JP2019505980A - Insulating layer manufacturing method and multilayer printed circuit board manufacturing method - Google Patents

Abstract

The present invention can be manufactured in a faster and simpler manner, can improve the process efficiency, can easily adjust the thickness of the insulating layer, and can form a high-resolution via hole without physical damage. The present invention relates to an insulating layer manufacturing method and a multilayer printed circuit board manufacturing method using an insulating layer obtained by the insulating layer manufacturing method.

Description

[Cross-reference of related applications]
This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0150510 dated November 11, 2016 and Korean Patent Application No. 10-2017-0144765 dated November 1, 2017, and All the contents disclosed in the Korean patent application literature are included as part of this specification.

  The present invention relates to an insulating layer manufacturing method and a multilayer printed circuit board manufacturing method. More specifically, it can be manufactured in a faster and simpler manner, can improve the process efficiency, can easily adjust the thickness of the insulating layer, and can form high-resolution via holes without physical damage. The present invention relates to an insulating layer manufacturing method and a multilayer printed circuit board manufacturing method using an insulating layer obtained by the insulating layer manufacturing method.

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

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

  The build-up PCB used in such an application area always requires connection between layers, and for this purpose, a method of forming a via hole corresponding to an interlayer electrical connection path of a multilayer printed circuit board is used. However, there is a limit to reducing the diameter of the via hole, and there is a limit that it is difficult to achieve high density.

  In view of this, a method has been proposed in which fine protrusions having a diameter smaller than that of the via hole are utilized for the interlayer electrical connection passage of the multilayer printed circuit board. However, in the conventional method, after forming a fine projection of a metal component on a single circuit, the fine projection is covered with an insulating layer, and the insulating layer is physically removed until the fine projection is exposed on the surface. Most of the methods are, and therefore, there is a limit that the insulating layer is easily broken during the physical removal process, and it is difficult to easily adjust the desired thickness.

  The present invention can be manufactured in a faster and simpler manner, can improve process efficiency, can easily adjust the thickness of the insulating layer, and can form a high-resolution via hole without physical damage. A method for manufacturing an insulating layer is provided.

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

  In the present specification, a step of sealing a semiconductor element having a metal protrusion on the surface with a polymer resin layer containing an alkali-soluble resin and a thermosetting binder; the semiconductor element having a metal protrusion formed on the surface is sealed Maintaining a state, forming a pattern on the polymer resin layer; first curing the polymer resin layer on which the pattern is formed; etching the surface of the cured polymer resin layer with an alkaline aqueous solution to form a metal There is provided a method for producing an insulating layer, comprising: exposing a protrusion; and secondarily curing the polymer resin layer with the metal protrusion exposed.

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

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

  According to one embodiment of the invention, sealing a semiconductor element having a metal protrusion on the surface with a polymer resin layer containing an alkali-soluble resin and a thermosetting binder; a semiconductor element having a metal protrusion on the surface Forming a pattern in the polymer resin layer while maintaining a sealed state; a step of first curing the polymer resin layer on which the pattern is formed; and a surface of the cured polymer resin layer with an alkaline aqueous solution. There may be provided a method for manufacturing an insulating layer, comprising: etching to expose metal protrusions; and second-curing the polymer resin layer with the metal protrusions exposed.

  When the inventors of the present invention use the method for manufacturing an insulating layer according to the embodiment, the metal protrusions sealed by the polymer resin layer are exposed through chemical etching with an alkaline aqueous solution to thereby physically expose the insulating layer. Through experiments, it is possible to prevent excessive damage and to easily adjust the thickness of the insulating layer to a desired range, and to manufacture the insulating layer through a simpler process in a faster time, thereby improving the efficiency of the process. Confirmed and completed the invention.

  In particular, in the method for manufacturing an insulating layer according to the embodiment, a metal resin can be easily exposed on the surface of the insulating layer by applying a polymer resin of a novel component that can be etched at a proper level with a specific alkaline aqueous solution. Therefore, the multilayer circuit board can be easily manufactured through the exposed metal protrusions.

  The method for manufacturing an insulating layer according to the embodiment includes a step of forming a pattern on the polymer resin layer while maintaining a state in which a semiconductor element having a metal protrusion formed on the surface is sealed. A high-resolution fine opening (via hole) can be formed in the polymer resin layer without affecting the element and without physical damage. In a method for manufacturing a multilayer printed circuit board, which will be described later, by filling the fine opening (via hole) with metal, it can serve as an electrical path between the lower substrate and the upper substrate with reference to the insulating layer. Therefore, it is possible to improve the degree of integration in a multilayer circuit board.

  More specifically, the method for manufacturing an insulating layer according to the embodiment includes a step of sealing a semiconductor element having a metal protrusion on a surface with a polymer resin layer containing an alkali-soluble resin and a thermosetting binder; A step of forming a pattern on the polymer resin layer while maintaining a state in which the semiconductor element on which the metal protrusion is formed is hermetically sealed; a step of first curing the polymer resin layer on which the pattern is formed; Etching the surface of the molecular resin layer with an alkaline aqueous solution to expose the metal protrusions; and secondly curing the polymer resin layer with the metal protrusions exposed.

  First, in the step of sealing a semiconductor element having a metal protrusion on the surface with a polymer resin layer containing an alkali-soluble resin and a thermosetting binder, the semiconductor element may have a metal protrusion formed on the surface. An example of a method for forming metal protrusions on the surface of the semiconductor element is not particularly limited. For example, a plating process for an opening of the photosensitive resin layer pattern or an adhesion process using an adhesive may be used. it can.

  As specific examples of the plating process for the openings of the photosensitive resin layer pattern, a step of laminating a photosensitive resin layer on a semiconductor element; a step of forming a pattern on the photosensitive resin layer; and a step of electroplating Including metal protrusion formation methods can be used.

  More specifically, the photosensitive resin layer can exhibit photosensitivity and alkali solubility. Therefore, the molecular structure is deformed by an exposure process of irradiating the photosensitive resin layer with light, and the resin layer can be etched or removed by a development process in which an alkaline developer is brought into contact.

  Accordingly, when alkali development is performed after selectively exposing a part of the photosensitive resin layer, the exposed part is not developed, and only the unexposed part is selectively etched and removed. be able to. Thus, a part of the photosensitive resin layer which remains as it is without being alkali-developed by exposure is referred to as a photosensitive resin pattern.

That is, when an example of a method for exposing the photosensitive resin layer is given, a photomask having a predetermined pattern formed on the photosensitive resin layer is contacted and irradiated with ultraviolet rays, or a predetermined mask included in the mask is exposed. After the pattern is imaged through the projection objective lens, it can be selectively exposed through a method such as irradiation with ultraviolet rays, direct imaging using a laser diode (Laser Diode) as a light source, and irradiation with ultraviolet rays. At this time, as an example of the ultraviolet irradiation condition, irradiation with a light amount of 5 mJ / cm ^{2 to} 600 mJ / cm ² may be mentioned.

  Moreover, the method of processing an alkali developing solution is mentioned as an example of the method of carrying out alkali development after exposure with respect to the said photosensitive resin layer. Examples of the alkaline developer are not particularly limited, and examples include alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, and amines. The concentration and temperature of the toner can be adjusted, and an alkaline developer sold as a product can also be used. Although the specific usage-amount of the said alkali developing solution is not restrict | limited in particular, Adjustment to the density | concentration and temperature which do not damage the said photosensitive resin pattern is required, for example, sodium carbonate 0.5-25% of 25 to 35 degreeC % Aqueous solution can be used.

