JP2018532270A - Insulating layer manufacturing method and multilayer printed circuit board manufacturing method - Google Patents

Abstract

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

Description

[Cross-reference of related applications]
This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0101420 dated August 9, 2016 and Korean Patent Application No. 10-2017-0097282 dated July 31, 2017. All the contents disclosed in the Korean patent application literature are included as part of this specification.

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

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

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

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

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

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

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

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

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

  On the other hand, with the miniaturization of electronic equipment, printed circuit boards are also becoming smaller and thinner, and the thickness of the printed circuit board is gradually reduced, so that the insulation material used for the board also has high rigidity. It is requested.

  In order to improve the rigidity of the photosensitive insulating material and solder resist, the ratio of the inorganic filler in the resin must be increased. However, in the case of an opaque inorganic filler, there is a problem that light does not pass through, and transparent Even in the case of such an inorganic filler, there is a limit that it becomes difficult to form an opening pattern using light sensitivity by scattering light.

  Therefore, there is a demand for the development of a method for manufacturing an insulating layer having excellent rigidity that can realize a uniform and fine pattern at a low cost while preventing desorption from the interface with the insulating layer or the conductive layer.

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

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

  In the present specification, a step of forming a polymer resin layer containing an alkali-soluble resin and a thermosetting binder on a conductor wiring; a step of forming a photosensitive resin layer on the polymer resin layer; A step of forming a photosensitive resin pattern by exposure and alkali development, and an alkali development of the polymer resin layer exposed by the photosensitive resin pattern; a step of thermosetting the polymer resin layer after the alkali development; and A method for manufacturing an insulating layer is provided, including a step of peeling the photosensitive resin pattern.

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

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

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

  In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but 1 to 40 is preferable. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl and pentyl. N-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl- Propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-and methyl hexyl and the like, but is not limited thereto.

  In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. Examples of the monocyclic aryl group as the aryl group include, but are not limited to, a phenyl group, a biphenyl group, and a terphenyl group. Examples of the polycyclic aryl group include, but are not limited to, naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrycenyl group, and fluorenyl group.

  According to an embodiment of the invention, forming a polymer resin layer containing an alkali-soluble resin and a thermosetting binder on a conductor wiring; forming a photosensitive resin layer on the polymer resin layer; The photosensitive resin layer is exposed to light and alkali developed to form a photosensitive resin pattern, and the polymer resin layer exposed by the photosensitive resin pattern is alkali developed; after the alkali development, the polymer resin layer is thermally cured And a method of manufacturing the insulating layer, including the steps of peeling the photosensitive resin pattern.

  According to the method for manufacturing an insulating layer of the one embodiment, the patterned photosensitive resin layer formed on the alkali-soluble polymer resin layer serves as a mask for an alkaline developer. The portion of the polymer resin layer exposed by the photosensitive resin layer pattern is removed through alkali development, and the portion of the polymer resin layer not exposed by the photosensitive resin layer pattern is protected from the alkaline developer. confirmed.

  Using this, it was confirmed through experiments that a more uniform and fine pattern can be formed quickly and at a lower cost compared to the laser processing process, and that excellent physical properties can be realized in the manufactured final insulating layer. To complete the invention.

  Specifically, a fine and uniform pattern can be formed on the photosensitive resin layer using photosensitive characteristics, and a part of the polymer whose surface is exposed through the pattern formed on the photosensitive resin layer. Only the resin layer is in selective contact with the alkaline developer, and a fine and uniform pattern can be formed as compared with a conventional laser processing step.

  Furthermore, the pattern formation through the development of the photosensitive resin layer and the pattern formation through the development of the polymer resin layer are performed at the same time, so that the fine pattern formed on the photosensitive resin layer is also applied to the polymer resin layer. The pattern forming process is easy and quick, and the efficiency of the process can be improved when applied to mass production.

