light amount of 5 mJ/cm ^{2 to} 600 mJ/cm ² .

Moreover, as an example of the method of carrying out alkali development after exposing the said photosensitive resin layer, the method of processing an alkali developing solution is mentioned. Examples of the alkaline developer are not particularly limited, and examples thereof include potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, amines. It is possible to adjust the concentration and temperature of the alkaline aqueous solution such as the above, and it is also possible to use the alkaline developer sold as a product. Although the specific amount of the alkaline developer used is not particularly limited, it is necessary to adjust the concentration and temperature so as not to damage the photosensitive resin pattern. For example, sodium carbonate 0.5% at 25°C to 35°C may be used. A 3% aqueous solution can be used.

On the other hand, in the electroplating step, examples of the plating method include a dry deposition process or a wet deposition process, and specific examples of the dry deposition process include vacuum deposition, ion plating, and a sputtering method. To be

On the other hand, as a specific example of the wet deposition process, there are electroless plating of various metals, etc., and electroless copper plating is generally used, and a roughening process process may be further included before or after the deposition.

The roughening treatment step also includes a dry method and a wet method depending on the conditions. Examples of the dry method include vacuum, atmospheric pressure, plasma treatment by gas, and Excimer UV treatment by gas. As an example, a desmear process can be used. By such a roughening treatment step, it is possible to increase the surface roughness of the metal thin film and improve the adhesion to the metal deposited on the metal thin film.

Further, a step of removing the photosensitive resin layer may be further included after the step of electroplating so as to leave only the metal protrusion. At the time of removing the photosensitive resin pattern, it is preferable to use a method in which only the photosensitive resin layer can be removed while the lower conductor wiring and the metal protrusion are not removed as much as possible.

As a specific example of the method for removing the photosensitive resin pattern, a photoresist removing solution can be treated, a desmear step or plasma etching can be performed, and the above methods can be mixed. it can.

On the other hand, to give a specific example of the bonding process using the adhesive, after forming a metal protrusion on the surface of a passive element such as micc or an active element such as a semiconductor chip, the opposite side of the formed metal protrusion is used. A method of adhering to the surface of the conductor wiring with an insulating adhesive or the like can be used. At this time, as the method of forming the metal protrusion on the surface of the passive element or the active element, the method of the plating process for the opening of the photosensitive resin layer pattern can be used as it is. For example, a method of forming a photosensitive resin layer pattern on the surface of a passive element or an active element and then plating a metal on the opening of the pattern can be used.

The polymer resin layer may have a thickness of 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 metal protrusion has a height of 1 μm to 20 μm. And can have a cross-sectional diameter of 5 μm to 30 μm. The cross-sectional diameter may mean a diameter of a cross section of the metal protrusion cut in a direction perpendicular to the height direction of the metal protrusion, or a maximum diameter. For example, the shape of the metal protrusion may be a cylinder, a truncated cone, a polygonal prism, a polygonal truncated cone, an inverted truncated cone, an inverted polygonal truncated cone, or the like. The example of the metal component contained in the metal protrusion is not particularly limited, and for example, a conductive metal such as copper or aluminum can be used.

The conductor wiring having the metal protrusion formed on the surface may be sealed with a polymer resin layer. More specifically, the conductor wiring can be present in a state of being formed on a base material containing a semiconductor material such as a circuit board, a sheet, and a multilayer printed wiring board at the bottom. With the conductor wiring present on the base material in this manner, the conductor wiring can be sealed by the method of forming the polymer resin layer on the base material.

The example of the method for forming the polymer resin layer on the substrate is not particularly limited, but for example, a polymer resin composition for forming the polymer resin layer may be directly coated on the substrate. Alternatively, a method of applying a polymer resin composition on a carrier film to form a polymer resin layer, and then laminating a base material and the polymer resin layer can be used.

By sealing the conductor wiring having the metal protrusion formed on the surface with the polymer resin layer, the conductor wiring is formed in all parts except the portion contacting the base material formed below and the portion contacting the metal protrusion. The surface of the can contact the polymer resin layer. Further, all the surfaces of the metal protrusions formed on the surface of the conductor wiring may be sealed with the polymer resin layer and contact the polymer resin layer.

The polymer resin layer means a film formed by drying a polymer resin composition containing an alkali-soluble resin and a thermosetting binder. The polymer resin layer may include 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 of 100 parts by weight of the alkali-soluble resin. it can. When the content of the thermosetting binder is too large, the developability of the polymer resin layer may be deteriorated and the strength may be decreased. On the other hand, 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.

The thermosetting binder is one or more functional groups 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, and an epoxy. A group can be included. That is, the thermosetting binder always 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 forms a cross-linking bond with an alkali-soluble resin or the like by thermosetting, and can ensure the heat resistance or mechanical properties of the insulating layer.

More specifically, as the thermosetting binder, a polyfunctional resin compound containing two or more of the above-described functional groups 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 a cyclic ether group having a 3-, 4-, or 5-membered ring in the molecule, or a cyclic thioether group, or two kinds thereof. It is possible to include a compound having at least two groups of the above.

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 epoxy groups in the molecule, a polyfunctional oxetane compound containing at least two oxetanyl groups in the molecule, or two molecules in the molecule. An 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 can be contained. ..

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, novolac type epoxy resin. 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, tetraglycidyl xylenoylethane resin, silicone modified epoxy resin, ε-caprolactone modified epoxy resin, etc. Are listed. Further, for the purpose of imparting flame retardancy, it is possible to use one in which an atom such as phosphorus is introduced into the structure. By heat-curing these epoxy resins, the properties of the cured coating such as adhesion, solder heat resistance and electroless plating resistance are improved.

