KR102038106B1 - Method for manufacturing insulating film and multilayered printed circuit board - Google Patents

Abstract

The present invention can be manufactured in a faster and simpler method to improve the efficiency of the process, to prevent physical damage of the insulating layer, and to control the thickness of the insulating layer manufacturing method and the insulating layer manufacturing method A method for manufacturing a multilayer printed circuit board using an insulating layer obtained.

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. More specifically, it is possible to manufacture in a faster and simpler method can improve the efficiency of the process, to prevent physical damage of the insulating layer, easy to control the thickness of the insulating layer manufacturing method and the insulating layer manufacturing method The present invention relates to a method for manufacturing a multilayer printed circuit board using an insulating layer obtained from the same.

Recently, electronic devices have become smaller, lighter and more functional. To this end, as the application field of build-up printed circuit boards (PCBs) is rapidly expanding around small devices, the use of multilayer printed circuit boards is rapidly increasing.

Multi-layer printed circuit boards can be made from planar wiring to three-dimensional wiring. Especially in the industrial electronics field, the integration of functional devices such as integrated circuit (IC) and large scale integration (LSI) is improved, along with the miniaturization, light weight, high functionality, and structure of electronic devices. It is an advantageous product for electrical function integration, assembly time reduction and cost reduction.

The build-up PCB used in these application areas required the connection between layers, and for this purpose, a via hole corresponding to the interlayer electrical connection passage of the multilayer printed circuit board has been used, but the diameter of the via hole is used. There is a limit in reducing the density, which makes it difficult to achieve high density.

Accordingly, a method of using a small protrusion having a diameter smaller than the via hole as an electrical connection passage between layers of a multilayer printed circuit board has been proposed. However, the conventional method is to form the fine protrusions of the metal component on a single circuit, then cover the fine protrusions with an insulating layer, and physically remove the insulating layer until the fine protrusions are exposed to the surface. Accordingly, there is a limit in that the insulating layer is easily broken in the physical removal process, or it is difficult to easily match the desired thickness.

The present invention is to provide a method for manufacturing an insulating layer that can be manufactured in a faster and simpler method to improve the efficiency of the process, to prevent physical damage of the insulating layer, and to easily control the thickness.

In addition, the present invention is to provide a method for manufacturing a multilayer printed circuit board using the insulating layer obtained from the insulating layer manufacturing method.

In the present specification, the step of sealing the conductor wiring formed with a metal projection on the surface with a polymer resin layer containing an alkali-soluble resin and a thermosetting binder; Primary curing the polymer resin layer; Etching the surface of the cured polymer resin layer with an aqueous alkali solution to expose metal protrusions; And second curing the polymer resin layer in the exposed state of the metal protrusions.

In the present specification, there is also provided a method of manufacturing a multilayer printed circuit board, the method including forming a metal pattern layer on the insulating layer manufactured by the insulating layer manufacturing method.

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

According to one embodiment of the invention, the step of sealing the conductor wiring formed with metal projections on the surface with a polymer resin layer containing an alkali-soluble resin and a thermosetting binder; Primary curing the polymer resin layer; Etching the surface of the cured polymer resin layer with an aqueous alkali solution to expose metal protrusions; And in the state where the metal protrusions are exposed, comprising the step of secondary curing the polymer resin layer, an insulating layer manufacturing method can be provided.

The present inventors, when using the method of manufacturing the insulating layer of the embodiment, by exposing the metal protrusions sealed by the polymer resin layer through chemical etching with an aqueous alkali solution, it is possible to prevent physical damage of the insulating layer, insulation Not only can the layer thickness be easily adjusted to a desired range, but also an insulating layer can be manufactured through an easier process in a faster time, and the experiment has confirmed that the efficiency of the process is improved and the invention has been completed.

In particular, in the method of manufacturing the insulating layer of the embodiment, by applying a polymer resin of a novel component capable of proceeding an appropriate level of stable etching by a specific alkaline aqueous solution, the metal protrusions may be easily exposed to the surface of the insulating layer. There is an advantage that can easily manufacture a multilayer circuit board through the metal projection.

More specifically, the insulating layer manufacturing method of the embodiment comprises the steps of sealing the conductor wiring formed with metal projections on the surface with a polymer resin layer including an alkali-soluble resin and a thermosetting binder; Primary curing the polymer resin layer; Etching the surface of the cured polymer resin layer with an aqueous alkali solution to expose metal protrusions; And second curing the polymer resin layer in a state in which the metal protrusions are exposed.

First, in the step of sealing the conductor wiring having a metal protrusion on the surface with a polymer resin layer including an alkali-soluble resin and a thermosetting binder, the conductor wiring may be formed with a metal protrusion on the surface. Examples of the method of forming the metal projection on the surface of the conductor wiring are not particularly limited, and for example, a plating process for the opening of the photosensitive resin layer pattern or an adhesion process using an adhesive may be used.

A specific example of a plating process for the opening of the photosensitive resin layer pattern, for example, laminating a photosensitive resin layer on a conductor wiring; Forming a pattern on the photosensitive resin layer; And a metal protrusion forming method including electroplating.

More specifically, the photosensitive resin layer may exhibit photosensitive and alkali solubility. Accordingly, deformation of the molecular structure may proceed by an exposure step of irradiating light to the photosensitive resin layer, and the resin layer may be etched or removed by a developing step of contacting an alkaline developer.

Accordingly, when a portion of the photosensitive resin layer is selectively exposed and then alkali developed, the exposed portion may not be developed, and only the unexposed portion may be selectively etched and removed. In this manner, a part of the photosensitive resin layer that remains as it is without alkali development by exposure is referred to as a photosensitive resin pattern.

That is, for example, a method of exposing the photosensitive resin layer may include contacting a photomask formed with a predetermined pattern on the photosensitive resin layer and irradiating ultraviolet rays, or imaging a predetermined pattern included in the mask through a projection objective lens. Next, ultraviolet rays may be selectively exposed using a method such as directly irradiating ultraviolet rays or irradiating ultraviolet rays using a laser diode as a light source. At this time, examples of ultraviolet irradiation conditions include irradiation with a light amount of 5 mJ / cm 2 to 600 mJ / cm 2.