  In addition, after the thermosetting has proceeded with respect to the polymer resin layer on which the pattern is formed, the photosensitive resin layer pattern is peeled off, and the pattern of the polymer resin layer is maintained as it is. The selective removal with respect to the resin layer can be easily performed.

  Moreover, the final manufactured insulating layer contains a cured product of a thermosetting resin that is a non-photosensitive insulating material, so that a photoinitiator or In some cases, the content of the polymerization inhibitor was greatly reduced or not used at all. This makes it possible to produce an insulating layer having excellent mechanical properties, such as an interface desorption property with an insulating layer or a conductive layer that can be generated by a photoinitiator or a polymerization inhibitor is reduced. In addition, since a non-photosensitive insulating material is included and a large amount of inorganic filler can be introduced regardless of the transparent degree of the inorganic filler, even if a large amount of inorganic filler is introduced, the photosensitivity of the insulating layer is not affected. Sometimes.

  Specifically, the manufacturing method of the insulating layer includes a step of forming a polymer resin layer containing an alkali-soluble resin and a thermosetting binder on a conductor wiring; a step of forming a photosensitive resin layer on the polymer resin layer A step in which the photosensitive resin layer is exposed and alkali developed to form a photosensitive resin pattern, and the polymer resin layer exposed by the photosensitive resin pattern is also alkali developed; after the alkali development, the polymer resin layer Heat-curing; and peeling the photosensitive resin pattern.

  Hereinafter, specific contents will be described for each stage.

  Forming a polymer resin layer containing an alkali-soluble resin and a thermosetting binder on the conductor wiring;

  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 can be present alone or in a state where it is formed on a base material containing a semiconductor material such as a circuit board, a sheet, or a multilayer printed wiring board. Although the example of the method to form on is not specifically limited, For example, it coated in the state which coated the said polymeric resin composition directly on the base material, or apply | coated the polymeric resin composition on the carrier film Thereafter, a method of removing the carrier film or the like can be used.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The 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 150 to 500 parts by weight, or 200 to 500 parts by weight.

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

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

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

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

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

  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. Therefore, 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.

  Forming a photosensitive resin layer on the polymer resin layer;

  The photosensitive resin layer contains a polymer that changes its molecular structure due to the action of light and changes its physical properties. Examples thereof include a photosensitive dry film resist (DFR) and a liquid resist.

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

  An example of a method for forming the photosensitive resin layer on the polymer resin layer is not particularly limited.For example, a method of laminating a film-shaped photosensitive resin such as a photosensitive dry film resist on the polymer resin layer, Alternatively, a method in which the photosensitive resin composition is coated on the polymer resin layer by spraying or dipping and then pressure-bonded can be used.

  The polymer resin layer may have a thickness of 1 μm to 500 μm, 3 μm to 500 μm, 3 μm to 200 μm, 1 μm to 60 μm, or 5 μm to 30 μm. The thickness of the photosensitive resin layer formed on the polymer resin layer may be 1 μm to 500 μm, 3 μm to 500 μm, 3 μm to 200 μm, 1 μm to 60 μm, or 5 μm to 30 μm. If the thickness of the photosensitive resin layer increases too much, the resolution of the polymer resin layer can be reduced.

  The photosensitive resin layer is exposed and alkali developed to form a photosensitive resin pattern, and the polymer resin layer exposed by the photosensitive resin pattern is also alkali developed.

  The photosensitive resin layer can exhibit photosensitivity and alkali solubility. Therefore, the molecular structure is deformed by the exposure process of irradiating the photosensitive resin layer with light, and the resin layer can be etched or removed by the 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 can be selectively exposed through a method such as irradiation with ultraviolet rays or direct imaging using a laser diode as a light source and irradiation with ultraviolet rays. In this case, examples of ultraviolet irradiation conditions include irradiating light quantity of 5 mJ / cm ² to 600 mJ / cm ^2.