  Meanwhile, in the electroplating stage, 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. It is done.

  On the other hand, examples of specific wet deposition processes include electroless plating of various metals, and electroless copper plating is common, and a roughening process may be further included before or after deposition.

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

  Further, in order to leave only the metal protrusions, a step of removing the photosensitive resin layer may be further included after the step of electroplating. When removing the photosensitive resin pattern, it is preferable to use a method in which only the photosensitive resin layer is removed without removing the lower semiconductor element and the metal protrusion as much as possible.

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

  On the other hand, as a specific example of the bonding process using the adhesive, a metal protrusion is formed on the surface of a passive element such as MLCC or an active element such as a semiconductor chip, and then the opposite side of the formed metal protrusion. A method of adhering to the surface of a semiconductor element using an insulating adhesive or the like can be used. At this time, as a 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, it is possible to use a method in which a photosensitive resin layer pattern is formed on the surface of a passive element or active element, and then a metal is plated on the opening of the pattern.

  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 It can have a cross-sectional diameter of 3 μm to 30 μm. The cross-sectional diameter means a diameter of a cross section obtained by cutting the metal protrusion in a direction perpendicular to the height direction of the metal protrusion, or a maximum diameter. For example, examples of the shape of the metal protrusion include a cylinder, a truncated cone, a polygonal column, a polygonal truncated cone, an inverted truncated cone, and an inverted polygonal truncated cone. Moreover, the example of the metal component contained in the said metal protrusion is not specifically limited, For example, conductive metals, such as copper and aluminum, can be used.

  The semiconductor element having the metal protrusion formed on the surface can be sealed with a polymer resin layer. More specifically, the semiconductor element may be present in a state where it is formed on a base material including a semiconductor material such as a circuit board such as a copper clad laminate, a sheet, a multilayer printed wiring board, or a silicon wafer. is there. In order to form the semiconductor element on the base material, it is possible to apply without limitation a method in which an adhesive layer is formed on the surface of the base material to bond the semiconductor element, or an adhesive layer is formed on the semiconductor element and bonded to the base material. it can.

  Examples of the adhesive layer are not particularly limited, and various adhesive layers widely known in the field of semiconductor elements and electrical and electronic materials can be used without limitation. For example, a debonding-type temporary fixing adhesive ( A Debondable Temporary Adhesive) or a die bonding film (Die Attach Film, DAF) can be used. Thus, the conductor wiring can be sealed through the method of forming the polymer resin layer on the base material in the state where the semiconductor element exists on the base material.

  An example of a method for forming the polymer resin layer on the substrate is not particularly limited. For example, the polymer resin composition for forming the polymer resin layer may be directly coated on the substrate, or on the carrier film. A method of laminating the base material and the polymer resin layer after applying the polymer resin composition to the substrate and forming the polymer resin layer can be used.

  When the semiconductor element having the metal protrusion formed on the surface is sealed with the polymer resin layer, the semiconductor element is all except for the part that contacts the base formed on the lower part and the part that contacts the metal protrusion. The surface of can be in contact with the polymer resin layer. In addition, all the surfaces of the metal protrusions formed on the surface of the semiconductor element can be sealed with the polymer resin layer and come into contact with the polymer resin layer.

  The polymer resin layer means a film formed through drying of 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, 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 there is too much content of the said thermosetting binder, the developability of the said polymeric resin layer will fall, and intensity | strength can fall. On the other hand, when the content of the thermosetting binder is too small, not only the polymer resin layer is excessively developed but also the uniformity during coating can be lowered.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Further, since a large number of the cyclic imide functional groups are present in the alkali-soluble resin, the polarity is increased by the carbonyl group and the tertiary amine group contained in the cyclic imide functional group, and the interfacial adhesive force of the alkali-soluble resin is increased. Can be increased. As a result, the polymer resin layer containing the alkali-soluble resin can increase the interfacial adhesive force with the metal layer laminated on the top.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Specifically, the alkali-soluble resin produced through the reaction of the carboxylic acid compound substituted with the amino group and the cyclic unsaturated imide compound has an acid value determined by KOH titration of 50 mg KOH / g to 250 mg KOH. / G, or 70 mg KOH / g to 200 mg KOH / g. Although the example of the method of measuring the acid value of the said alkali-soluble resin is not specifically limited, For example, the following methods can be used. A 0.1N concentration KOH solution (solvent: methanol) was prepared as a base solution, and alpha-naphtholbenzene (pH: 0.8-8) was used as an indicator. .2 yellow, 10.0 blue green). Next, about 1 to 2 g of an alkali-soluble resin as a sample was collected and dissolved in 50 g of a dimethylformaldehyde (DMF) solvent, and after adding a label, it was titrated with a base solvent. The acid value was determined in units of mg KOH / g by the amount of base solvent used at the completion of the titration.

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

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

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

In addition, the polyfunctional amine compound containing two or more amino groups is a compound containing two or more amino groups (—NH ₂ ) in the molecule, and depending on the type of hydrocarbon bonded to the amino group, All aromatic, alicyclic or aromatic polyfunctional amines can be included. Through the polyfunctional amine compound containing two or more amino groups, the flexibility and toughness of the alkali-soluble resin, the adhesive strength of the copper foil, and the like 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, 1,4 -Bis (aminomethyl) -cyclohexane, bis (aminomethyl) -norbornene, octahydro-4,7-methanoindene-1 (2), 5 (6) -dimethanamine, 4,4'-methylenebis (cyclohexylamine), 4, 4'-methylenebis (2-methylcyclohexylamine), isophoronediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,3,5,6- Tetramethyl-1,4-phenylenediamine, 2,4,5,6-tetrafluoro-1,3-pheny Diamine, 2,3,5,6-tetrafluoro-1,4-phenylenediamine, 4,6-diaminoresinol, 2,5-diamino-1,4-benzenedithiol, 3-aminobenzylamine, 4- Aminobenzylamine, m-xylenediamine, p-xylenediamine, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 2,6-diaminoanthraquinone, m-tolidine, o-tolidine, 3,3 ', 5 5'-tetramethylbenzidine (TMB), o-dianisidine, 4,4'-methylenebis (2-chloroaniline), 3,3'-diaminobenzidine, 2,2'-bis (trifluoromethyl) -benzidine, 4 , 4′-diaminooctafluorobiphenyl, 4,4′-diamino-p-terphenyl, 3,3′-diaminodiphe Rumethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-methylenebis (2-ethyl-6-methylaniline), 4,4′-methylenebis (2,6-diethylaniline), 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 4,4′-ethylenedianiline, 4,4′-diamino-2,2 '-Dimethylbibenzyl, 2,2'-bis (3-amino-4-hydroxyphenyl) propane, 2,2'-bis (3-aminophenyl) -hexafluoropropane, 2,2'-bis (4- Aminophenyl) -hexafluoropropane, 2,2′-bis (3-amino-4-methylphenyl) -hexafluoropropane, 2,2′- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,1′-bis (4-aminophenyl) -cyclohexane, 9,9′-bis (4-aminophenyl) -fluorene, 9,9′-bis (4-amino-3- Chlorophenyl) fluorene, 9,9′-bis (4-amino-3-fluorophenyl) fluorene, 9,9′-bis (4-amino-3-methylphenyl) fluorene, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 1,3-bis (3-aminophenoxy) -benzene, 1,3-bis (4-aminophenoxy) -benzene, 1,4- (4-aminophenoxy) -benzene, 1,4-bis (4-amino-2-trifluoromethylphenoxy) -benzene, 4,4′-bis (4-aminophenoxy) -biphenyl, 2,2′- Bis [4- (4-aminophenoxy) -phenyl] propane, 2,2′-bis [4- (4-aminophenoxy) -phenyl] hexafluoropropane, bis (2-aminophenyl) sulfide, bis (4- Aminophenyl) sulfide, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, bis (3-amino-4-hydroxy) sulfone, bis [4- (3-aminophenoxy) -phenyl] sulfone, Bis [4- (4-aminophenoxy) -phenyl] sulfone, o-tolidinesulfone, 3,6-diaminocarbazole, 1,3,5- Tris (4-aminophenyl) -benzene, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, 4,4′-diaminobenzanilide, 2- (3-aminophenyl) -5-aminobenzimidazole 2- (4-aminophenyl) -5-aminobenzoxazole, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, 4,6 -Diaminoresorcinol, 2,3,5,6-pyridinetetraamine, polyfunctional amine containing siloxane structure of Shin-Etsu silicone (PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012) , KF-8008, X-22-1660B-3, X-22-9409), a polyfunctional amine containing a Dow Corning siloxane structure Dow Corning3055), polyfunctional amine containing polyether structure (Huntsman Corporation, BASF Corporation).