In addition, an example of a method of developing alkali after exposure to the photosensitive resin layer may include a method of treating an alkali developer. Examples of the alkali developer are not particularly limited, but, for example, concentrations and temperatures of alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, and amines It can be used to adjust the alkali developer sold as a product. Although the specific amount of the alkaline developer is not particularly limited, it is necessary to adjust the concentration and the temperature so as not to damage the photosensitive resin pattern. For example, an aqueous solution of 0.5% to 3% sodium carbonate at 25 ° C to 35 ° C may be used. .

Meanwhile, in the electroplating step, examples of the plating method may include a dry deposition process or a wet deposition process, and specific examples of the dry deposition process may include vacuum deposition, ion plating, and sputtering methods.

Meanwhile, examples of specific wet deposition processes include electroless plating of various metals, electroless copper plating is common, and may further include a roughening process before or after deposition.

The roughening process also includes dry and wet methods depending on conditions. Examples of the dry method include vacuum, atmospheric pressure, plasma treatment by gas, and gas treatment by Excimer UV. Examples of the wet method include desmear. Processing can be used. Through such a roughening process, the surface roughness of the metal thin film may be increased to improve adhesion to the metal deposited on the metal thin film.

In addition, in order to leave only the metal protrusions, after the electroplating, the method may further include removing the photosensitive resin layer. When removing the said photosensitive resin pattern, it is preferable to use the method which can remove only the photosensitive resin layer, without removing the lower conductor wiring and metal protrusion as much as possible.

As a specific example of the peeling method of the photosensitive resin pattern, the photoresist stripping liquid may be treated, a desmear process or plasma etching may be performed, and the above methods may be used in combination.

On the other hand, a specific example of the bonding process using the adhesive, for example, to form a metal projection on the surface of the passive element such as micc or active element such as a semiconductor chip, and then the surface of the conductor wiring using the insulating adhesive or the like on the opposite side of the formed metal projection Can be used. At this time, the method of forming the metal projection on the surface of the passive element or the active element can be used as the method of the plating step for the opening of the photosensitive resin layer pattern described above. For example, the method of forming a photosensitive resin layer pattern on the surface of a passive element or an active element, and then plating metal on the opening part of a 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 may be 1 μm. It may have a height of 20 to 20 ㎛ and a cross-sectional diameter of 5 to 30 ㎛. 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 protrusions may include a cylinder, a truncated cone, a polygonal pillar, a polygonal truncated cone, an inverted truncated cone or an inverted polygonal truncated cone. Examples of the metal component included in the metal protrusions are also not particularly limited, and for example, a conductive metal such as copper or aluminum may be used.

The conductor wiring formed with the metal protrusions on the surface may be sealed with the polymer resin layer. More specifically, the conductor wiring may be present in a state formed on a substrate including a semiconductor material such as a circuit board, a sheet, a multilayer printed wiring board, and the like. In such a state that the conductor wiring is present on the substrate, the conductor wiring can be sealed by a method of forming a polymer resin layer on the substrate.

Although the example of the method of forming a polymer resin layer on a base material is not restrict | limited, For example, the polymer resin composition for forming the said polymer resin layer is directly coated on a base material, or a polymer resin composition is apply | coated on a carrier film. To form a polymer resin layer, and then a method of laminating the substrate and the polymer resin layer may be used.

As the conductor wiring having the metal protrusions formed on the surface is sealed with the polymer resin layer, all the surfaces of the conductor wiring may contact the polymer resin layer except for the portion in contact with the substrate formed below and the portion in contact with the metal protrusion. In addition, all surfaces of the metal protrusions formed on the surface of the conductor wiring may also be sealed by the polymer resin layer to be in contact with the polymer resin layer.

The polymer resin layer means a film formed through drying of a polymer resin composition including 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 with respect to 100 parts by weight of the alkali-soluble resin. When the content of the thermosetting binder is excessively high, the developability of the polymer resin layer may be lowered, and the strength may be lowered. On the contrary, when the content of the thermosetting binder is too low, not only the polymer resin layer is excessively developed, but also uniformity may be reduced during coating.

The thermosetting binder may include one or more functional groups and epoxy groups selected from the group consisting of thermosetting functional groups, oxetanyl groups, cyclic ether groups, cyclic thio ether groups, cyanide groups, maleimide groups and benzoxazine groups. That is, the thermosetting binder necessarily includes an epoxy group, and in addition to the epoxy group, an oxetanyl group, a cyclic ether group, a cyclic thio ether group, a cyanide group, a maleimide group, a benzoxazine group or these It may contain two or more kinds of. Such a thermosetting binder may form a crosslinking bond with an alkali-soluble resin or the like by thermosetting to secure heat resistance or mechanical properties of the insulating layer.

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

The thermosetting binder including two or more cyclic (thio) ether groups in the molecule includes a compound having at least two or more of three, four or five membered cyclic ether groups, or cyclic thioether groups in the molecule. can do.

As a compound which has two or more cyclic thioether group in the said molecule | numerator, bisphenol A episulfide resin YL7000 by the Japan epoxy resin company, etc. are mentioned, for example.

In addition, the polyfunctional resin compound may be a polyfunctional epoxy compound containing at least two or more epoxy groups in a molecule, a polyfunctional oxetane compound including at least two or more oxetanyl groups in a molecule, or an episulfate containing two or more thioether groups in a molecule A feed resin, a polyfunctional cyanate ester compound containing at least two or more cyanide groups in a molecule, or a multifunctional benzoxazine compound containing at least two or more benzoxazine groups in a molecule.

As a specific example of the said polyfunctional epoxy compound, bisphenol-A epoxy resin, hydrogenated bisphenol-A epoxy resin, brominated bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, novolak-type epoxy resin, for example , 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, glyc Oxal type epoxy resin, amino group containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenolic epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoyl ethane resin, silicone modified epoxy resin and (epsilon) -caprolactone modified epoxy resins. In addition, in order to impart flame retardancy, those in which atoms such as phosphorus are introduced into the structure may be used. By thermosetting these epoxy resins, characteristics, such as adhesiveness of a cured film, 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) methylacrylic Latex, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or these In addition to polyfunctional oxetanes such as oligomers and copolymers, oxetane alcohols and novolac resins, poly (p-hydroxystyrenes), cardo-type bisphenols, charixarenes, carlixresolecinarenes, or silses And etherates with resins having hydroxy groups such as quoxane. In addition, the copolymer etc. of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate are mentioned.