  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 alkali developer are not particularly limited. For example, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, and amines can be used. The concentration and temperature can be adjusted and used, and an alkaline developer sold as a product can also be used. The specific amount of the alkali developer used is not particularly limited, but it is necessary to adjust the concentration and temperature so as not to damage the photosensitive resin pattern. For example, sodium carbonate 0.5 to 3 at 25 ° C. to 35 ° C. % 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.

  Therefore, in the method for producing the insulating layer, 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 layer exposed through the pattern formed on the photosensitive resin layer. While substituting the conventional laser-etching process through a process in which only the surface of the substrate is in selective contact with the alkaline developer, it is possible to ensure a precision equal to or higher than this and a higher process economy.

  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, a portion of the polymer resin layer in contact with the alkali developer is dissolved. Can be removed.

  Accordingly, the polymer resin layer exposed by the photosensitive resin pattern means a portion of the polymer resin layer whose surface does not contact the photosensitive resin pattern, and the polymer resin layer exposed by the photosensitive resin pattern is alkalinized. The developing step may include a step in which the alkaline developer used in forming the photosensitive resin pattern passes through the photosensitive resin pattern and comes into contact with the lower polymer resin layer.

  Through the step of alkali developing the polymer resin layer exposed by the photosensitive resin pattern, a polymer resin pattern having the same shape as the photosensitive resin pattern is formed on the polymer resin layer as shown in FIG. be able to. 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.

  Meanwhile, the photosensitive resin layer is exposed and alkali developed to form a photosensitive resin pattern, and the polymer resin layer exposed by the photosensitive resin pattern is exposed by the photosensitive resin pattern after the step of alkali developing. Based on the total weight of the polymer resin layer, 0.1 wt% to 85 wt%, or 0.1 wt% to 50 wt%, or 0.1 wt% to 10 wt% can remain. This is because the alkali-soluble resin contained in the polymer resin layer is removed by the alkali developer, but the thermosetting binder or the inorganic filler having almost no alkali developability remains without being removed.

  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, 20 parts by weight to 100 parts by weight of the thermosetting binder and 100 parts by weight to 600 parts by weight of the inorganic thermosetting resin can be added to 100 parts by weight of the alkali-soluble resin, and the acid value (acid value) on the surface of the inorganic filler can be added. ) May be from 0 mgKOH / g to 5 mgKOH / g, or from 0.01 mgKOH / g to 5 mgKOH / 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 photosensitive resin pattern, a part of the polymer resin layer remains undeveloped, so that the target in the subsequent photosensitive resin pattern removal step Instead of removing the polymer resin pattern, the expansion of the via hole due to the removal of the polymer resin pattern can be prevented while the remaining polymer resin layer is removed.

  After the alkali development, a step of thermosetting the polymer resin layer

  The method for manufacturing the insulating layer may include a step of thermosetting the polymer resin layer after the alkali development. By including the step of thermosetting the polymer resin layer, damage to the polymer resin layer can be minimized during the subsequent photosensitive resin pattern peeling process.

  At this time, the specific thermosetting conditions are not limited, and the process can be carried out by adjusting preferable conditions by the method of peeling the photosensitive resin pattern. For example, when the photosensitive resin pattern is peeled by treating a photoresist stripping solution, the step of thermosetting the polymer resin layer may proceed at a temperature of 60 to 150 ° C. for 5 minutes to 2 hours. When the thermosetting temperature of the polymer resin layer is too low or the thermosetting time is shortened, the polymer resin pattern can be damaged by the peeling solution, and the thermosetting temperature of the polymer resin layer is high, If the time is long, it may be difficult to remove the photosensitive resin pattern with the stripping solution.

  As another example, when the resist mask is removed by a desmear process, the step of thermally curing the polymer resin layer may proceed at a temperature of 150 to 230 ° C. for 1 to 4 hours.