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

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

In Formula 4, R ₃ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and R ₄ is —H, —OH, -NR ₅ R _6, halogen, or an alkyl group having 1 to 20 carbon atoms, wherein _{R 5} and _{R 6} are each independently hydrogen, alkyl group having 1 to 20 carbon atoms or 6 to 20 carbon atoms, It may be an aryl group, and “ ^* ” means a point of attachment.

Preferably, in Chemical Formula 3, R ₂ may be phenylene, and in Chemical Formula 4, R ₃ may be phenylene and R ₄ may be —OH.

  Meanwhile, the alkali-soluble resin may further include a vinyl-based repeating unit in addition to the repeating unit represented by Chemical Formula 3; and the repeating unit represented by Chemical Formula 4. The vinyl repeating unit is a repeating unit contained in a homopolymer of a vinyl monomer containing at least one vinyl group in the molecule, and examples of the vinyl monomer are particularly limited. Examples thereof include ethylene, propylene, isobutylene, butadiene, styrene, acrylic acid, methacrylic acid, maleic anhydride, and maleimide.

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

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

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

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

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

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

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

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

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

  Although the example of the said phenol group containing resin is not specifically limited, For example, novolak resins, such as a phenol novolak resin, a cresol novolak resin, a 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) propan-2-yl) Bisphenol A resins such as phenyl) ether-1,1-diyl) diphenol] can be used alone or in combination.

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

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

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

  An example of the content of the inorganic filler is not particularly limited, but in order to achieve high rigidity of the polymer resin layer, with respect to 100 parts by weight of all the resin components contained in the polymer resin layer, The inorganic filler can be added at 100 parts by weight or more, or 100 to 600 parts by weight, or 100 to 500 parts by weight.

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

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

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

  The polymer resin layer may further include a resin or elastomer having a molecular weight of 5000 g / mol or more that can induce phase separation. This makes it possible to roughen the cured product of the polymer resin layer. The example of the molecular weight measuring method of the resin or elastomer having a molecular weight of 5000 g / mol or more is not particularly limited, and means, for example, a weight average molecular weight in terms of polystyrene measured by GPC method. In the process of measuring the polystyrene-equivalent weight average molecular weight measured by the GPC method, a commonly known analyzer and a detector such as a differential refractive index detector (Refractive Index Detector) and an analytical column can be used. Temperature conditions, solvent, flow rate can be applied. Specific examples of the measurement conditions include a temperature of 30 ° C., a chloroform solvent (Chloroform), and a flow rate of 1 mL / min.

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

  The content of the photoinitiator contained in the polymer resin layer may be 0.01% by weight or less with respect to the weight of the whole polymer resin layer. The content of the photoinitiator contained in the polymer resin layer is 0.01% by weight or less with respect to the weight of the whole polymer resin layer, which means that the photoinitiator contained in the polymer resin layer is It means that the content is very small or does not contain any photoinitiator. Accordingly, the interface desorption property with the insulating layer and the conductive layer that can be generated by the photoinitiator is reduced, so that the adhesiveness and durability of the insulating layer can be improved.

  The method for manufacturing an insulating layer according to the embodiment may include forming a pattern on the polymer resin layer while maintaining a sealed state of the semiconductor element having the metal protrusion formed on the surface. .

  The method for manufacturing an insulating layer according to the embodiment includes a step of forming a pattern on a polymer resin layer while maintaining a sealed state of a semiconductor element having a metal protrusion formed on a surface thereof. Can be used to form a fine opening (via hole) with high resolution without physical damage without affecting the polymer resin layer. In the method of manufacturing a multilayer printed circuit board described later, the fine openings (via holes) can be filled with metal, thereby serving as an electrical path between the lower substrate and the upper substrate based on the insulating layer. The degree of integration on a circuit board having a multilayer structure can be improved.

  The pattern formed in the polymer resin layer means a state in which openings (opening) are partially formed in the polymer resin layer, and specifically, a pattern is formed in the polymer resin layer. Thus, a part of the surface of the base material layer below the polymer resin layer can be exposed through the opening. That is, the step of forming the pattern on the polymer resin layer while the semiconductor element having the metal protrusion formed on the surface is hermetically sealed is the state in which the semiconductor element having the metal protrusion formed on the surface is sealed. The method may include forming a via hole in the polymer resin layer while maintaining the above.

  In the step of forming the pattern on the polymer resin layer, the semiconductor element having the metal protrusion formed on the surface can be maintained in a sealed state. That is, in the process of partially forming the opening in the polymer resin layer, the opening is not formed near the portion where the semiconductor element is located. Therefore, even if a pattern is formed on the polymer resin layer, the semiconductor element and the metal protrusion on the surface are maintained as they are without physical and chemical influences, and the sealed state in which all surfaces are in contact with the polymer resin layer is maintained. It will be.

  Meanwhile, as an example of a method for forming a pattern on the polymer resin layer, a chemical layer is formed by forming a pattern layer on the polymer resin layer and etching the polymer resin layer using the pattern layer as an etching mask pattern. Etching methods can be used. That is, forming the pattern on the polymer resin layer may include forming a pattern layer on the polymer resin layer; and alkali developing the polymer resin layer exposed by the pattern layer. . At this time, as an example of the pattern layer, a photosensitive resin pattern layer or a metal pattern layer can be used.

  Meanwhile, after the step of alkali developing the polymer resin layer exposed by the pattern layer, 0.1 wt% to 85 wt% based on the total weight of the polymer resin layer exposed by the pattern layer, or 0. 1% to 50% by weight, or 0.1% to 10% by weight can remain. This is thought to be because the alkali-soluble resin contained in the polymer resin layer was removed by the alkali developer, but the thermosetting binder or inorganic filler having almost no alkali developability remained without being removed. It is done.

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

  In this way, in the step of alkali developing the polymer resin layer exposed by the pattern layer, a part of the polymer resin layer remains without being developed, so that the target polymer resin is removed during the subsequent pattern layer removal step. Instead of removing the pattern, via hole expansion due to removal of the polymer resin pattern can be prevented while the remaining polymer resin layer is removed.