Examples of the multifunctional 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 cyanate ester resins, phenol novolac cyanate ester resins, cresol novolac cyanate ester resins, novolac cyanate ester resins of bisphenol A, biphenol cyanate ester resins or oligomers or air thereof Coalescence, etc. are mentioned.

Examples of the multifunctional maleimide compound include 4,4'-diphenylmethane bismaleimide, phenylmethane bismaleimide, and m-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'-diphenylmethane 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.

Examples of the multifunctional benzoxazine compounds include bisphenol A benzoxazine resins, bisphenol F benzoxazine resins, phenolphthalein benzoxazine resins, thiodiphenol type benzoxazine resins, dicyclopentadiene benzoxazine resins, and 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 multifunctional resin compound include YDCN-500-80P manufactured by Kukdo Chemical Co., Ltd., phenol novolac type cyanide ester resin PT-30S manufactured by Lonza, phenylmethane type maleimide resin BMI-2300 manufactured by Daiwa Corporation, and Pd of Shikoku Corporation. Type benzoxazine resin etc. are mentioned.

On the other hand, the alkali soluble resin is an acidic functional group; And at least two cyclic imide functional groups each substituted with an amino group. Examples of the acidic functional group are not particularly limited, but may include, for example, a carboxyl group or a phenol group. The alkali-soluble resin may include at least two acidic functional groups to allow the polymer resin layer to exhibit higher alkali developability and control the development speed of the polymer resin layer.

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 two or more groups. As 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 large number of active hydrogens contained in the amino group are present, thereby reacting with the thermosetting binder during curing. As this improves, the curing density can be increased to increase heat resistance reliability and mechanical properties.

In addition, as the cyclic imide functional group is present in a large number in the alkali-soluble resin, the polarity is increased by the carbonyl group and the tertiary amine group included in the cyclic imide functional group, thereby increasing the interfacial adhesion of the alkali-soluble resin. Accordingly, the polymer resin layer containing the alkali-soluble resin may increase the interfacial adhesion with the metal layer stacked thereon.

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

[Formula 1]

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

The term "substituted" means that another functional group is bonded instead of a hydrogen atom in the compound, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent may be substituted, and when two or more are substituted, two or more The substituents may be the same or different from one another.

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

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

[Formula 2]

In Formula 2, "*" 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. In this case, the cyclic imide functional group and the acidic functional group substituted with the amino group may be bonded through a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, for example, a cyclic substituted with the amino group. An acidic functional group may be bonded to a terminal of an amino group included in an imide functional group through a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and is already contained in the cyclic imide functional group substituted with the amino group. The acidic functional group may be bonded to the terminal of the functional group via a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group.

More specifically, 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 1, and is already contained in the cyclic imide functional group substituted with the amino group. The terminal of the de-functional group may mean a nitrogen atom included in the cyclic imide functional group in Chemical Formula 1.

The alkylene group is a divalent functional group derived from an alkane, and is, for example, a linear, branched or cyclic group, such as a methylene group, an ethylene group, a propylene group, an isobutylene group, a sec-butylene group, tert-butylene group, pentylene group, hexylene group and the like. One or more hydrogen atoms included in the alkylene group may be substituted with another substituent, 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 carbon atoms Aryl group of 12 to 12 carbon atoms, 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.

The arylene group is a divalent functional group derived from arene, and may be, for example, a phenyl group or a naphthyl group as a cyclic type. One or more hydrogen atoms included in the arylene group may be substituted with another substituent, 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 carbon atoms Aryl group of 12 to 12 carbon atoms, 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.

Examples of the method for producing the alkali-soluble resin are not particularly limited, for example, a cyclic unsaturated imide compound; And amine compounds. At this time, the cyclic unsaturated imide compound; And at least one of the amine compounds 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 two compounds. Details of the acidic functional group are as described above.

The cyclic imide compound is a compound including the cyclic imide functional group described above, and the cyclic unsaturated imide compound means a compound including at least one unsaturated bond, ie, a double bond or a triple bond, in the cyclic imide compound. do.

The alkali soluble resin may be prepared through a reaction of an amino group included in the amine compound and a double bond or triple bond included in a cyclic unsaturated imide compound.

Examples of the weight ratio for reacting the cyclic unsaturated imide compound and the amine compound are not particularly limited. For example, 10 parts by weight to 80 parts by weight of the amine compound based on 100 parts by weight of the cyclic unsaturated imide compound. Part, or 30 to 60 parts by weight can be mixed and reacted.

Examples of the cyclic unsaturated imide compound include N-substituted maleimide compounds. N-substituted means that a functional group is bonded to a hydrogen atom bonded to a nitrogen atom included in the maleimide compound, wherein the N-substituted maleimide compound is monofunctional N-substituted maleimide according to the number of N-substituted maleimide compounds Compounds and polyfunctional N-substituted maleimide compounds.

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

In the monofunctional N-substituted maleimide compound, a functional group substituted with the nitrogen atom included in the maleimide compound may include various known aliphatic, alicyclic or aromatic functional groups, and a 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. Details of the acidic functional group are as described above.

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

 In the multifunctional N-substituted maleimide compound, the functional group that mediates the bond between nitrogen atoms included in each of two or more maleimide compounds may include various known aliphatic, alicyclic or aromatic functional groups, and specific examples thereof. , 4,4'-diphenylmethane functional group and the like can be used. The functional group substituted with the nitrogen atom may include a functional group in which an acidic functional group is substituted with an aliphatic, alicyclic or aromatic functional group. Details of the acidic functional group are as described above.

Specific examples of the polyfunctional N-substituted maleimide compound include 4,4'-diphenylmethane bismaleimide (BMI-1000, BMI-1100, etc. of Daiwakasei), phenylmethane bismaleimide, m-phenylene methane bismaleim Mead, bisphenol A diphenylether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide Mid, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane etc. are mentioned.

The amine compound may be a primary amine compound containing at least one amino group (-NH ₂ ) in the molecular structure, more preferably a carboxylic acid compound substituted with an amino group, a polyfunctional amine compound including two or more amino groups or Mixtures of these can be used.

In the carboxylic acid compound substituted with the amino group, the carboxylic acid compound is a compound containing a carboxylic acid (-COOH) functional group in a molecule, and may include all aliphatic, alicyclic or aromatic carboxylic acids depending on the type of hydrocarbon bonded to the carboxylic acid functional group. . As the carboxylic acid compound substituted with the amino group includes a plurality of carboxylic acid functional groups which are acidic functional groups in the alkali soluble resin, developability of the alkali soluble resin may be improved.