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) ) Methyl acrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate, and other polyfunctional oxetanes such as oligomers or copolymers thereof, oxetane alcohol and novolac resin, Examples thereof include poly(p-hydroxystyrene), cardo type bisphenols, calixarenes, calixresorcinarenes, and etherified products with a resin having a hydroxy group such as silsesquioxane. 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, novolac 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, Bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (3,3'-dimethyl-5,5'-diethyl- 4,4′-diphenymethane 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) and the like can be mentioned.

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 Kukdo Chemical Co., phenol novolac type cyanate ester resin PT-30S manufactured by Lonza, and phenylmethane type maleimide resin BMI-2300 manufactured by Daiwa. Pd type benzoxazine resin of Shikokusha etc. are mentioned.

On the other hand, the alkali-soluble resin may include at least two acidic functional groups and at least two cyclic imide functional groups substituted with amino groups. Examples of the acidic functional group are not particularly limited, but may include, for example, a carboxy group or a phenol group. The alkali-soluble resin contains at least two acidic functional groups so that the polymer resin layer exhibits higher alkali developability, and the developing rate of the polymer resin layer can be adjusted.

The cyclic imide functional group substituted with the amino group contains an amino group and a cyclic imide group in the functional group structure, and is contained in at least two or more. When the alkali-soluble resin contains at least two or more cyclic imide functional groups substituted with the amino group, the alkali-soluble resin has a structure in which a plurality of active hydrogens contained in the amino group are present, and curing At this time, as the reactivity with the thermosetting binder is improved, the curing density can be increased to improve heat resistance reliability and mechanical properties.

In addition, the presence of a plurality of the cyclic imide functional groups in the alkali-soluble resin increases the polarity by the carbonyl group and the tertiary amine group contained in the cyclic imide functional group, and enhances the interfacial adhesion of the alkali-soluble resin. be able to. As a result, the polymer resin layer containing the alkali-soluble resin has an increased interfacial adhesion with the metal layer laminated on top.

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

In Chemical Formula 1, R ₁ is an alkylene group or an alkenyl group having 1 to 10, or 1 to 5, or 1 to 3 carbon atoms, and “*” means a bonding point. The alkylene group is a divalent functional group derived from an alkane, and is, for example, linear, branched or cyclic, and is a methylene group, an ethylene group, a propylene group, an isobutylene group or a sec-butylene group. , Tert-butylene group, pentylene group, hexylene group and the like. One or more hydrogen atoms contained in the alkylene group may be substituted with other substituents, and examples of the substituents include an alkyl group having 1 to 10 carbon atoms and an alkyl group having 2 to 10 carbon atoms. Alkenyl group, 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, Examples thereof include an amidino group, a nitro group, an amide group, a carbonyl group, a hydroxy group, a sulfonyl group, a carbamate group, and an alkoxy group having 1 to 10 carbon atoms.

The term “substituted” means that another functional group is bonded instead of the hydrogen atom in the compound, and the position of substitution is the position of substitution of the hydrogen atom, that is, the position at which the substituent can be substituted. It is not limited as long as it is substituted with two or more, and the two or more substituents may be the same or different from each other.

The alkenyl group means one having at least one carbon-carbon double bond at the middle or terminal of the above-mentioned 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 substituents as in the alkylene group.

Preferably, the cyclic imide functional group substituted with the amino group may be a functional group represented by Chemical Formula 2 below.

In Chemical Formula 2, “*” means a bonding point.

As described above, the alkali-soluble resin contains a cyclic imide functional group substituted with an amino group together with an acidic functional group, and specifically, at least one end of the cyclic imide functional group substituted with the amino group is attached to the terminal. An acidic functional group may be attached. 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. At the terminal of the amino group contained in the cyclic imide functional group substituted with a group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group, an acidic functional group may be bonded, At the terminal of the imide functional group contained in the cyclic imide functional group substituted with the amino group, even if an acidic functional group is bonded via a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group. Good.

More specifically, the term “terminal of the amino group contained in the cyclic imide functional group substituted with the amino group” means the nitrogen atom contained in the amino group in Chemical Formula 1, The term “terminal of the imide functional group contained in the substituted cyclic imide functional group” can mean the nitrogen atom contained in the cyclic imide functional group in Formula 1 above.

The alkylene group is a divalent functional group derived from an alkane, and is, for example, linear, branched or cyclic, and is a methylene group, an ethylene group, a propylene group, an isobutylene group or a sec-butylene group. , Tert-butylene group, pentylene group, hexylene group and the like. One or more hydrogen atoms contained in the alkylene group may be substituted with other substituents, and examples of the substituents include an alkyl group having 1 to 10 carbon atoms and an alkyl group having 2 to 10 carbon atoms. Alkenyl group, 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, Examples thereof include an amidino group, a nitro group, an amide group, a carbonyl group, a hydroxy group, a sulfonyl group, a carbamate group, and an alkoxy group having 1 to 10 carbon atoms.

The arylene group is a divalent functional group derived from arene, and may be, for example, a cyclic group such as a phenyl group or a naphthyl group. One or more hydrogen atoms contained in the arylene group may be substituted with other substituents, and examples of the substituents include an alkyl group having 1 to 10 carbon atoms and 2 to 10 carbon atoms. Alkenyl group, 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, Examples thereof include an amidino group, a nitro group, an amide group, a carbonyl group, a hydroxy group, a sulfonyl group, a carbamate group, and an alkoxy group having 1 to 10 carbon atoms.