  When a photosensitive resin pattern layer is used as the mask pattern of the polymer resin layer, the step of forming a pattern on the polymer resin layer includes the step of forming a photosensitive resin layer on the polymer resin layer; The photosensitive resin layer may be exposed and alkali-developed to form a photosensitive resin pattern, and the polymer resin layer exposed by the photosensitive resin pattern may be alkali-developed.

  The photosensitive resin layer can exhibit photosensitivity and alkali solubility. Therefore, the molecular structure is deformed by an exposure process of irradiating the photosensitive resin layer with light, and the resin layer can be etched or removed by a development process in which an alkaline developer is brought into contact.

  Therefore, when the photosensitive resin layer is selectively exposed to a portion and then developed with alkali, the exposed portion is not developed, and only the unexposed portion is selectively etched and removed. Can. Thus, a part of the photosensitive resin layer which is not alkali-developed by exposure and remains as it is is called a photosensitive resin pattern.

That is, the method for exposing the photosensitive resin layer is, for example, contacting a photomask having a predetermined pattern formed on the photosensitive resin layer and irradiating ultraviolet rays, or applying a predetermined pattern included in the mask. After imaging through the projection objective lens, it is possible to selectively expose through a method such as irradiation with ultraviolet rays, direct imaging using a laser diode as a light source, and irradiation with ultraviolet rays. At this time, as an example of the ultraviolet irradiation condition, irradiation with a light amount of 5 mJ / cm ^{2 to} 600 mJ / cm ² may be mentioned.

  Moreover, the method of processing an alkali developing solution is mentioned as an example of the method of carrying out alkali development after exposure with respect to the said photosensitive resin layer. Examples of the alkaline developer are not particularly limited, and examples include alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, and amines. The concentration and temperature of the toner can be adjusted, and an alkaline developer sold as a product can also be used. Although the specific usage-amount of the said alkali developing solution is not restrict | limited in particular, Adjustment is required by the density | concentration and temperature which do not damage the said photosensitive resin pattern, for example, sodium carbonate 0.5-3% of 25 to 35 degreeC An aqueous solution can be used.

  A ratio at which the photosensitive resin pattern is removed may be 0.01% by weight or less based on the weight of the entire photosensitive resin pattern. The ratio at which the photosensitive resin pattern is removed is 0.01% by weight or less with respect to the weight of the entire photosensitive resin pattern. This means that the ratio at which the photosensitive resin pattern is removed is very small or photosensitive. It means that the resin pattern is not removed at all.

  Thus, the photosensitive resin layer can be exposed and alkali-developed to form a photosensitive resin pattern, and the polymer resin layer exposed by the photosensitive resin pattern can be alkali-developed. As described above, the photosensitive resin layer may have a fine and uniform pattern using photosensitivity, and a portion of the polymer resin exposed through the pattern formed on the photosensitive resin layer. Through the process in which only the surface of the layer is selectively in contact with the alkaline developer, it is possible to ensure a precision equal to or higher than this and higher process economy while replacing the conventional laser etching process.

  That is, at the stage of alkali development of the polymer resin layer exposed by the photosensitive resin pattern, the photosensitive resin pattern remains as it is and is used as a resist mask due to the property that it is not removed by an alkaline developer. Through the opening, the alkaline developer can contact the polymer resin layer located under the photosensitive resin layer. At this time, since the polymer resin layer contains an alkali-soluble resin, the polymer resin layer has an alkali-solubility that is dissolved by an alkali developer. Therefore, the portion in contact with the alkali developer in the polymer resin layer is dissolved, Can be removed.

  Therefore, the polymer resin layer exposed by the photosensitive resin pattern means a polymer resin layer portion whose surface does not contact the photosensitive resin pattern, and the polymer resin layer exposed by the photosensitive resin pattern is alkali-developed. The step of performing may include a step in which the alkaline developer used in forming the photosensitive resin pattern passes through the photosensitive resin pattern and contacts the lower polymer resin layer.

  A polymer resin pattern having the same shape as the photosensitive resin pattern may be formed on the polymer resin layer by performing an alkali development on the polymer resin layer exposed by the photosensitive resin pattern. A part of the polymer resin layer that remains as it is without being alkali-developed like the photosensitive resin pattern can be said to be a polymer resin pattern.

  As described above, since pattern formation through development of the photosensitive resin layer and pattern formation through development of the polymer resin layer are simultaneously performed with one alkali developer, rapid mass production is possible. The efficiency of the process can be improved, and a fine pattern having the same shape as the fine pattern formed on the photosensitive resin layer can be easily introduced into the polymer resin layer by a chemical method.

  In the case where a metal pattern layer is used as the mask pattern of the polymer resin layer, the step of forming the pattern on the polymer resin layer is such that the opposite surface of the metal layer having the carrier film bonded on one side is placed on the polymer resin layer Forming a patterned photosensitive resin layer on the carrier film; removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer; and patterning the metal layer Separating the carrier film from the patterned metal layer and removing the carrier film; and alkali-developing the polymer resin layer exposed by the patterned metal layer.

  In the method of adhering the opposite surface of the metal layer having the carrier film bonded to the one surface on the polymer resin layer, the opposite surface of the metal layer having the carrier film bonded to the one surface is bonded to the polymer resin layer. As an example, a method in which a polymer resin composition is applied to the opposite surface of the metal layer having a carrier film bonded to the one surface and dried can be used.

  The step of forming a patterned photosensitive resin layer on the carrier film may include the steps of forming a photosensitive resin layer on the carrier film, exposing the photosensitive resin layer and alkali developing, The contents relating to the photosensitive resin layer and the exposure and development thereof include those described above for the photosensitive resin pattern layer used for the mask pattern of the polymer resin layer.

  In the step of removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer, the photosensitive resin pattern forms a pattern on the carrier film and the metal layer. Used as a resist role. Therefore, the carrier film and the metal layer exposed by the photosensitive resin layer pattern mean a carrier film and a metal layer portion that do not come into contact with the photosensitive resin layer on the surface.

  Specifically, the step of removing the carrier film and the metal layer exposed by the photosensitive resin layer pattern is a step in which the etching solution passes through the photosensitive resin layer on which the pattern is formed and contacts the carrier film and the metal layer. Can be included.

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

  By using the same material as the metal layer as the material for the carrier film, the carrier film and the metal layer can be removed simultaneously or sequentially with the same etching solution, and a pattern can be easily formed.

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

  That is, the etchant used in the step of removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form the patterned metal layer is physically applied to the polymer resin layer. The polymer resin layer is stably maintained until the fine metal pattern layer is formed without chemically affecting it at all, and the aspect ratio is lowered by using the fine metal pattern layer as a resist mask. The resolution of via holes can be increased.

  After passing through the step of forming the patterned metal layer by removing the carrier film and metal layer exposed by the patterned photosensitive resin layer, the patterned metal layer and pattern on the polymer resin layer The patterned carrier film and the patterned photosensitive resin layer can be sequentially laminated.

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

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

  Since the adhesive force between the carrier film and the metal layer is smaller than the adhesive force between the polymer resin layer and the metal layer, the polymer resin layer and the metal layer are prevented from peeling when the carrier film and the metal layer are physically peeled. can do.

  In addition, since the carrier film and the photosensitive resin layer formed on the carrier film are removed together in the process of separating the carrier film and the metal layer, a separate developer or etching solution is used. The resolution of the via hole can be increased by easily leaving only the fine metal pattern mask on the polymer resin layer without using it and reducing the aspect ratio through the patterning process.