Specifically, the alkali-soluble resin prepared by the reaction of the carboxylic acid compound substituted with the amino group with the cyclic unsaturated imide compound has an acid value obtained by KOH titration of 50 mgKOH / g to 250 mgKOH / g, Or 70 mgKOH / g to 200 mgKOH / g. Although the example of the method of measuring the acid value of the said alkali-soluble resin is not restrict | limited very much, For example, the following method can be used. Prepare a KOH solution (solvent: methanol) at a concentration of 0.1 N as a base solvent, and alpha-naphtholbenzein (pH: 0.8 to 8.2 yellow, 10.0 blue green) as an indicator. Was prepared. Subsequently, about 1 to 2 g of an alkali soluble resin as a sample was taken, dissolved in 50 g of dimethylformaldehyde (DMF) solvent, and then added with a marker, followed by titration with a base solvent. The acid value was determined in mg KOH / g by 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 low, it may be difficult to proceed with the development 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 resin may occur due to increased polarity.

The term "substituted" means that another functional group is bonded instead of a hydrogen atom in the compound, and the position at which the amino group is substituted in the carboxylic acid compound is not limited as long as the position at which the hydrogen atom is substituted, and the number of amino groups to be substituted is one or more. Can be.

Specific examples of the carboxylic acid compound substituted with the amino group include 20 kinds of α-amino acid, 4-aminobutanoic acid, 5-aminopentanoic acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8, which are known as raw materials for proteins. -Aminooctanoic acid, 4-aminobenzoic acid, 4-aminophenylacetic acid, 4-amino cyclohexane carboxylic acid, etc. are mentioned.

In addition, the polyfunctional amine compound including two or more amino groups is a compound containing two or more amino groups (-NH ₂ ) in the molecule, and may include all aliphatic, alicyclic or aromatic polyfunctional amines depending on the type of hydrocarbon bonded to the amino group. have. Through the polyfunctional amine compound including two or more amino groups, flexibility, toughness, copper adhesion, etc. of the alkali-soluble resin may 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, -tetramethyl-1,4-phenylenediamine, 2,4,5,6-tetrafluoro-1,3-phenylenediamine, 2,3,5 , 6-tetrafluoro-1,4-phenylenediamine, 4,6-diaminoresosinol, 2,5-diamino-1,4-benzenedithiol, 3-aminobenzylamine, 4-aminobenzyl Amines, m-xylenediamine, p-xylenediamine, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 2,6-diaminoanthraquinone, m-tolidine, o-tolidine, 3 , 3 ', 5,5'-tetramethylbenzidine (TMB), o-diazinidine, 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) -hexa Fluoropropane, 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'-diaminodiphenylether, 4,4'-diaminodiphenylether, 1,3-bis (3-aminophenoxy C) -benzene, 1,3-bis (4-aminophenoxy) -benzene, 1,4-bis (4-aminophenoxy) -benzene, 1,4-bis (4-amino-2-trifluoro Methylphenoxy) -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) -phen ] 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-diaminoresosinol, 2,3,5,6-pyridinetetraamine, polyfunctional amines including 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 including Dow Corning siloxane structure (Dow Corning 3055), polyfunctional amines including polyether structure (Huntsman, BASF), etc. Can be.

In addition, the alkali-soluble resin is a repeating unit represented by the following formula (3); And at least one repeating unit represented by Formula 4 below.

[Formula 3]

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

[Formula 4]

In Formula 4, R ₃ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and R ₄ is —H, —OH, or —NR ₅ R ₆ , a halogen, or an alkyl group having 1 to 20 carbon atoms, wherein 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 "*" represents a point of attachment. it means.

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

On the other hand, the alkali-soluble resin is a repeating unit represented by the formula (3); And in addition to the repeating unit represented by Formula 4 may further include a vinyl-based repeating unit. The vinyl repeating unit is a repeating unit included in a homopolymer of a vinyl monomer including at least one vinyl group in a molecule, and examples of the vinyl monomer are not particularly limited. For example, ethylene, propylene, isobutylene , Butadiene, styrene, acrylic acid, methacrylic acid, maleic anhydride, maleimide and the like.

A repeating unit represented by Formula 3 above; And an alkali-soluble resin each containing at least one or more repeating units represented by Formula 3 may include a polymer including a repeating unit represented by Formula 5 below, an amine represented by Formula 6 below, and an amine represented by Formula 7 below: Can be prepared.

[Formula 5]

[Formula 6]

[Formula 7]

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

Specific examples of the polymer including the repeating unit represented by Formula 5 are not particularly limited, but for example, Cray valley SMA, Polyscope Xiran, Solenis Scripset, Kuraray Isobam, Chevron Phillips Chemical Polyanhydride resin, Lindau Chemicals Maldene etc. of the company can be mentioned.

In addition, the repeating unit represented by the above formula (3); And alkali-soluble resins each including at least one or more repeating units represented by Formula 3 may be prepared by the reaction of a compound represented by Formula 8 and a compound represented by Formula 9.

[Formula 8]

[Formula 9]

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

In addition, the said alkali-soluble resin can use the well-known conventional carboxyl group-containing resin or phenol group containing resin which contains a carboxyl group or a phenol group in a molecule | numerator. Preferably, a phenol group containing resin can be mixed and used for the said carboxyl group-containing resin or the said carboxyl group-containing resin.

As an example of the said carboxyl group-containing resin, resin of (1)-(7) enumerated below is mentioned.

(1) carboxyl group-containing resin obtained by making a polyfunctional epoxy resin react with saturated or unsaturated monocarboxyl group, and then making polybasic acid anhydride react,

(2) a carboxyl group-containing resin obtained by reacting a bifunctional phenol and / or a dicarboxyl group with a bifunctional epoxy resin, followed by reacting a polybasic anhydride,

(3) carboxyl group-containing resin obtained by making a polyfunctional phenol resin react with the compound which has one epoxy group in a molecule | numerator, and then reacting polybasic acid anhydride,

(4) Carboxyl group-containing resin formed by making polybasic acid anhydride react with the compound which has two or more alcoholic hydroxyl groups in a molecule | numerator.