The method for producing the alkali-soluble resin is not particularly limited, but for example, it is produced by reacting a cyclic unsaturated imide compound; and an amine compound. At this time, at least one or more of the cyclic unsaturated imide compound and the amine compound may include a terminal substituted acidic functional group. That is, an acidic functional group may be substituted at all terminals of the cyclic unsaturated imide compound, the amine compound, or these two compounds. The content regarding the acidic functional group is as described above.

The cyclic imide compound is a compound containing a cyclic imide functional group described above, the cyclic unsaturated imide compound is an unsaturated bond in the cyclic imide compound, that is, a compound containing at least one double bond or triple bond. means.

The alkali-soluble resin is produced by the reaction between the amino group contained in the amine compound and the double bond or triple bond contained in the cyclic unsaturated imide compound.

The example of the weight ratio for reacting the cyclic unsaturated imide compound and the amine compound is not particularly limited, but for example, 10 parts by weight to 80 parts by weight of the amine compound relative to 100 parts by weight of the cyclic unsaturated imide compound. It is possible to react by mixing by weight, or 30 to 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 the hydrogen atom bonded to the nitrogen atom contained in the maleimide compound, and the N-substituted maleimide compound is the number of N-substituted maleimide compounds. Are classified into monofunctional N-substituted maleimide compounds and polyfunctional N-substituted maleimide compounds.

The monofunctional N-substituted maleimide compound is a compound in which a nitrogen atom contained in one maleimide compound is substituted with a functional group, and the polyfunctional N-substituted maleimide compound is contained in each of two or more maleimide compounds. It is a compound in which the nitrogen atom is bound via a functional group.

In the monofunctional N-substituted maleimide compound, the functional group substituted on the nitrogen atom contained in the maleimide compound may include various known aliphatic, alicyclic or aromatic functional groups without limitation. The functional group substituted on 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 content regarding the acidic functional group is 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 intervening the bond between the nitrogen atoms contained in each of the two or more maleimide compounds is limited to various known aliphatic, alicyclic or aromatic functional groups. For example, 4,4′-diphenylmethane functional group can be used. The functional group substituted on 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 content regarding the acidic functional group is as described above.

Specific examples of the polyfunctional N-substituted maleimide compound include 4,4′-diphenylmethane bismaleimide (BMI-1000, BMI-1100 and the like from Daiwakasei), phenylmethane bismaleimide, m-phenylenemethane bismaleimide, bisphenol A. Diphenyl ether 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 and the like can be mentioned.

As the amine compound, a primary amine compound containing 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, or two or more Polyfunctional amine compounds containing amino groups, or mixtures thereof can be used.

In the carboxylic acid compound substituted with an amino group, the carboxylic acid compound is a compound containing a carboxylic acid (—COOH) functional group in the molecule, and is a fatty acid depending on the type of hydrocarbon bonded to the carboxylic acid functional group. It can include all group, alicyclic or aromatic carboxylic acids. When a plurality of carboxylic acid functional groups of acidic functional groups are contained in the alkali-soluble resin via the carboxylic acid compound substituted with the amino group, the developability of the alkali-soluble resin can be improved.

Specifically, the alkali-soluble resin produced by the reaction of the carboxylic acid compound substituted with the amino group and the cyclic unsaturated imide compound has an acid value (acid value) determined by KOH titration of 50 mgKOH/g to 250 mgKOH/ It may be g, or 70 mgKOH/g to 200 mgKOH/g. The method of measuring the acid value of the alkali-soluble resin is not particularly limited, but the following method can be used, for example. A KOH solution (solvent: methanol) having a concentration of 0.1N was prepared as a base solution, and alpha-naphtholbenzein (pH: 0.8 to 8.) was used as an indicator. 2 yellow, 10.0 blue green) was prepared. Next, about 1 to 2 g of the alkali-soluble resin as a sample was sampled and dissolved in 50 g of dimethylformaldehyde (DMF) solvent, and after adding a indicator, titration was performed as a base solvent. The acid value was determined in mg KOH/g with the amount of base solvent used at the end 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 may be low and the development process may be difficult to proceed. In addition, when the acid value of the alkali-soluble resin excessively increases to more than 250 mgKOH/g, the polarity may increase to cause phase separation with other resins.

The term "substituted" means that another functional group is bonded to the compound in place of a hydrogen atom, and the position where the amino group is substituted on the carboxylic acid compound is the position where the hydrogen atom is substituted. It is not limited as long as it is present, and the number of substituted amino groups may be 1 or more.

Specific examples of the carboxylic acid compound substituted with an amino group include 20 kinds of α-amino acids known as raw materials for proteins, 4-aminobutanoic acid, 5-aminopentanoic acid, 6-aminohexanoic acid, 7 -Aminoheptanoic acid, 8-aminooctanoic acid, 4-aminobenzoic acid, 4-aminophenylacetic acid, 4-aminocyclohexanecarboxylic acid and the like can be mentioned.

Further, a polyfunctional amine compound containing the two or more amino groups is a compound containing 2 or more amino group (-NH ₂₎ in the molecule, aliphatic depending on the type of hydrocarbon bonded with an amino group, fat All cyclic or aromatic polyfunctional amines can be included. Through the polyfunctional amine compound containing two or more amino groups, the flexibility, toughness, and copper foil adhesion of the alkali-soluble resin can be improved.

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, and 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,-tetra Methyl-1,4-phenylenediamine, 2,4,5,6-tetrafluoro-1,3-phenylenediamine, 2,3,5,6-tetrafluoro-1,4-phenylenediamine, 4,6-diamino Resorcinol, 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'-diamino Diphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-methylenebis(2-ethyl-6-methylaniline), 4,4'-methylenebis(2,6-diethylaniline), 3,3'-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-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]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-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-inden-5-amine, 4,6-diaminoresorcinol, 2,3,5,6-pyridinetetraamine, a polyfunctional amine containing a 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), Dow Corning siloxane structure. Examples thereof include polyfunctional amines (Dow Corning 3055) and polyfunctional amines having a polyether structure (Huntsman, BASF).