  Peeling off the photosensitive resin pattern

  The method for manufacturing the insulating layer may include a step of peeling the photosensitive resin pattern after the thermosetting. When removing the photosensitive resin pattern, it is preferable to use a method that can remove only the photosensitive resin layer while removing the lower polymer resin layer as much as possible. Further, in order to adjust the shape of the opening pattern or to remove the residue of the polymer resin layer remaining on the bottom surface of the opening pattern, a part of the polymer resin layer may be removed.

  That is, in the step of peeling the photosensitive resin pattern, the ratio of removing the polymer resin layer is 10% by weight or less, or 1% by weight or less, or 0.01% by weight or less with respect to the weight of the whole polymer resin layer. It is possible. The ratio at which the polymer resin layer is removed is 0.01% by weight or less with respect to the weight of the entire polymer resin layer. It means that the resin layer is not removed at all.

  As a specific example of the method for peeling off the photosensitive resin pattern, a photoresist stripping solution can be processed, a desmear process, plasma etching, or the like can be performed.

  An example of a stripping method using a photoresist stripping solution is not particularly limited. For example, it can be used by adjusting the concentration and temperature of an alkaline aqueous solution such as potassium hydroxide or sodium hydroxide, and Atotech Resistrip. Commercially available products such as ORC-731, ORC-723K, ORC-740, and SLF-6000 manufactured by Orchem can also be used. The specific amount of the photoresist stripping solution is not particularly limited, but it is necessary to adjust the concentration and temperature so as not to damage the lower polymer resin layer pattern. For example, sodium hydroxide 1 at 25 ° C. to 60 ° C. A 5% aqueous solution can be used.

  The example of the peeling method using a desmear process is not specifically limited, For example, as a desmear process chemical | medical agent of Atotech, Securiganth E, Securigan HP, Securiganth BLG, Securigan MV SWELLER, SecurSweth WelSWE Chemicals, Securiganth P500, Securigan MV ETCHP, Permanganate Chemicals such as Securiganth SAP ETCHP, Securiganth E Reduction Cleaner, Securigan HP Redaction Cleaner, Securgan HP Redaction Cleaner Reducing agent chemicals such as uriganth MV Reduction Cleaner, Securiganth SAP Reduction Cleaner, and desmear process chemicals of Orchem, such as SWC 40 ORC such as ORC-310A, ORC-315A, ORC-315H, ORC-312, Commercially available products such as permanganic acid chemicals such as ORC-370, ORC-372 and other reducing agent chemicals can be used for each process condition.

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

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

  The insulating layer can be used as an interlayer insulating material for a multilayer printed circuit board, and can include an alkali-soluble resin and a thermoset of a thermosetting binder. The content regarding the alkali-soluble resin and the thermosetting binder includes the content described above in the embodiment.

  The step of forming a metal substrate having a pattern formed on the insulating layer is a micro circuit pattern forming process known as Semi Additive Process (SAP) in the industry, wherein the SAP process is performed on the insulating layer. This means that a fine circuit pattern is formed in a state in which there is nothing.

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

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

  On the other hand, specific examples of the wet deposition process include electroless plating of various metals, and 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.

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

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

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

  Therefore, the number of stacked layers included in the multilayer printed circuit board manufactured by the 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.

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

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

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

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

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

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

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

<Example>
<Example 1: Production of insulating layer>
Referring to the contents of FIG. 1 below, 16 g of the alkali-soluble resin synthesized in Production Example 1, 5 g of MY-510 (manufactured by Huntsman) as a thermosetting binder, SC2050 MTO (solid content 70%, A polymer resin composition mixed with 35 g (manufactured by Adamatech) was applied to a PET film and dried to produce a polymer resin layer 1 having a thickness of 15 μm. Then, the polymer resin layer 1 was vacuum laminated at 85 ° C. on the circuit board on which the copper line 2 was formed on the copper foil laminate 3, and the PET film was removed. A photosensitive dry film resist (KL1015; manufactured by Kolon Industry Co., Ltd.) 4 having a thickness of 15 μm was laminated on the polymer resin layer 1 at 110 ° C.