(5) Polyamic acid resin or copolymer resin of polyamic acid resin which reacted diamine and dianhydride

(6) polyacrylic acid resin or copolymer of polyacrylic acid resin reacted with acrylic acid

(7) resins prepared by ring opening anhydrides of polymaleic anhydride resins and polymaleic anhydride resin copolymers reacted with maleic anhydride with weak acids, diamines, imidazoles, and dimethyl sulfoxides; Although it is mentioned, it is not limited to these.

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

Although the example of the said phenol group containing resin is not restrict | limited greatly, For example, novolak resins, such as a phenol novolak resin, cresol novolak resin, bisphenol F (BPF) 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-Hydroxyphenyl) bisphenol A resins such as propan-2-yl) phenyl) ethane-1,1-diyl) diphenol] may 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 mold release agent, and a metal adhesion promoter.

The thermosetting catalyst serves to promote thermosetting of the thermosetting binder. As said thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, Imidazole derivatives such as 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, 4-methyl-N, N-dimethylbenzylamine compound; Hydrazine compounds such as adipic dihydrazide and sebacic acid dihydrazide; Phosphorus compounds, such as a triphenylphosphine, etc. are mentioned. Moreover, as what is marketed, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are brand names of an imidazole compound) by the Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N and UCAT3502T by San Apro Corporation (All are brand names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATS A102, U-CAT5002 (both bicyclic amidine compounds and salts thereof), and the like. It is not specifically limited to these, It may be the thing which accelerates reaction of the thermosetting catalyst of an epoxy resin or an oxetane compound, or an epoxy group and / or an oxetanyl group, and a carboxyl group, It can also be used individually or in mixture of 2 or more types. . Also, 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-isosaururic acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isosaanuric acid S-triazine derivatives, such as an adduct, can also be used, Preferably, the compound which also functions as these adhesive imparting agents can be used together with the said 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.

Examples of the content of the inorganic filler are not particularly limited, but in order to achieve high rigidity of the polymer resin layer, the inorganic filler may be 100 parts by weight or more, based on 100 parts by weight of all the resin components included in the polymer resin layer, or 100 parts by weight to 600 parts by weight, or 100 parts by weight to 500 parts by weight may be added.

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

The metal adhesion promoter may be a material that does not cause problems in surface alteration or transparency of the metal material, for example, a silane coupling agent or an organometallic coupling agent.

The leveling agent serves to remove the popping or crater of the surface when the film coating, for example, BYK-380N, BYK-307, BYK-307, BYK-378, BYK-350 of BYK-Chemie GmbH may 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 that can cause phase separation. Accordingly, the roughening treatment of the cured product of the polymer resin layer may be possible. Examples of the molecular weight measuring method of the resin or the elastomer having a molecular weight of 5000 g / mol or more are not particularly limited, and for example, the weight average molecular weight of polystyrene conversion measured by the GPC method is meant. In the process of measuring the weight average molecular weight of polystyrene conversion measured by the GPC method, it is possible to use a detector and an analytical column, such as a conventionally known analytical device, a differential index detector, and the like. 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.

In addition, the polymer resin layer may further include an alkali-soluble resin including a thermosetting binder or a photoreactive unsaturated group and a photoinitiator in order to impart photocurable properties to the polymer resin layer. 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 particularly limited, and various compounds used in the art related to the photocurable resin composition may 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 total weight of the polymer resin layer. When the content of the photoinitiator contained in the polymer resin layer is less than 0.01% by weight based on the total weight of the polymer resin layer, the content of the photoinitiator contained in the polymer resin layer may be very insignificant or may not include any photoinitiator. . Accordingly, the interface detachability with the insulating layer or the conductive layer which can be generated by the photoinitiator can be reduced, and the adhesion and durability of the insulating layer can be improved.

In addition, the insulating layer manufacturing method of the embodiment may include the step of first curing the polymer resin layer. In the step of curing the polymer resin layer, examples of the specific curing method is not particularly limited, and any thermosetting or photocuring method may be used without limitation.

Through the first curing step, a main chain including an ester bond may be formed in the polymer resin layer. As an example of the said ester bond, the method of photocuring through acrylic resin in which acrylic acid is ester-bonded, or thermosetting so that ester bond may be formed by reaction of carboxylic acid and an epoxy is mentioned.

At this time, specific thermosetting conditions are not limited, and may be performed by adjusting preferred conditions according to the etching method of the polymer resin layer described later. For example, when the photoresist stripper is treated to etch the polymer resin layer, the first curing step of the polymer resin layer may be performed at a temperature of 50 ° C. to 150 ° C. for 0.1 hour to 2 hours. When the thermosetting temperature of the polymer resin layer is too low or the thermosetting time is short, the polymer resin layer may be excessively damaged by the stripping solution, the thermosetting temperature of the polymer resin layer is high, or the thermosetting time is high. If it becomes longer, the etching of the polymer resin layer by the stripping solution may be difficult to proceed.

In addition, the insulating layer manufacturing method of the embodiment may include the step of etching the surface of the cured polymer resin layer with an aqueous alkali solution to expose the metal projections. As the surface of the cured polymer resin layer is etched with an aqueous alkali solution to expose the metal protrusions, electrical signals may be connected to the conductor wiring sealed inside the cured polymer resin layer through the exposed metal protrusions.

The exposure of the metal protrusions described above may be performed through etching with an aqueous alkali 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, a photoresist stripping solution may be used. The alkaline aqueous solution may etch away the polymer resin layer by breaking the ester bond in the polymer resin layer in which the main chain including the ester bond is formed through the primary curing. At this time, by controlling the concentration and temperature of the alkaline aqueous solution, it is possible to control the etching rate of the polymer resin layer by the alkaline aqueous solution, while maintaining the etching rate of the appropriate level within the above range to ensure the process efficiency easily polymer The thickness of the resin layer can be adjusted.

The alkaline aqueous solution may be an aqueous solution of a metal hydroxide such as potassium hydroxide and sodium hydroxide, and may also be used for commercially available products such as Atotech's Resistrip product group, Oalchem's ORC-731, ORC-723K, ORC-740, and SLF-6000. This is possible.

Etching by the alkaline aqueous solution may proceed from the surface of the cured polymer resin layer. The cured polymer resin layer surface refers to an area in which the polymer resin layer sealing the conductor wiring with metal protrusions on the surface is in contact with air, and the conductor wiring with metal protrusions formed on the surface from the cured polymer resin layer surface. As the etching proceeds into the polymer resin layer sealing the metal protrusions, the metal protrusions may be exposed.