Further, 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 Chemical Formula 3, R ₂ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and “*” indicates a bonding point. Meaning,

In Chemical Formula 4, R ₃ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and R ₄ is —H or —. 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 carbon atoms 6, It may be 20 aryl groups, where "*" means the point of attachment.

Preferably, in Formula 3, R ₂ may be phenylene, in 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 the chemical formula 3; and the repeating unit represented by the 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 largely limited. Instead, for example, ethylene, propylene, isobutylene, butadiene, styrene, acrylic acid, methacrylic acid, maleic anhydride, maleimide or the like can be mentioned.

The alkali-soluble resin containing at least one repeating unit represented by the chemical formula 3 and the repeating unit represented by the chemical formula 4 is a polymer containing the repeating unit represented by the chemical formula 5 below, or a polymer containing the repeating unit represented by the chemical formula 6 below. And an amine represented by Chemical Formula 7 below.

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

Specific examples of the polymer containing the repeating unit represented by the chemical formula 5 are not particularly limited, and examples thereof include SMA of Cray valley, Xiran of Polyscope, Scripset of Solenis, Isobam and Chevron of Kuraray. Polyanhydride resin from Philips Chemicals, Maldene from Lindau Chemicals and the like can be mentioned.

Further, the alkali-soluble resin containing at least one repeating unit represented by the chemical formula 3 and at least one repeating unit represented by the chemical formula 4 is a compound represented by the chemical formula 8 below or a compound represented by the chemical formula 9 below. It is manufactured by the reaction of.

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

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

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 it 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 phenolic resin with a compound having one epoxy group in the molecule and then reacting it with a polybasic acid anhydride,
(4) Carboxy group-containing resin obtained by reacting a compound having two or more alcoholic hydroxyl groups in the molecule with a polybasic acid anhydride,
(5) Polyamic acid resin obtained by reacting diamine and dianhydride or a copolymer resin of polyamic acid resin,
(6) Polyacrylic acid resin reacted with acrylic acid or a copolymer of polyacrylic acid resin,
(7) The maleic anhydride resin reacted with the maleic anhydride and the anhydride of the polymaleic anhydride resin copolymer are subjected to ring opening with a weak acid, a diamine, imidazole, or dimethyl sulfoxide. Examples include, but are not limited to, manufactured resins.

More specific examples of the carboxy group-containing resin include Nippon Kayaku's CCR-1291H, Shina T&C's SHA-1216CA60, Lubrizol's Noverite K-700, or a mixture of two or more thereof.

Examples of the phenol group-containing resin are not particularly limited, but examples thereof include novolac resins such as phenol novolac resin, cresol novolac resin, and 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) phenyl) ethane-1, 1-diyl) diphenol] and the like, bisphenol A resins can be used alone or in combination.

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

The 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, Imidazole derivatives such as 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N- Examples thereof include amine compounds such as dimethylbenzylamine and 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Further, as commercially available products, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both are trade names of imidazole compounds) manufactured by Shikoku Chemicals, U-CAT3503N, UCAT3502T manufactured by San-Apro Co., Ltd. Examples thereof include trade names of dimethylamine blocked isocyanate compounds), DBU, DBN, U-CATS A102, and U-CAT5002 (all are bicyclic amidine compounds and salts thereof). It is not particularly limited to these, and may be a thermosetting catalyst for an epoxy resin or an oxetane compound, or one that promotes the reaction between an epoxy group and/or an oxetanyl group and a carboxy group, alone or in combination of two or more. It can also be used as a mixture. Further, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl-4,6-diamino. An S-triazine derivative such as an -S-triazine-isocyanuric acid adduct or a 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct may be used, and preferably, adhesion of these is imparted. A compound that also functions as an 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, 100 parts by weight of all resin components contained in the polymer resin layer are added. On the other hand, 100 parts by weight or more, or 100 parts by weight to 600 parts by weight, or 100 parts by weight to 500 parts by weight of the inorganic filler can be added.

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

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

The leveling agent plays a role of removing surface popping and craters during film coating, and for example, BYK-380N, BYK-307, BYK-378, and BYK-350 of BYK-Chemie GmbH can be used. ..

In addition, the polymer resin layer may further include a resin or elastomer having a molecular weight of 5000 g/mol or more, which can induce phase separation. This allows roughening of the cured product of the polymer resin layer. The example of the method for measuring the molecular weight of the resin or elastomer having a molecular weight of 5000 g/mol or more is not particularly limited, and means, for example, the polystyrene equivalent weight average molecular weight measured by the 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. The temperature conditions, the solvent, and the 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.

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

The content of the photoinitiator contained in the polymer resin layer may be 0.01% by weight or less based on the weight of the entire polymer resin layer. The content of the photoinitiator contained in the polymer resin layer is 0.01% by weight or less relative to the weight of the entire polymer resin layer means that the content of the photoinitiator contained in the polymer resin layer is It can mean very little or no photoinitiator at all. Thereby, the interfacial desorption property with the insulating layer or the conductive layer which can be generated by the photoinitiator can be reduced, and the adhesive property and durability of the insulating layer can be improved.

In addition, the method of manufacturing the insulating layer according to the exemplary embodiment may include a step of primary curing the polymer resin layer. At the stage of curing the polymer resin layer, a specific example of a curing method is not particularly limited, and any heat curing or photo-curing method can be used without limitation.