A circular negative photomask having a diameter of 30 μm is brought into contact with the photosensitive dry film resist 4 and irradiated with ultraviolet rays (light amount of 25 mJ / cm ² ). The dry film resist 4 and the polymer resin layer 1 were sequentially developed.

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

  Thereafter, after thermosetting at a temperature of 100 ° C. for 1 hour, the residue and the photosensitive dry film resist 4 are removed using a 3% sodium hydroxide resist stripping solution at a temperature of 50 ° C., and then at a temperature of 200 ° C. for 1 hour. The process of thermosetting was further advanced to manufacture an insulating layer having a via hole diameter shown in Table 1 below.

<Example 2: Production of multilayer printed circuit board>
Referring to the contents of FIG. 2 below, titanium (Ti) is formed through a sputtering method while supplying a mixed gas of argon and oxygen to the upper surface of the insulating layer 7 and the side surface of the via hole 5 manufactured in Example 1 by vapor deposition equipment. A seed layer 8 was formed by evaporating metal to a thickness of 50 nm and copper (Cu) metal to a thickness of 0.5 μm.

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

<Example 3: Production of insulating layer>
During production of the polymer resin layer, 16 g of the alkali-soluble resin synthesized in Production Example 3, 6 g of MY-510 (manufactured by Huntsman) as a thermosetting binder, and SC2050 MTO (manufactured by Adamate) as an inorganic filler. An insulating layer having a via hole diameter shown in Table 1 below was produced in the same manner as in Example 1 except that a polymer resin composition mixed with 35 g was used.

<Example 4: Production of multilayer printed circuit board>
A multilayer printed circuit board was manufactured in the same manner as in Example 2 except that the insulating layer manufactured in Example 3 was used instead of the insulating layer manufactured in Example 1.

<Example 5: Production of insulating layer>
At the time of production of the polymer resin layer, 16 g of the alkali-soluble resin synthesized in Production Example 1, 5 g of MY-510 (manufactured by Huntsman) as a thermosetting binder, SC2050 MTO (manufactured by Adamate Co., Ltd.) as an inorganic filler An insulating layer having a via hole diameter shown in Table 1 below was manufactured in the same manner as in Example 1 except that the polymer resin composition mixed with 43 g was used.

<Example 6: Production of insulating layer>
During production of the polymer resin layer, 16 g of the alkali-soluble resin synthesized in Production Example 2, 5 g of MY-510 (manufactured by Huntsman) as a thermosetting binder, and SC2050 MTO (manufactured by Adamate) as an inorganic filler An insulating layer having a via hole diameter shown in Table 1 below was manufactured in the same manner as in Example 1 except that the polymer resin composition mixed with 43 g was used.

<Example 7: Production of insulating layer>
During the production of the polymer resin layer, 16 g of the alkali-soluble resin synthesized in Production Example 3, 5 g of MY-510 (manufactured by Huntsman) as a thermosetting binder, and SC2050 MTO (manufactured by Adamate Co., Ltd.) as an inorganic filler An insulating layer having a via hole diameter shown in Table 1 below was manufactured in the same manner as in Example 1 except that the polymer resin composition mixed with 43 g was used.

<Example 8: Production of insulating layer>
During production of the polymer resin layer, 16 g of the alkali-soluble resin synthesized in Production Example 4, 5 g of MY-510 (manufactured by Huntsman) as a thermosetting binder, and SC2050 MTO (manufactured by Adamate) as the inorganic filler. An insulating layer having a via hole diameter shown in Table 1 below was manufactured in the same manner as in Example 1 except that the polymer resin composition mixed with 43 g was used.

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

Thereafter, the polymer resin layer was thermally cured at a temperature of 200 ° C. for 1 hour and then etched using a CO ₂ laser drill to produce an insulating layer having a via hole diameter shown in Table 1 below.