In order for the etching by the aqueous alkali solution to proceed from the surface of the cured polymer resin layer, the alkali aqueous solution may contact the surface of the cured polymer resin layer. In this case, in order to ensure thickness uniformity by uniform removal without physical damage to the polymer resin layer, the alkaline aqueous solution may be contacted to the surface of the polymer resin layer through a method such as spraying through a spray.

In addition, the insulating layer manufacturing method of the embodiment may include the step of second curing the polymer resin layer in a state in which the metal projection is exposed. Through the secondary curing step, the chemical resistance of the insulating layer finally manufactured through the secondary curing step can be improved.

At this time, 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 hour to 2 hours.

On the other hand, after the second step of curing the polymer resin layer in a state where the metal protrusions are exposed, if necessary, further comprising the step of removing the substrate formed under the conductor wiring. As described above, the conductor wiring may be present in a state formed on a substrate including a semiconductor material such as a circuit board, a sheet, a multilayer printed wiring board, and the like. In order to form a multilayer circuit board having a finer structure, the substrate under the conductor wiring may be removed, if necessary, and the substrate may be in an adhesive or adhered state with the polymer resin layer and may be physically peeled off. .

Meanwhile, according to another embodiment of the present invention, a method of manufacturing a multilayer printed circuit board including forming a metal pattern layer having a pattern formed on the insulating layer manufactured in the above embodiment may be provided.

The inventors of the present invention provide the insulating layer manufactured in the above embodiment includes a conductor wiring having metal protrusions formed on a surface thereof, and the metal protrusions are exposed to the outside of the insulating layer to newly stack the metal pattern layer on the insulating layer. In this case, it was confirmed that the metal pattern layer can exchange electrical signals with the conductor wiring inside the insulating layer through the metal protrusions, and completed the invention.

The insulating layer may be used as an interlayer insulating material of a multilayer printed circuit board, and may include a cured product of an alkali-soluble resin and a thermosetting binder, specifically, a thermosetting or photocuring material. The content of the alkali-soluble resin and the thermosetting binder includes the content described above in the embodiment.

For example, forming a metal pattern layer on the more 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; And removing the photosensitive resin layer and removing the exposed metal thin film.

In the forming of the metal thin film on the insulating layer, examples of the metal thin film forming method may include a dry deposition process or a wet deposition process. Examples of the specific dry deposition process include vacuum deposition, ion plating, and sputtering methods. Etc. can be mentioned.

Meanwhile, specific wet deposition processes include electroless plating of various metals, and electroless copper plating is common, and may further include a roughening process before or after deposition.

The roughening process also includes dry and wet methods depending on conditions. Examples of the dry method include vacuum, atmospheric pressure, plasma treatment by gas, and gas treatment by Excimer UV. Examples of the wet method include desmear. Processing can be used. Through such a roughening process, the surface roughness of the metal thin film may be increased to improve adhesion to the metal deposited on the metal thin film.

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

Specifically, as an example of a method of forming a surface treatment layer on the insulating layer, at least one of an ion assist reaction method, an ion beam treatment method, and a plasma treatment method may be used. The plasma treatment method may include any one of an atmospheric pressure plasma treatment method, a DC plasma treatment method, and an RF plasma treatment method. As a result of the surface treatment process, a surface treatment layer including a reactive functional group may be formed on the surface of the insulating layer. As another example of a method for forming a surface treatment layer on the insulating layer, a method of depositing 50 nm to 300 nm of chromium (Cr) and titanium (Ti) metal on the surface of the insulating layer may be used.

Meanwhile, the forming of the photosensitive resin layer having the pattern formed on the metal thin film may include exposing and developing the photosensitive resin layer formed on the metal thin film. Information on the photosensitive resin layer and the exposure and development may include the above-described details in the embodiment.

In particular, the pattern formed on the metal thin film is preferably formed so that the openings included in the pattern may contact the metal protrusions exposed to the outside of the insulating layer. The opening included in the pattern means a portion removed through exposure and development of the photosensitive resin layer, and corresponds to a portion where metal is deposited through metal deposition to be described later to form the metal pattern layer. Therefore, the openings included in the pattern should be formed to be in contact with the metal protrusions exposed to the outside of the insulating layer, so that the metal pattern layer may contact the metal protrusions to exchange electrical signals with the conductor wiring inside the insulating layer.

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 that is not in contact with the photosensitive resin layer on the surface. The metal to be deposited may be copper, and examples of the deposition method are not particularly limited, and various known physical or chemical deposition methods may be used without limitation, and one example of the metal may be an 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 above-described metal pattern layer, more specifically, the metal pattern layer is connected to the conductor wiring through the metal projection. Can be formed. Through this, the metal pattern layer may transmit and receive electrical signals with the conductor wiring included in the insulating layer. More specifically, one end of the metal protrusion may contact the conductor wire, and the other end of the metal protrusion may contact the metal pattern layer to electrically connect the conductor wire and the metal pattern layer.

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

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

Accordingly, the number of stacked layers included in the multilayer printed circuit board manufactured by the multilayer printed circuit board manufacturing method is also not particularly limited, and for example, one or more layers, or one to twenty layers, depending on the purpose of use and use. Can have

According to the present invention, it is possible to manufacture in a faster and simpler method to improve the efficiency of the process, to prevent physical damage of the insulating layer, and to easily control the thickness of the insulating layer manufacturing method and the insulating layer manufacturing method A method for manufacturing a multilayer printed circuit board using an insulating layer obtained from the same can be provided.

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

< Production Example : Alkali  Preparation of Soluble Resin>

Preparation Example 1

632 g of dimethylformamide (DMF) as a solvent in a heated and cooled volume 2 liter reaction vessel equipped with a manufacturing thermometer, a stirring device, a reflux condenser, a water quantifier, and a N-substituted maleimide compound, BMI-1100 (Daiwakasei 358 g), 151 g of 4-aminophenylacetic acid was mixed with an amine compound, and stirred at 85 ° C. for 24 hours to prepare an alkali-soluble resin solution having a solid content of 50%.

Preparation Example 2

632 g of dimethylformamide (DMF) as a solvent in a heated and cooled volume 2 liter reaction vessel equipped with a production thermometer, a stirring device, a reflux condenser, a moisture meter, and a N-substituted maleimide compound. 434 g of mid and 198 g of 4,4'-diaminodiphenylmethane were mixed with an amine compound, and stirred at 85 ° C. for 24 hours to prepare an alkali soluble resin solution having a solid content of 50%.