The primary curing step forms a main chain containing an ester bond in the polymer resin layer. Examples of the ester bond include a method of photo-curing acrylic acid via an acrylic resin having an ester bond, or a method of heat curing so that an ester bond is formed by the reaction of carboxylic acid and epoxy.

At this time, the specific thermosetting conditions are not limited, and preferable conditions can be adjusted to proceed according to the method for etching the polymer resin layer described later. For example, when the photoresist stripper is treated to etch the polymer resin layer, the primary curing step of the polymer resin layer may be performed at a temperature of 50° C. to 150° C. for 0.1 hours to 2 hours. it can. If the thermosetting temperature of the polymer resin layer is excessively low or the thermosetting time becomes short, the polymer resin layer may be excessively damaged by the peeling liquid, and the thermosetting temperature of the polymer resin layer may be high. If the heat-curing time is long, the etching of the polymer resin layer by the stripping solution may be difficult to proceed.

In addition, the method of manufacturing the insulating layer of the exemplary embodiment may include a step of exposing the surface of the cured polymer resin layer with an alkaline aqueous solution to expose the metal protrusion. By etching the surface of the cured polymer resin layer with an alkaline aqueous solution to expose the metal protrusions, the conductive wiring and the electrical signal sealed inside the cured polymer resin layer through the exposed metal protrusions. Can be connected.

The exposure of the metal protrusions described above can be progressed by etching with an alkaline aqueous solution. The alkaline aqueous solution may have a temperature of 10° C. to 100° C., or 25° C. to 60° C., and a concentration of 1% to 10%, or 1% to 5%, and more specifically, photoresist stripping. A liquid can be used. The alkaline aqueous solution can remove the polymer resin layer by etching by cutting the ester bond in the polymer resin layer in which the main chain containing the ester bond is formed by the primary curing. At this time, it is possible to control the etching rate of the polymer resin layer by the alkaline aqueous solution by adjusting the concentration and temperature of the alkaline aqueous solution, and to maintain an appropriate level of the etching rate within the above range to improve the process efficiency. The thickness of the polymer resin layer can be easily adjusted while ensuring the thickness.

The alkaline aqueous solution may be an aqueous solution of a metal hydroxide such as potassium hydroxide or sodium hydroxide, and may be a resist product group of Atotech, ORC-731, ORC-723K, ORC-740, SLF of ORCHEM. Commercially available products such as -6000 can also be used.

The etching with the alkaline aqueous solution may proceed from the surface of the cured polymer resin layer. The surface of the cured polymer resin layer means the area where the polymer resin layer that seals the conductor wiring on which the metal protrusions are formed contacts the air, and the surface of the cured polymer resin layer. The metal protrusions can be exposed as the etching progresses inside the polymer resin layer that seals the conductor wiring having the metal protrusions formed on the surface.

Since the etching with the alkaline aqueous solution proceeds from the surface of the cured polymeric resin layer, the alkaline aqueous solution may contact the surface of the cured polymeric resin layer. At this time, the alkaline aqueous solution may be contacted on the surface of the polymer resin layer by a method such as spraying in order to ensure thickness uniformity by uniform removal without physical damage of the polymer resin layer. ..

In addition, the method of manufacturing the insulating layer according to the exemplary embodiment may include a step of secondarily curing the polymer resin layer with the metal protrusion exposed. The second hardening step may improve the chemical resistance of the insulating layer finally manufactured by the second hardening step.

At this time, the specific curing conditions are not limited, and for example, the secondary curing step of the polymer resin layer may be performed at a temperature of 150°C to 250°C for 0.1 hours to 2 hours. ..

On the other hand, after the step of secondarily curing the polymer resin layer with the metal protrusion exposed, a step of removing the base material formed under the conductor wiring may be further included, if necessary. As described above, the conductor wiring may exist in a state of being formed on a base material containing a semiconductor material such as a circuit board, a sheet, and a multilayer printed wiring board on the lower portion. In order to form a multilayer circuit board having a finer structure, the base material under the conductor wiring can be removed, if necessary, and the base material is adhered or adhered to the polymer resin layer. It is present and can be physically stripped and removed.

Meanwhile, according to another embodiment of the present invention, there is provided a method of manufacturing a multilayer printed circuit board, which includes the step of forming a patterned metal pattern layer on the insulating layer manufactured according to the one embodiment.

According to the inventors, the insulating layer manufactured in the one embodiment includes a conductor wiring having a metal protrusion formed on the surface thereof, the metal protrusion being exposed to the outside of the insulating layer, In the case of newly laminating a metal pattern layer on, the present invention was completed by confirming that the metal pattern layer can exchange electrical signals with the conductor wiring inside the insulating layer through the metal protrusion.

The insulating layer can be used as an interlayer insulating material of a multilayer printed circuit board, and can include a cured product of an alkali-soluble resin and a thermosetting binder, specifically, a thermoset product or a photocured product. The contents regarding the alkali-soluble resin and the thermosetting binder include the contents described above in the one embodiment.

More specifically, to give an example of a step of forming a metal pattern layer on the insulating layer, a step of forming a metal thin film on the insulating layer and a photosensitive resin having a pattern formed on the metal thin film. The method may include forming a 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 a 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 specific examples of the dry deposition process include vacuum deposition and ion deposition. Examples include plating and sputtering methods.

On the other hand, as a specific example of the wet deposition process, there is electroless plating of various metals, and electroless copper plating is generally used, and a roughening process may be further included before or after the deposition.