  In the step of alkali developing the polymer resin layer exposed by the metal layer pattern, the metal layer pattern is used as a resist for forming a pattern on the polymer resin layer. Therefore, the polymer resin layer exposed by the metal layer pattern means a polymer resin layer portion whose surface does not contact the metal layer.

  Specifically, the step of alkali developing the polymer resin layer exposed by the metal layer pattern includes a step in which an alkali developer passes through the metal layer having the pattern formed thereon and contacts the polymer resin layer. it can.

  Since the polymer resin layer contains an alkali-soluble resin, the polymer resin layer has an alkali-solubility that is dissolved by an alkali developer. Therefore, a portion of the polymer resin layer that contacts the alkali developer may be dissolved and removed. it can.

  Examples of the alkaline developer are not particularly limited, and examples include alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, and amines. Preferably, a 1% sodium carbonate developer at 30 ° C. can be used. The specific usage amount of the alkali developer is not particularly limited.

  At this time, the portion dissolved and removed by contact with the alkaline developer in the polymer resin layer can form a via hole, and the average of the via holes contained in the polymer resin layer in which the pattern is formed The diameter can be 1 μm to 500 μm, or 100 μm to 300 μm.

  The method for manufacturing an insulating layer according to the embodiment may include a step of first curing the polymer resin layer on which the pattern is formed. In the step of curing the polymer resin layer, specific examples of the curing method are not particularly limited, and any of thermosetting or photocuring methods can be used without limitation.

  Through the primary curing step, a main chain including an ester bond may be formed in the polymer resin layer. Examples of the ester bond include a method of photocuring through an acrylic resin in which acrylic acid is ester-bonded, or heat curing so that an ester bond is formed by a reaction between carboxylic acid and epoxy.

  At this time, the specific thermosetting conditions are not limited, and the conditions can be adjusted by a polymer resin layer etching method to be described later. For example, when the polymer resin layer is etched by treating a photoresist stripping solution, the primary curing stage of the polymer resin layer may proceed at a temperature of 50 ° C. to 150 ° C. for 0.1 hour to 2 hours. it can. If the thermosetting temperature of the polymer resin layer is too low or the thermosetting time is shortened, the polymer resin layer is excessively damaged by the peeling solution, and the thermosetting temperature of the polymer resin layer is high or the thermosetting time is When the length becomes longer, the etching of the polymer resin layer by the stripping solution may not proceed easily.

  The method for manufacturing an insulating layer according to the embodiment may include a step of exposing the metal protrusion by etching the surface of the cured polymer resin layer with an alkaline aqueous solution. Etching the surface of the cured polymer resin layer with an alkaline aqueous solution to expose the metal protrusions, thereby connecting the electrical signal to the conductor wiring sealed inside the cured polymer resin layer through the exposed metal protrusions. Can do.

  The above-described exposure of the metal protrusion can proceed through 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, use a photoresist stripping solution. can do. The aqueous alkaline solution can be removed by etching the polymer resin layer by cutting out 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 adjusting the concentration and temperature of the alkaline aqueous solution, the etching rate of the polymer resin layer by the alkaline aqueous solution can be controlled, and the process efficiency is maintained while maintaining an appropriate etching rate within the above-mentioned range. It is possible to easily adjust the thickness of the polymer resin layer while securing the thickness.

  As the alkaline aqueous solution, an aqueous solution of a metal hydroxide such as potassium hydroxide or sodium hydroxide can be used, Atotech's Resistrip product group, Orchem's ORC-731, ORC-723K, Commercially available products such as ORC-740 and SLF-6000 can also be used.

  The etching with the alkaline aqueous solution can proceed from the surface of the cured polymer resin layer. The surface of the cured polymer resin layer means an area where the polymer resin layer sealing the conductor wiring having metal protrusions formed on the surface is in contact with air, and the surface from the cured polymer resin layer surface to the surface. As the etching progresses inside the polymer resin layer that seals the conductor wiring on which the metal protrusions are formed, the metal protrusions can be exposed.

  Since the etching with the alkaline aqueous solution proceeds from the surface of the cured polymer resin layer, the alkaline aqueous solution can contact the surface of the cured polymer resin layer. At this time, in order to ensure uniformity in thickness by uniform removal without physical damage to the polymer resin layer, the alkaline aqueous solution is brought into contact with the surface of the polymer resin layer through a method such as spraying through a spray. be able to.

  If necessary, a step of removing the pattern layer remaining on the polymer resin layer may be performed before the step of etching the cured polymer resin layer surface with an aqueous alkali solution to expose the metal protrusions. An example of a method for removing the photosensitive resin pattern layer or the metal pattern layer used for the pattern layer is not particularly limited, and a photoresist stripping solution is processed or a desmear process or plasma etching is performed. The thickness of the copper foil of the metal layer can be made very thin to 3 μm or less, and the metal layer can be removed while removing a part of the lower copper line, or the metal layer is removed, but the lower copper line is affected. It is possible to use an etching solution that does not give any. However, it is preferable to use a method that selectively removes only the pattern layer and does not affect the lower polymer resin layer.

  The method for manufacturing an insulating layer according to the embodiment may include a step of secondarily curing the polymer resin layer in a state where the metal protrusion is exposed. Through the secondary curing step, the chemical resistance of the finally manufactured insulating layer can be improved.

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

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

  The inventors of the present invention include an insulating layer manufactured in the embodiment including a semiconductor element having a metal protrusion formed on an inner surface, the metal protrusion being exposed to the outside of the insulating layer, and on the insulating layer. In the case of further laminating a metal pattern layer, the present invention was completed by confirming that the metal pattern layer can exchange an electrical signal with a semiconductor element inside the insulating layer through a 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 or a photocured product. The content regarding the alkali-soluble resin and the thermosetting binder includes the content described above in the embodiment.

  More specifically, the step of forming the metal pattern layer on the insulating layer includes, for example, 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 to remove the exposed metal thin film.

  In the step of forming the metal thin film on the insulating layer, examples of the method of forming the metal thin film include a dry deposition process or a wet deposition process. Specific examples of the dry deposition process include vacuum deposition and ion deposition. Examples thereof include plating and sputtering methods.

  On the other hand, specific examples of the wet deposition process include electroless plating of various metals. Electroless copper plating is generally used, and a roughening treatment process is further performed before or after deposition. Can be included.

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

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

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

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

  In particular, it is preferable that the pattern formed on the metal thin film is formed so that the opening included in the pattern can come into contact with the metal protrusion exposed to the outside of the insulating layer. The opening included in the pattern means a portion that is removed through exposure and development of the photosensitive resin layer, and corresponds to a portion where metal is deposited through metal deposition described later to form the metal pattern layer. . Therefore, if the opening included in the pattern is not formed so as to be able to contact the metal protrusion exposed outside the insulating layer, the semiconductor element inside the insulating layer while the metal pattern layer is in contact with the metal protrusion. And cannot exchange electrical signals.

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

  At this time, the metal deposited on the metal thin film exposed by the photosensitive resin layer pattern can form the above-described metal pattern layer, and more specifically, the metal pattern layer is a semiconductor element through a metal protrusion. And can be formed to be connected to each other. Accordingly, the metal pattern layer can exchange an electrical signal with the semiconductor element included in the insulating layer. More specifically, one end of the metal protrusion may be in contact with a semiconductor element, and the other end of the metal protrusion may be in contact with the metal pattern layer to electrically connect the conductor wiring and the metal pattern layer.