Preparation Example 3

543 g of dimethylacetamide (DMAc) was added as a solvent to a 2-liter, heated and coolable reaction vessel equipped with a manufacturing thermometer, a stirring device, a reflux condenser, and a water quantifier, and 350 ml of CMA Valley SMA1000, 4-aminobenzo Iksan (4-aminobenzoic acid, PABA) 144g, 4-aminophenol (4-aminophenol, PAP) 49g was added and mixed. Under nitrogen atmosphere, the temperature of the reactor was set at 80 ° C., and the acid anhydride and the aniline derivative reacted to form amic acid for 24 hours. The temperature of the reactor was set at 150 ° C. and the reaction was continued for 24 hours to proceed with imidization reaction. , An alkaline soluble resin solution having a solid content of 50% was prepared.

Preparation Example 4

516 g of methylethylketone (MEK) was added to a 2-liter reaction vessel equipped with a manufacturing thermometer, a stirring device, a reflux condenser, a water quantifier, and a p-carboxyphenylmaleimide as a solvent. ) 228g, p-hydroxyphenylmaleimide (85g), styrene (203g), azobisisobutyronitrile (AIBN) 0.12g was added and mixed. After slowly raising the temperature of the reactor to 70 ° C. under a nitrogen atmosphere, an alkali-soluble resin solution having a solid content of 50% was prepared by continuing for 24 hours.

< Example : Insulation layer  And Fabrication of Multilayer Printed Circuit Boards>

Example 1

(1) Preparation of Insulation Layer

The polymer resin composition of 16 g of the alkali-soluble resin synthesized in Preparation Example 1, 5 g of MY-510 (manufactured by Huntsman) as a thermosetting binder, and 35 g of SC2050 MTO (70% solids, manufactured by Adamatech) as an inorganic filler was used. It was applied to the treated PET film and dried to prepare an 18 탆 thick polymer resin layer.

And. Dry film (RY-5319, Hitachi Chemical) was laminated on a copper foil laminated plate (LG-500GA VB / VB, LG Chemical) to which ultra-thin copper foil was bonded to form a pattern, and electroplated to form a circuit by the MSAP method. Thereafter, a dry film (RY-5319, Hitachi Chemical) was laminated on the circuit to form a pattern, and electroplating to form a copper bump having a height of 15 μm and a diameter of 20 μm.

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

In addition, the insulating layer was manufactured by thermally curing the polymer resin layer having the copper bumps exposed on the surface at a temperature of 200 ° C. for 1 hour.

(2) Manufacture of multilayer printed circuit board

A copper thin film was deposited on the insulating layer using an electroless copper plating, heated at 100 ° C. for 30 minutes to improve adhesion to the electroless copper plating, and then dried a dry film (RY-5319, Hitachi Chemical). To form a pattern and electroplating to form a circuit by the SAP method. Then, the copper foil laminated plate and the ultrathin copper foil were separated and removed from the insulating layer to complete the multilayer printed circuit board.

Example 2

The insulating layer and the multilayer printed circuit in the same manner as in Example 1, except that the alkali-soluble resin synthesized in Preparation Example 2 was used instead of the alkali-soluble resin synthesized in Preparation Example 1 in the insulating layer manufacturing step of Example 1. The substrate was prepared.

Example 3

The insulating layer and the multilayer printed circuit in the same manner as in Example 1, except that the alkali-soluble resin synthesized in Preparation Example 3 was used instead of the alkali-soluble resin synthesized in Preparation Example 1 in the insulating layer manufacturing step of Example 1. The substrate was prepared.

Example 4

The insulating layer and the multilayer printed circuit in the same manner as in Example 1, except that the alkali-soluble resin synthesized in Preparation Example 4 was used instead of the alkali-soluble resin synthesized in Preparation Example 1 in the insulating layer manufacturing step of Example 1. The substrate was prepared.

< Comparative example : Insulation layer  And Fabrication of Multilayer Printed Circuit Boards>

Comparative Example 1

(1) Preparation of Insulation Layer

Using a 100 μm thick molding sheet (LE-T17B, Ajinomoto) instead of the polymer resin layer of Preparation Example 1, vacuum laminated at 120 ℃, and thermally cured at 170 ℃ temperature for 1 hour, the thermosetting polymer An insulating layer was prepared in the same manner as in Example 1, except that the surface of the resin layer was ground with a grinding machine to expose copper bumps.

At this time, the process of exposing the copper bump was carried out for 10 minutes to 20 minutes per panel in a batch process, it was confirmed that takes a longer time than the embodiment.

(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 was first thermally cured at a temperature of 100 ° C. for 1 hour, and then, instead of spraying a 3% sodium hydroxide resist stripping solution at a temperature of 50 ° C. onto the surface of the polymer resin layer, the polymer resin layer was 200 Heat cured at a temperature of 1 ° C. for 1 hour and then sweller (Atotech, Sweller-p, 40%), etching (KMnO ₄ 9%, NaOH, 6%) and neutralization (H ₂ SO ₄ , 9) according to conventional methods. %) Was prepared in the same manner as in Example 1 except that the copper bump was exposed on the surface by removing the desmear by about 3㎛ depth from the surface of the polymer resin layer in order to prepare an insulating layer and a multilayer printed circuit board.

In this case, the desmear process exposing the copper bumps is a continuous batch process, which proceeds 5 minutes to 10 minutes per panel only in an etching step, and takes a longer time than the embodiment, and harmful chemicals such as potassium permanganate should be added. In addition, it was confirmed that there is a limit that it is difficult to control the thickness of the polymer resin layer.

Comparative Example 3

The polymer resin composition of 16 g of the alkali-soluble resin synthesized in Preparation 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 was added to an untreated PET film having a thickness of 25 μm. It was applied and dried to prepare a polymer resin layer having a thickness of 18 μm.

And. Dry film (RY-5319, Hitachi Chemical) was laminated on a copper foil laminated plate (LG-500GA VB / VB, LG Chemical) to which ultra-thin copper foil was bonded to form a pattern, and electroplated to form a circuit by the MSAP method. Thereafter, a dry film (RY-5319, Hitachi Chemical) was laminated on the circuit to form a pattern, and electroplating to form a copper bump having a height of 15 μm and a diameter of 20 μm.