The roughening treatment step also includes a dry method and a wet method depending on the conditions. Examples of the dry method include vacuum, atmospheric pressure, plasma treatment by gas, and Excimer UV treatment by gas. As an example, a desmear process can be used. By such a roughening treatment step, it is possible to increase the surface roughness of the metal thin film and improve the adhesion to the metal deposited on the metal thin film.

Further, the step of forming the metal thin film on the insulating layer may further include the step of forming a surface treatment layer on the insulating layer before depositing the metal thin film. Accordingly, the adhesive force between the metal thin film and the insulating layer can be improved.

Specifically, as an example of a method of forming a surface treatment layer on the insulating layer, 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 an atmospheric 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 is formed on the surface of the insulating layer. Another example of the method of forming the surface treatment layer on the insulating layer is a method of depositing chromium (Cr) or titanium (Ti) metal having a thickness of 50 nm to 300 nm on the surface of the insulating layer. ..

Meanwhile, the step of forming the patterned photosensitive resin layer on the metal thin film may include exposing and developing the photosensitive resin layer formed on the metal thin film. The contents relating to the photosensitive resin layer and exposure and development may include the contents described above in the one embodiment.

In particular, the pattern formed on the metal thin film is preferably formed so that the openings included in the pattern can contact the metal protrusions exposed to the outside of the insulating layer. The opening portion included in the pattern means a portion removed by exposure and development of the photosensitive resin layer, and corresponds to a portion where metal is deposited by metal deposition described below to form the metal pattern layer. .. Therefore, it is necessary that the openings included in the pattern are formed so as to contact the metal protrusions exposed to the outside of the insulating layer, and the metal pattern layer is in contact with the metal protrusions while the conductor wiring inside the insulating layer is being formed. Can exchange electrical signals with.

In the step of depositing a metal on the metal thin film exposed by the photosensitive resin layer pattern, the metal thin film exposed by the photosensitive resin layer pattern means a metal thin film portion which is not in contact with the photosensitive resin layer on the surface. To do. As the metal to be deposited, copper may be used, examples of the deposition method are not particularly limited, and various known physical or chemical vapor deposition methods may be used without limitation. Can use the electrolytic copper plating method.

At this time, the metal deposited on the metal thin film exposed by the photosensitive resin layer pattern may form the metal pattern layer described above, and more specifically, the metal pattern layer may be formed through metal protrusions. It is formed so as to be connected to the conductor wiring. As a result, the metal pattern layer can exchange electrical signals with the conductor wiring included inside the insulating layer. More specifically, one end of the metal protrusion is in contact with a conductor wiring, and the other end of the metal protrusion is in contact with the metal pattern layer to electrically connect the conductor wiring and the metal pattern layer. be able to.

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

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

Accordingly, the number of laminated layers included in the multilayer printed circuit board manufactured by the method for manufacturing a multilayer printed circuit board is not particularly limited, and for example, one or more layers may be used depending on the purpose of use and application. Alternatively, it can have 1 to 20 layers.

ADVANTAGE OF THE INVENTION According to this invention, it can be manufactured by a quicker and simpler method, the efficiency of a process can be improved, physical damage to an insulating layer can be prevented, and the thickness of the insulating layer can be easily adjusted. There is provided a method of manufacturing a multilayer printed circuit board using an insulating layer obtained from the method of manufacturing.

The invention is explained in more detail in the examples below. However, the following examples merely exemplify the present invention, and the contents of the present invention are not limited to the following examples.

<Production Example: Production of alkali-soluble resin>

Production example 1
In a reaction vessel having a heating and cooling capacity of 2 liters, equipped with a production thermometer, a stirrer, a reflux condenser, and a water content meter, 632 g of dimethylformamide (DMF) as a solvent and BMI as an N-substituted maleimide compound were used. -1100 (manufactured by Daiwakasei Co., Ltd.) was mixed with 358 g of 4-aminophenylacetic acid as an amine compound, and the mixture was stirred at 85° C. for 24 hours to prepare an alkali-soluble resin solution having a solid content of 50%.

Production example 2
In a reaction vessel having a volume of 2 liters capable of heating and cooling, equipped with a production thermometer, a stirrer, a reflux condenser, and a moisture meter, 632 g of dimethylformamide (DMF) as a solvent and p as an N-substituted maleimide compound were used. -434 g of carboxyphenylmaleimide and 198 g of 4,4'-diaminodiphenylmethane 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
In a reaction vessel having a heating and cooling capacity of 2 liters equipped with a production thermometer, a stirrer, a reflux condenser, and a moisture meter, 543 g of dimethylacetamide (Dimethylacetamide, DMAc) was put as a solvent, and a Cray Valley company 350 g of SMA1000, 144 g of 4-aminobenzoic acid (PABA) and 49 g of 4-aminophenol (4-aminophenol, PAP) were added and then mixed. Under a nitrogen atmosphere, the temperature of the reactor was set to 80° C., the acid anhydride and the aniline derivative were reacted with each other for 24 hours to form an amic acid, and then the temperature of the reactor was set to 150° C. and continued for 24 hours. The imidization reaction was allowed to proceed to produce an alkali-soluble resin solution having a solid content of 50%.

Production Example 4
Into a reaction vessel having a heating and cooling capacity of 2 liters equipped with a production thermometer, a stirrer, a reflux condenser, and a moisture meter, 516 g of methyl ethyl ketone (methylethylketone, MEK) was placed as a solvent, and p-carboxyphenylmaleimide. 228 g of (p-carboxyphenylmaleimide), 85 g of p-hydroxyphenylmaleimide (p-hydroxyphenylmaleimide), 203 g of styrene (styrene), and 0.12 g of azobisisobutyronitrile (AIBN) were added and then mixed. After gradually raising the temperature of the reactor to 70° C. under a nitrogen atmosphere, the reaction was continued for 24 hours to prepare an alkali-soluble resin solution having a solid content of 50%.