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

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

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

  Forming the metal pattern layer on the insulating layer may include filling a via hole included in the insulating layer internal pattern with metal. As described above, the insulating layer manufactured in the embodiment includes a pattern including a via hole (opening) therein, and the insulating layer is formed in the process of forming the metal pattern layer on the insulating layer. Internal via holes (openings) can be filled with metal. Specifically, in the step of forming the metal thin film on the insulating layer, the metal thin film may be formed on the surface of the insulating layer surrounding the via hole (opening) included in the insulating layer and the lower base material. The via hole (opening) can be filled with the metal while the metal is deposited inside the via hole (opening) through the step of depositing the metal on the metal thin film.

  By filling the fine opening (via hole) with metal as described above, it can serve as an electrical path between the lower substrate and the upper substrate with respect to the insulating layer, and can be a multilayer circuit board. The degree of integration can be improved.

  Meanwhile, after the step of forming the metal pattern layer on the insulating layer, the method may further include a step of removing a base material formed under the semiconductor element, if necessary. As described above, the semiconductor element may exist in a state where it is formed on a base material including a semiconductor material such as a circuit board, a sheet, or a multilayer printed wiring board. If necessary, the lower base material of the semiconductor element can be removed to form a multilayer circuit board having a finer structure, and the base material is present in a state of being adhered or adhered to the polymer resin layer. Can be physically peeled off.

  According to the present invention, it is possible to manufacture in a faster and simpler manner, to improve process efficiency, to easily adjust the thickness of the insulating layer, and to form a high resolution via hole without physical damage. The manufacturing method of the insulating layer which can be formed, and the manufacturing method of the multilayer printed circuit board using the insulating layer obtained by the manufacturing method of the said insulating layer can be provided.

FIG. 3 is a diagram schematically showing a manufacturing process of an insulating layer of Example 1. It is the figure which showed schematically the manufacturing process of the multilayer printed circuit board of Example 1. FIG. 6 is a diagram schematically showing a manufacturing process of an insulating layer of Example 2. FIG. FIG. 10 is a diagram schematically illustrating a manufacturing process of a multilayer printed circuit board according to Example 2.

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

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

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

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

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

<Examples 1 and 2: Production of insulating layer and multilayer printed circuit board>
Example 1
(1) Production of Insulating Layer An insulating layer was produced in the order of steps <1> to <10> as follows.

  <1> A debonding-type temporary fixing adhesive (Debondable Temporary Adhesive) 2 was formed on the silicon wafer 1.

  <2> A pattern is formed by spin-coating a photoresist on a semiconductor chip 3 having a thickness of 80 μm, and after electroplating to form a copper bump 4 having a height of 15 μm and a diameter of 20 μm, the copper bump 4 is formed. The laminated semiconductor chip 3 is laminated on a debonding-type temporary fixing adhesive 2 on the silicon wafer 1, and the silicon wafer 1-debonding-type temporary fixing adhesive (Debondable Temporary Adhesive) 2-semiconductor chip. The structure laminated | stacked in order of 3-copper bump 4 was formed.

  <3> Alkali synthesized in Production Example 1 on the opposite surface of 3 μm-thick ultrathin copper foil 6 (trade name: MT18SD-H, manufactured by Mitsui Kinzoku Mining Co., Ltd.) with carrier copper foil 7 bonded to one surface A polymer resin composition in which 16 g of a soluble resin, 5 g of a thermosetting binder (trade name: MY-510, manufactured by Huntsman) and 35 g of an inorganic filler (trade name: SC2050 MTO, manufactured by Adamate) is mixed to a thickness of 100 μm. After coating and drying to produce a structure in which the carrier copper foil 7 -the ultrathin copper foil 6 -the polymer resin layer 5 are laminated in this order, a debonding-type temporary fixing adhesive (Debondable) on the silicon wafer 1 is prepared. Temporary Adhesive) 2 and the polymer resin layer 5 are vacuum laminated at 85 ° C. to form a silicon wafer 1-debonding type temporary fixing contact The structure laminated | stacked in order of the adhesive agent (Debondable Temporary Adhesive) 2-semiconductor chip 3-copper bump 4-polymer resin layer 5-ultra-thin copper foil 6-carrier copper foil 7 is formed, and the semiconductor chip 3 and The copper bump 4 was sealed.

<4> A 15 μm-thick photosensitive dry film resist 8 (trade name: KL1015, manufactured by Kolon Industry Co., Ltd.) is laminated on the carrier copper foil 7 at 110 ° C., and the diameter on the photosensitive dry film resist 8 Is contacted with a circular negative photomask having a thickness of 150 μm, irradiated with ultraviolet rays (light amount of 25 mJ / cm ² ), and then developed the photosensitive dry film resist 8 through a 1% sodium carbonate developer at 30 ° C. Pattern was formed. And the etching liquid was processed and the carrier copper foil 7 and the ultra-thin copper foil 6 were etched. At this time, the photosensitive dry film resist 8 with the pattern formed acts as a protective layer for the carrier copper foil 7 and the ultrathin copper foil 6, and the photosensitive dry film is also applied to the carrier copper foil 7 and the ultrathin copper foil 6. The same pattern as the resist 8 was formed.

  <5> The ultrathin copper foil 6 and the carrier copper foil 7 were separated, and the photosensitive copper film 7 and the photosensitive dry film resist 8 laminated on the carrier copper foil 7 were removed.

  <6> The polymer resin layer 5 was developed through 30 ° C. and 1% sodium carbonate developer. At this time, the ultrathin copper foil 6 on which the pattern is formed acts as a protective layer for the polymer resin layer 5, and the same pattern as the ultrathin copper foil 6 is formed on the polymer resin layer 5. A 200 μm via hole 9 was formed.

  <7> The polymer resin layer 5 on which the pattern was formed was thermally cured at a temperature of 100 ° C. for 1 hour.

  <8> The ultrathin copper foil 6 remaining on the polymer resin layer 5 was removed by treating the etching solution.

  <9> A 3% sodium hydroxide resist stripping solution at a temperature of 50 ° C. is sprayed onto the surface of the polymer resin layer 5 to remove the copper bump 4 on the surface by removing about 3 μm from the surface of the polymer resin layer 5. Exposed to water, washed with water and dried. At this time, the process of exposing the copper bumps 4 was performed for 10 to 60 seconds per panel in a continuous process.

  <10> The polymer resin layer 5 with the copper bumps 4 exposed on the surface was thermally cured at a temperature of 200 ° C. for 1 hour to produce an insulating layer.

(2) Manufacture of multilayer printed circuit board A multilayer printed circuit board was manufactured in the order of steps <11> to <13> as follows.

  <11> A titanium-copper thin film is deposited on the manufactured insulating layer using a sputter and heated at 100 ° C. for 30 minutes to improve adhesion with the sputtered layer, and then dried. (Trade name: RY-5319, manufactured by Hitachi Chemical Co., Ltd.) was laminated to form a pattern, and a metal pattern circuit was formed by electroplating, and at the same time, the via hole 9 was filled with metal.

<12> A photosensitive dry film resist (trade name: KL1015, manufactured by Kolon Industry Co., Ltd.) having a thickness of 15 μm is laminated on the circuit at 110 ° C., and a circular shape having a diameter of 30 μm is formed on the photosensitive dry film resist. After contacting a negative photomask and irradiating with ultraviolet rays (light intensity of 25 mJ / cm ² ), the photosensitive dry film resist is developed through a 1% sodium carbonate developer at 30 ° C. to form a solder resist having a certain pattern. 10 was formed.

  <13> The silicon wafer 1 and the Debondable Temporary Adhesive 2 were separated and removed from the insulating layer to complete a multilayer printed circuit board.