Thereafter, the polymer resin layer was vacuum laminated on the copper-clad laminate at 85 to seal the circuit and the copper bumps, and the PET film was removed from the polymer resin layer. Thereafter, the step of performing the first thermal curing of the laminated polymer resin layer at a temperature of 100 ° C. for 1 hour is omitted, and the 3% sodium hydroxide resist stripping solution of 50 ° C. is directly added to the laminated polymer resin layer of the polymer resin layer. Spray sprayed on the surface.

At this time, in the case of Comparative Example 3, all of the polymer resin layers were removed within 10 seconds after the sodium hydroxide resist stripping solution was injected, and the technical limitations of the copper bumps and the lower circuits were confirmed.

That is, when the curing step for the polymer resin layer is not performed before spraying the release liquid as in Comparative Example 3, it is difficult to control the degree to which the polymer resin layer is removed, so that only a part of the copper bump is exposed to the polymer resin layer surface. It was found not to be suitable.

< Experimental Example  : Example  And In the comparative example  Obtained Insulation layer  Measurement of Physical Properties of Multilayer Printed Circuit Boards>

The physical properties of the insulating layer obtained in the Examples and Comparative Examples were measured by the following method, the results are shown in Table 1.

One. To moisture absorption  Metal adhesion

After leaving the multilayer printed circuit board obtained in the above Examples and Comparative Examples for 48 hours at 135 ° C. and 85% moisture absorption, the peel strength of the metal was measured according to the IPC-TM-650 standard, and the metal adhesion strength was determined from the obtained PCB. It was.

2. HAST ( Highly Accelerated Temp  & Humidity Stress Test Resistance

The HAST resistance of the multilayer printed circuit boards obtained in the above Examples and Comparative Examples was confirmed according to JESD22-A101 standard. Specifically, after applying a voltage of 3V to the specimen circuit board having a width, an interval, and a thickness of 50 μm, 50 μm, and 12 μm, respectively, and leaving it for 168 hours, the sample circuit board was inspected under the following criteria. It was.

OK: No abnormality observed in the appearance of the coating

NG: blisters or peelings are observed on the film

Experimental Example Results of Examples and Comparative Examples division Metal adhesion (kgf / cm) HAST characteristic (㎛) Example 1 0.3 OK Example 2 0.3 OK Example 3 0.3 OK Example 4 0.3 OK Comparative Example 1 0.3 OK Comparative Example 2 0.3 OK Comparative Example 3 - -

Claims (19)

Sealing the conductor wiring having metal projections on the surface with a polymer resin layer including an alkali-soluble resin and a thermosetting binder;
Primary curing the polymer resin layer;
Etching the surface of the cured polymer resin layer with an aqueous alkali solution to expose metal protrusions; And
In the state where the metal projections are exposed, comprising the step of secondary curing the polymer resin layer,
1) The alkali soluble resin is an acidic functional group; And at least two cyclic imide functional groups each substituted with an amino group, or
2) the alkali-soluble resin is a repeating unit represented by the following formula (3); And at least one or more repeating units represented by the following formula (4):
[Formula 3]

In Formula 3, R ₂ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and “*” means a bonding point,
[Formula 4]

In Formula 4, R ₃ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms,
R ₄ is —H, —OH, —NR ₅ R ₆ , halogen, or an alkyl group having 1 to 20 carbon atoms,
R ₅ and R ₆ may be each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
"*" Means joining point.
delete The method of claim 1,
The cyclic imide functional group substituted with the amino group comprises a functional group represented by the following formula (1), a method for producing an insulating layer:
[Formula 1]

In Formula 1, R ₁ is an alkylene group or alkenyl group having 1 to 10 carbon atoms, and "*" means a point of attachment.
The method of claim 1,
The alkali-soluble resin has an acid value (50 mgKOH / g to 250 mgKOH / g) obtained by KOH titration, insulating layer manufacturing method.
The method of claim 1,
1) The alkali soluble resin is a cyclic unsaturated imide compound; And an amine compound, wherein at least one or more of the cyclic unsaturated imide compound and the amine compound include an acidic functional group substituted at an end thereof.
The method of claim 5,
The amine compound comprises at least one member 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, insulating layer manufacturing method.
delete The method of claim 1,
2) The alkali-soluble resin is prepared by the reaction of a polymer comprising a repeating unit represented by the following formula (5), an amine represented by the formula (6), and an amine represented by the formula (7):
[Formula 5]

[Formula 6]

[Formula 7]

In Chemical Formulas 5 to 7, R ₂ to R ₄ are as defined in claim 1, and "*" means a point of attachment.
The method of claim 1,
2) The alkali-soluble resin is prepared by the reaction of a compound represented by the following formula (8) and a compound represented by the formula (9), an insulating layer manufacturing method
[Formula 8]

[Formula 9]

In Chemical Formulas 8 to 9, R ₂ to R ₄ are as defined in claim 1.
The method of claim 1,
The polymer resin layer comprises 1 part by weight to 150 parts by weight of the thermosetting binder with respect to 100 parts by weight of the alkali-soluble resin, insulating layer manufacturing method.
The method of claim 1,
The thermosetting binder includes at least one functional group and an epoxy group selected from the group consisting of oxetanyl group, cyclic ether group, cyclic thio ether group, cyanide group, maleimide group and benzoxazine group.
The method of claim 1,
The alkaline aqueous solution has a temperature of 10 ° C to 100 ° C and a concentration of 1% to 10%, insulation layer manufacturing method.
The method of claim 1,
The primary curing is carried out at a temperature of 50 ℃ to 150 ℃ for 0.1 hour to 2 hours, the insulating layer manufacturing method.
The method of claim 1,
The secondary curing is carried out at 150 ℃ to 250 ℃ temperature for 0.1 hour to 2 hours, the insulating layer manufacturing method.
The method of claim 1,
The polymer resin layer further comprises at least one selected from the group consisting of a thermosetting catalyst, an inorganic filler, a leveling agent, a dispersant, a mold release agent and a metal adhesion promoter, insulating layer manufacturing method.
A method for manufacturing a multilayer printed circuit board, comprising the step of forming a metal pattern layer on the insulating layer prepared by claim 1.
The method of claim 16,
The insulating layer comprises a cured product of an alkali-soluble resin and a thermosetting binder, a multilayer printed circuit board manufacturing method.
The method of claim 17,
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; And
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.
The method of claim 16,
The metal pattern layer is connected to the conductor wiring via a metal projection, multilayer printed circuit board manufacturing method.