<Example: Manufacturing of insulating layer and multilayer printed circuit board>

Example 1
(1) Production of Insulating Layer 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 (70% solid content, manufactured by Adamatech) as an inorganic filler are mixed. The polymer resin composition prepared above was applied to an untreated PET film having a thickness of 25 μm and dried to produce a polymer resin layer having a thickness of 18 μm.

Then, a dry film (RY-5319, Hitachi Chemical Co., Ltd.) is laminated on a copper foil laminated plate (LG-500GA VB/VB, LG Chemical) to which an ultra-thin copper foil is adhered to form a pattern, and electroplating is performed. Then, a circuit was formed by the MSAP method. Then, a dry film (RY-5319, Hitachi Chemical Co., Ltd.) was laminated on the circuit to form a pattern, and electroplating was performed to form a copper bump having a height of 15 μm and a diameter of 20 μm.

Then, a polymer resin layer was vacuum laminated on the copper foil laminate at 85° C. to seal the circuit and the copper bump, and the PET film was removed from the polymer resin layer. The laminated polymer resin layer was first heat-cured at a temperature of 100° C. for 1 hour, and then a 3% sodium hydroxide resist stripping solution at a temperature of 50° C. was spray-sprayed on the surface of the polymer resin layer. The copper bumps were removed from the surface of the polymer resin layer by a depth of about 3 μm to expose the copper bumps on the surface, washed with water and dried. At this time, the process of exposing the copper bump was performed in a continuous process for 10 to 60 seconds per panel.

Then, the polymer resin layer with the copper bumps exposed on the surface was thermoset at a temperature of 200° C. for 1 hour to manufacture an insulating layer.

(2) Manufacture of multilayer printed circuit board After depositing a copper thin film on the insulating layer using electroless copper plating and heating at a temperature of 100° C. for 30 minutes to improve the adhesion with the electroless copper plating , A dry film (RY-5319, Hitachi Chemical Co., Ltd.) was laminated to form a pattern, and electroplating was performed to form a circuit by the SAP method. Then, the copper foil laminate and the ultrathin copper foil were separated and removed from the insulating layer to complete a multilayer printed circuit board.

Example 2
Insulation was performed in the same manner as in Example 1 except that the alkali-soluble resin synthesized in Production Example 1 was used in place of the alkali-soluble resin synthesized in Production Example 1 in the step of producing the insulating layer of Example 1. Layer and multilayer printed circuit boards were manufactured.

Example 3
Insulation was performed in the same manner 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 in the step of producing the insulating layer of Example 1. Layer and multilayer printed circuit boards were manufactured.

Example 4
Insulation was performed in the same manner as in Example 1 except that the alkali-soluble resin synthesized in Production Example 4 was used in place of the alkali-soluble resin synthesized in Production Example 1 in the step of producing the insulating layer of Example 1. Layer and multilayer printed circuit boards were manufactured.

<Comparative example: manufacture of insulating layer and multilayer printed circuit board>

Comparative Example 1
(1) Production of Insulating Layer Instead of the polymer resin layer of Production Example 1, a 100 μm-thick molding sheet (LE-T17B, Ajinomoto) was used, vacuum laminated at 120° C., and 170° C. After heat curing for a period of time, an insulating layer was formed in the same manner as in Example 1 except that the surface of the heat cured polymer resin layer was ground by a grinding machine to expose the copper bumps. Manufactured.

At this time, it was confirmed that the step of exposing the copper bumps was performed in a batch process for 10 to 20 minutes per panel, and a longer time was spent as compared with the example.

(2) Manufacture of multilayer printed circuit board A multilayer printed circuit board was manufactured in the same manner as in Example 1 with respect to the insulating layer obtained in Comparative Example 1.

Comparative example 2
The laminated polymer resin layer is first thermally cured at a temperature of 100° C. for 1 hour, and then a 3% sodium hydroxide resist stripping solution at a temperature of 50° C. is sprayed onto the surface of the polymer resin layer instead of spraying. After heat-curing the polymer resin layer at a temperature of 200° C. for 1 hour, a sweller (Atotech, Sweller-p, 40%), etching (KMnO ₄ 9%, NaOH, 6%) and neutralization are performed by a usual method. (H ₂ SO ₄ , 9%) in the same order as in Example 1, except that the copper bumps were exposed on the surface by desmearing the surface of the polymer resin layer to a depth of about 3 μm. An insulating layer and a multilayer printed circuit board were manufactured.

At this time, the desmearing process of exposing the copper bumps proceeds for 5 to 10 minutes per panel only in an etching step in a continuous batch process, and a longer time is spent as compared with the embodiment. It was confirmed that not only such harmful chemical substances had to be added, but it was difficult to control the thickness of the polymer resin layer.

Comparative Example 3
A polymer resin composition having a thickness of 25 μm was prepared 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. It was applied on an untreated PET film and dried to produce a polymer resin layer having a thickness of 18 μm.

Then, a dry film (RY-5319, Hitachi Chemical Co., Ltd.) is laminated on a copper foil laminated plate (LG-500GA VB/VB, LG Chemical) to which an ultra-thin copper foil is adhered to form a pattern, and electroplating is performed. Then, a circuit was formed by the MSAP method. Then, a dry film (RY-5319, Hitachi Chemical Co., Ltd.) was laminated on the circuit to form a pattern, and electroplating was performed to form a copper bump having a height of 15 μm and a diameter of 20 μm.