Example 2
Insulating layers were manufactured in the order of steps <1> to <10> as described below.

  <1> An ultrathin copper foil 6 was formed on a copper clad laminate (trade name: LG-500GA VB / VB, LG Chemical Co., Ltd.) 1 and a carrier copper foil 7 was formed on the ultrathin copper foil 6. .

  <2> A semiconductor chip on which a copper bump 4 having a height of 15 μm and a diameter of 20 μm is formed by spin coating a photoresist on the semiconductor chip 3 and electroplating to form a copper bump 4. 3 is laminated to the carrier copper foil 7 on the copper-clad laminate 1 by the die bonding film 2, and the copper-clad laminate 1-ultra thin copper foil 6-carrier copper foil 7-die bonding film 2-semiconductor chip 3- The structure laminated | stacked in order of the copper bump 4 was formed.

  <3> Alkali synthesized in Production Example 1 on the opposite surface of 3 μm-thick ultrathin copper foil 6 (trade name: MT18SD-H, manufactured by Mitsui Kinzoku Mining Co., Ltd.) with carrier copper foil 7 bonded to one surface A polymer resin composition in which 16 g of a soluble resin, 5 g of a thermosetting binder (trade name: MY-510, manufactured by Huntsman) and 35 g of an inorganic filler (trade name: SC2050 MTO, manufactured by Adamate) is mixed to a thickness of 100 μm. After coating and drying to produce a structure laminated in the order of carrier copper foil 7-ultra thin copper foil 6-polymer resin layer 5, the carrier copper foil 7 on the copper-clad laminate 1 and the high The molecular resin layer 5 is vacuum-laminated at 85 ° C., and the copper-clad laminate 1-ultra thin copper foil 6-carrier copper foil 7-die bonding film 2-semiconductor chip 3-copper bump 4-polymer resin layer 5-electrode Thin copper foil 6-ca To form a sequentially with laminated structure of Adohaku 7 was sealed semiconductor chip 3 and the copper bumps 4.

<4> A 15 μm-thick photosensitive dry film resist 8 (trade name: KL1015, manufactured by Kolon Industry Co., Ltd.) is laminated on the carrier copper foil 7 at 110 ° C., and the diameter on the photosensitive dry film resist 8 Is contacted with a circular negative photomask having a thickness of 150 μm, irradiated with ultraviolet rays (light amount of 25 mJ / cm ² ), and then developed the photosensitive dry film resist 8 through a 1% sodium carbonate developer at 30 ° C. Pattern was formed. And the etching liquid was processed and the carrier copper foil 7 and the ultra-thin copper foil 6 were etched. At this time, the photosensitive dry film resist 8 with the pattern formed acts as a protective layer for the carrier copper foil 7 and the ultrathin copper foil 6, and the photosensitive dry film is also applied to the carrier copper foil 7 and the ultrathin copper foil 6. The same pattern as the resist 8 was formed.

  <5> The ultrathin copper foil 6 and the carrier copper foil 7 were separated, and the photosensitive copper film 7 and the photosensitive dry film resist 8 laminated on the carrier copper foil 7 were removed.

  <6> The polymer resin layer 5 was developed through 30 ° C. and 1% sodium carbonate developer. At this time, the ultrathin copper foil 6 on which the pattern is formed acts as a protective layer for the polymer resin layer 5, and the same pattern as the ultrathin copper foil 6 is formed on the polymer resin layer 5. A 200 μm via hole 9 was formed.

  <7> The polymer resin layer 5 on which the pattern was formed was thermally cured at a temperature of 100 ° C. for 1 hour.

  <8> The ultrathin copper foil 6 remaining on the polymer resin layer 5 was removed by treating the etching solution.

  <9> A 3% sodium hydroxide resist stripping solution at a temperature of 50 ° C. is sprayed onto the surface of the polymer resin layer 5 to remove the copper bump 4 on the surface by removing about 3 μm from the surface of the polymer resin layer 5. Exposed to water, washed with water and dried. At this time, the process of exposing the copper bumps 4 was performed for 10 to 60 seconds per panel in a continuous process.

  <10> The polymer resin layer 5 with the copper bumps 4 exposed on the surface was thermally cured at a temperature of 200 ° C. for 1 hour to produce an insulating layer.

(2) Manufacture of multilayer printed circuit board A multilayer printed circuit board was manufactured in the order of steps <11> to <14> as follows.

  <11> After depositing a copper thin film on the manufactured insulating layer using electroless copper plating and heating at 100 ° C. for 30 minutes to improve adhesion with the electroless copper plating, dry film (Trade name: RY-5319, manufactured by Hitachi Chemical Co., Ltd.) was laminated to form a pattern, and a metal pattern circuit was formed by electroplating, and at the same time, the via hole 9 was filled with metal.

<12> A photosensitive dry film resist (trade name: KL1015, manufactured by Kolon Industry Co., Ltd.) having a thickness of 15 μm is laminated on the circuit at 110 ° C., and a circular shape having a diameter of 30 μm is formed on the photosensitive dry film resist. After contacting a negative photomask and irradiating with ultraviolet rays (light intensity of 25 mJ / cm ² ), the photosensitive dry film resist is developed through a 1% sodium carbonate developer at 30 ° C. to form a solder resist having a certain pattern. 10 was formed.

  <13> The ultrathin copper foil 6 and the carrier copper foil 7 were separated, and the ultrathin copper foil 6 and the copper clad laminate 1 laminated on the lower part of the ultrathin copper foil 6 were removed.

  <14> The carrier copper foil 7 remaining under the insulating layer was removed by etching to complete a multilayer printed circuit board.

Example 3
Except that the alkali-soluble resin synthesized in Production Example 2 was used in place of the alkali-soluble resin synthesized in Production Example 1 at the production stage of the insulating layer of Example 1, the same as in Example 1 above. An insulating layer and a multilayer printed circuit board were manufactured by the method.

Example 4
The same procedure as in Example 1 except that the alkali-soluble resin synthesized in Production Example 3 was used in place of the alkali-soluble resin synthesized in Production Example 1 at the production stage of the insulating layer of Example 1. An insulating layer and a multilayer printed circuit board were manufactured by the method.

Example 5
The same procedure as in Example 1 except that the alkali-soluble resin synthesized in Production Example 4 was used instead of the alkali-soluble resin synthesized in Production Example 1 at the production stage of the insulating layer in Example 1. An insulating layer and a multilayer printed circuit board were manufactured by the method.

Example 6
During production of the polymer resin layer, 16 g of the alkali-soluble resin synthesized in Production Example 1, 5 g of a thermosetting binder (trade name: MY-510, manufactured by Huntsman), an inorganic filler (trade name: SC2050 MTO, solid content 70) %, Manufactured by Adamatech), an insulating layer and a multilayer printed circuit board were produced in the same manner as in Example 1 except that a polymer resin composition mixed with 43 g was used.

Example 7
An insulating layer and a multilayer printed circuit board are manufactured in the same manner as in Example 6 except that the alkali-soluble resin synthesized in Production Example 2 is used instead of the alkali-soluble resin synthesized in Production Example 1. did.

Example 8
An insulating layer and a multilayer printed circuit board are manufactured in the same manner as in Example 6 except that the alkali-soluble resin synthesized in Production Example 3 was used instead of the alkali-soluble resin synthesized in Production Example 1. did.

Example 9
An insulating layer and a multilayer printed circuit board are manufactured in the same manner as in Example 6 except that the alkali-soluble resin synthesized in Production Example 4 is used instead of the alkali-soluble resin synthesized in Production Example 1. did.