Then, a polymer resin layer was vacuum laminated on the copper foil laminate at 85° C. to seal the circuit and the copper bump, and the PET film was removed from the polymer resin layer. Thereafter, the step of first thermosetting the laminated polymer resin layer at a temperature of 100° C. for 1 hour is omitted, and the laminated polymer resin layer is immediately added with a 3% sodium hydroxide resist at a temperature of 50° C. The stripping solution was sprayed onto the surface of the polymer resin layer.

At this time, in the case of Comparative Example 3, it was confirmed that the polymer resin layer was completely removed within 10 seconds after the sodium hydroxide resist stripping solution was sprayed, and the copper bump and the underlying circuit were exposed to a technical limit. It was

That is, as in Comparative Example 3, when the curing step for the polymer resin layer is not advanced before the stripping solution is sprayed, it is difficult to control the degree of removal of the polymer resin layer and only a part of the copper bump is controlled. It was confirmed that it was not suitable for being exposed on the surface of the polymer resin layer.

<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 above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1.

1. Adhesion of metal by moisture absorption The multilayer printed circuit boards obtained in the examples and comparative examples were allowed to stand for 48 hours in a moisture absorption state of 135° C. and 85%, and then peel strength of metal according to IPC-TM-650 standard. Was measured and the metal adhesion was determined from this.

2. HAST (High Accelerated Temp & Humidity Stress Test) Resistance The multilayer printed circuit boards obtained in the above-mentioned Examples and Comparative Examples were confirmed to have HAST resistance according to the JESD22-A101 standard. Specifically, a voltage of 3 V is applied to a test piece circuit board having widths, intervals, and thicknesses of 50 μm, 50 μm, and 12 μm, respectively, and the test piece circuit board is allowed to stand for 168 hours. It was confirmed whether or not there was an abnormality in appearance.

OK: No abnormality is observed in the appearance of the coating. NG: Water bubbles or peeling are observed in the coating.

Claims (18)

A step of sealing the conductor wiring having a metal protrusion formed on the surface thereof with a polymer resin layer containing an alkali-soluble resin and a thermosetting binder,
First curing the polymer resin layer,
Etching the surface of the cured polymer resin layer with an alkaline aqueous solution to expose the metal protrusions;
Wherein in a state where the metal projection is exposed, see contains a step of curing the polymeric resin layer secondary,
The said polymeric resin layer is a manufacturing method of an insulating layer containing 1 weight part-100 weight part of thermosetting binders with respect to 100 weight part of alkali-soluble resin . The method for producing an insulating layer according to claim 1, wherein the alkali-soluble resin includes at least two acidic functional groups and at least two cyclic imide functional groups substituted with amino groups. The method for producing an insulating layer according to claim 2, wherein the cyclic imide functional group substituted with an amino group includes a functional group represented by the following Chemical Formula 1.
In Chemical Formula 1, R ₁ is an alkylene group or an alkenyl group having 1 to 10 carbon atoms, and “*” means a bonding point. The method for producing 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 alkali-soluble resin is produced by a reaction of a cyclic unsaturated imide compound; and an amine compound, and at least one or more of the cyclic unsaturated imide compound and the amine compound contains a terminal substituted acidic functional group, The method for manufacturing an insulating layer according to claim 1. The method for producing an insulating layer according to claim 5, 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. .. 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 Chemical Formula 3, R ₂ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and “*” indicates a bonding point. Meaning,
In Chemical Formula 4, R ₃ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms,
R ₄ is —H, —OH, —NR ₅ R ₆ , halogen, or an alkyl group having 1 to 20 carbon atoms,
R ₅ and R ₆ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
"*" means a binding point. The said alkali-soluble resin is manufactured by reaction of the polymer containing the repeating unit represented by the following chemical formula 5, the amine represented by the following chemical formula 6, and the amine represented by the following chemical formula 7. Insulation layer manufacturing method:
In Chemical Formulas 5 to 7, R _{2 to} R ₄ are the same as those defined in claim 7, and “*” means a bonding point. The method for producing an insulating layer according to claim 7, 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 Chemical Formulas 8 to 9, R _{2 to} R ₄ are the same as defined in claim 7. The thermosetting binder contains one or more functional groups selected from the group consisting of an oxetanyl group, a cyclic ether group, a cyclic thioether group, a cyanide group, a maleimide group, and a benzoxazine group, and an epoxy group. The method for producing an insulating layer according to. The method for producing an insulating layer according to claim 1, wherein the alkaline aqueous solution has a temperature of 10° C. to 100° C. and a concentration of 1% to 10%. The method for producing an insulating layer according to claim 1, wherein the primary curing is performed at a temperature of 50° C. to 150° C. for 0.1 hours to 2 hours. The method for producing an insulating layer according to claim 1, wherein the secondary curing is performed at a temperature of 150°C to 250°C for 0.1 hours to 10 hours. The polymer resin layer according to claim 1, further comprising 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. Method of manufacturing insulating layer. Claim including on the 1 to 1 4 insulating layer produced by any one of a step of forming a metal pattern layer, manufacturing method for a multilayer printed circuit board. The method for manufacturing a multilayer printed circuit board according to claim 15 , wherein the insulating layer contains a cured product of an alkali-soluble resin and a thermosetting binder. Forming a metal pattern layer on the insulating layer,
Forming a metal thin film on the insulating layer,
Forming a photosensitive resin layer having a pattern formed on the metal thin film;
Depositing a metal on the metal thin film exposed by the photosensitive resin layer pattern,
The method of manufacturing a multilayer printed circuit board according to claim 16 , further comprising: removing the photosensitive resin layer and removing the exposed metal thin film. The method of claim 15 , wherein the metal pattern layer is connected to the conductor wiring via a metal protrusion.