<Comparative Examples 1 to 3: Production of Insulating Layer and Multilayer Printed Circuit Board>
Comparative Example 1
In step <3>, a 100 μm-thick molding sheet (trade name: LE-T17B, Ajinomoto Co., Inc.) is used instead of the polymer resin layer of the production example, and vacuum lamination is performed at 120 ° C. In step 7>, after thermosetting at 170 ° C. for 1 hour, in step <9>, the surface of the thermosetting polymer resin layer was ground with a grinding machine to expose copper bumps. Except for, an insulating layer was manufactured in the same manner as in Example 1.

  At this time, since the process of exposing the copper bumps proceeds for 10 to 20 minutes per panel in the placement process, it was confirmed that it takes a longer time than the example.

Comparative Example 2
Instead of spraying a 3% sodium hydroxide resist stripping solution at a temperature of 50 ° C. onto the surface of the polymer resin layer in the <9> step, a swerer (manufactured by Atotech, Sweller-p, 40%) is used. Etching (KMnO ₄ 9%, NaOH, 6%) and neutralization (H ₂ SO ₄ , 9%) in this order, desmear treatment, removing about 3 μm depth from the surface of the polymer resin layer to remove the copper bump surface An insulating layer and a multilayer printed circuit board were manufactured in the same manner as in Example 1 except that it was exposed above.

  At this time, since the desmear process for exposing the copper bumps is a continuous arrangement process and proceeds for 5 minutes to 10 minutes per panel only in the etching stage, it takes longer time than the embodiment, and the potassium permanganate It was confirmed that there was a limit that it was difficult to adjust the thickness of the polymer resin layer as well as having to introduce such harmful chemical substances.

Comparative Example 3
The step of primary thermosetting the polymer resin layer in the <7> stage at a temperature of 100 ° C. for 1 hour was omitted, and an insulating layer was produced in the same manner as in Example 1.

  At this time, in the case of Comparative Example 3, there is a technical limit that the polymer resin layer is completely removed within 10 seconds after spraying the sodium hydroxide resist stripping solution and the copper bumps and the lower circuit are exposed. confirmed.

  That is, as in Comparative Example 3, when the curing step for the polymer resin layer does not proceed before the release of the release liquid, it becomes difficult to control the degree to which the polymer resin layer is removed. It was confirmed that it is not suitable for exposing to the surface of the polymer resin layer.

DESCRIPTION OF SYMBOLS 1 Silicon wafer or copper clad laminated board 2 Debonding type temporary fixing adhesive or die bonding film 3 Semiconductor chip 4 Copper bump 5 Polymer resin layer 6 Ultrathin copper foil 7 Carrier copper foil 8 Photosensitive dry film resist 9 Via hole 10 Solder resist <1> to <14> Process progression order

Claims (20)

Sealing the semiconductor element having a metal protrusion on the surface with a polymer resin layer containing an alkali-soluble resin and a thermosetting binder;
Forming a pattern in the polymer resin layer while maintaining a sealed state of the semiconductor element having the metal protrusion formed on the surface;
Primary curing the polymer resin layer on which the pattern is formed;
Etching the surface of the cured polymer resin layer with an aqueous alkaline solution to expose metal protrusions; and secondarily curing the polymer resin layer with the metal protrusions exposed. Production method. The step of forming a pattern on the polymer resin layer includes:
The method for producing an insulating layer according to claim 1, comprising: forming a pattern layer on the polymer resin layer; and alkali-developing the polymer resin layer exposed by the pattern layer. The step of forming a pattern layer on the polymer resin layer includes:
Adhering the opposite surface of the metal layer having the carrier film bonded on one side onto the polymer resin layer;
Forming a patterned photosensitive resin layer on the carrier film;
Removing the carrier film and metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer; and separating and removing the carrier film from the patterned metal layer The manufacturing method of the insulating layer of Claim 2 containing this. In the step of adhering the opposite surface of the metal layer to which the carrier film is bonded to the one surface onto the polymer resin layer containing the alkali-soluble resin and the thermosetting binder,
The method for manufacturing an insulating layer according to claim 3, wherein an adhesive force between the carrier film and the metal layer is smaller than an adhesive force between the polymer resin layer and the metal layer.   The method for producing an insulating layer according to claim 1, wherein the alkali-soluble resin includes at least two cyclic imide functional groups each having an acidic functional group and an amino group. The method for producing an insulating layer according to claim 5, wherein the cyclic imide functional group substituted with the amino group includes a functional group represented by the following chemical formula 1:

In the chemical formula 1, R ₁ is an alkylene group or alkenyl group having 1 to 10 carbon atoms, and “ ^* ” means a bonding point.   The alkali-soluble resin is produced through a reaction of a cyclic unsaturated imide compound; and an amine compound, and at least one of the cyclic unsaturated imide compound and the amine compound includes an acidic functional group substituted at a terminal. Item 2. A method for producing an insulating layer according to Item 1.   The insulating layer according to claim 7, wherein the amine compound includes at least one selected from the group consisting of a carboxylic acid compound substituted with an amino group and a polyfunctional amine compound including two or more amino groups. Production method. The method for producing an insulating layer according to claim 1, wherein the alkali-soluble resin includes at least one repeating unit represented by the following chemical formula 3; and at least one repeating unit represented by the following chemical formula 4:

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

In Formula 4, R ₃ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms,
R ₄ is —H, —OH, —NR ₅ R ₆ , halogen, or an alkyl group having 1 to 20 carbon atoms;
R ₅ and R ₆ may be independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
“ ^* ” Means a connection point. The alkali-soluble resin is produced by a reaction of a polymer containing a repeating unit represented by the following chemical formula 5, an amine represented by the following chemical formula 6, and an amine represented by the following chemical formula 7. The manufacturing method of the insulating layer of 9:

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

In the chemical formulas 8 to 9, R _{2 to} R ₄ are as defined in claim 9.   The said polymer resin layer is a manufacturing method of the insulating layer of Claim 1 containing 1 weight part-150 weight part of thermosetting binders with respect to 100 weight part of alkali-soluble resin. After the step of alkali developing the polymer resin layer exposed by the pattern layer,
The method for manufacturing an insulating layer according to claim 2, wherein 0.1 wt% to 85 wt% remains based on the total weight of the polymer resin layer exposed by the pattern layer.   The said polymer resin layer is a manufacturing method of the insulating layer of Claim 1 which contains an inorganic filler in 100 weight part or more with respect to 100 weight part of total weight of alkali-soluble resin and a thermosetting binder.   The method for manufacturing an insulating layer according to claim 1, wherein the primary curing proceeds at a temperature of 50 ° C. to 150 ° C. for 0.1 hour to 2 hours.   The method for producing an insulating layer according to claim 1, wherein the secondary curing proceeds at a temperature of 150 ° C. to 250 ° C. for 0.1 hour to 10 hours.   A method of manufacturing a multilayer printed circuit board, comprising forming a metal pattern layer on an insulating layer manufactured according to claim 1.   The method for manufacturing a multilayer printed circuit board according to claim 17, wherein the insulating layer includes 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; and depositing a metal on the metal thin film exposed by the photosensitive resin layer pattern; and removing and exposing the photosensitive resin layer. The method of manufacturing a multilayer printed circuit board according to claim 17, comprising removing the metal thin film.   The method of claim 17, wherein the metal pattern layer is connected to a semiconductor element through a metal protrusion.

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