<Comparative Example 2: Production of insulating layer>
30 g of CCR-1291H (manufactured by Nippon Kayaku Co., Ltd.) as the acid-modified acrylate resin, 5 g of TMPTA (manufactured by ETNIS) as the polyfunctional acrylate monomer, 2 g of Irgacure TPO-L (manufactured by BASF) as the photoinitiator, polyfunctional epoxy A photosensitive resin composition in which 6 g of YDCN-500-8P (manufactured by Kokuto Chemical Co., Ltd.) and 0.2 g of 2E4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a thermosetting catalyst was mixed was applied onto a circuit board and dried. Thus, a photosensitive resin layer was produced.

A circular negative photomask having a diameter of 30 μm is brought into contact with the photosensitive resin layer, irradiated with ultraviolet rays (amount of light of 400 mJ / cm ² ), and then developed through a 1% sodium carbonate developer at 30 ° C. A layer was produced.

<Comparative Example 3: Production of multilayer printed circuit board>
A multilayer printed circuit board was manufactured in the same manner as in Example 2 except that the insulating layer manufactured in Comparative Example 2 was used instead of the insulating layer manufactured in Example 1.

<Comparative Example 4: Production of insulating layer>
As in Example 5, 16 g of the alkali-soluble resin synthesized in Production Example 1, 6 g of MY-510 (manufactured by Huntsman) as a thermosetting binder, and 43 g of SC2050 MTO (solid content 70%, manufactured by Adamatech) as an inorganic filler The polymer resin composition mixed with was applied to a PET film and dried to produce a polymer resin layer 1 having a thickness of 15 μm. Then, the polymer resin layer 1 was vacuum laminated at 85 ° C. on the circuit board on which the copper line 2 was formed on the copper foil laminate 3, and the PET film was removed.

Thereafter, the polymer resin layer was thermally cured at a temperature of 200 ° C. for 1 hour and then etched using a CO ₂ laser drill to produce an insulating layer having a via hole diameter shown in Table 1 below.

<Comparative Example 5: Production of insulating layer>
As in Example 7, 16 g of the alkali-soluble resin synthesized in Production Example 3, 5 g of MY-510 (manufactured by Huntsman) as a thermosetting binder, 43 g of SC2050 MTO (solid content 70%, manufactured by Adamatech) as an inorganic filler The polymer resin composition mixed with was applied to a PET film and dried to produce a polymer resin layer 1 having a thickness of 15 μm. Then, the polymer resin layer 1 was vacuum laminated at 85 ° C. on the circuit board on which the copper line 2 was formed on the copper foil laminate 3, and the PET film was removed.

Thereafter, the polymer resin layer was thermally cured at a temperature of 200 ° C. for 1 hour and then etched using a CO ₂ laser drill to produce an insulating layer having a via hole diameter shown in Table 1 below.

<Comparative Example 6: Production of insulating layer>
30 g of CCR-1291H (manufactured by Nippon Kayaku Co., Ltd.) as the acid-modified acrylate resin, 5 g of TMPTA (manufactured by ETNIS) as the polyfunctional acrylate monomer, 2 g of Irgacure TPO-L (manufactured by BASF) as the photoinitiator, polyfunctional epoxy YDCN-500-8P (manufactured by Kokuto Chemical Co., Ltd.) 6 g, thermosetting catalyst 2E4MZ (manufactured by Shikoku Chemicals Co., Ltd.) 0.2 g, inorganic filler SC2050 MTO (solid content 70%, manufactured by Adamatech) 49 g The photosensitive resin composition mixed with was applied onto a circuit board and dried to produce a photosensitive resin layer.

A circular negative photomask having a diameter of 30 μm is brought into contact with the photosensitive resin layer, irradiated with ultraviolet rays (amount of light of 400 mJ / cm ² ), and then developed through a 1% sodium carbonate developer at 30 ° C. A layer was produced.

<Experimental example: Measurement of physical properties of insulating layers obtained in Examples and Comparative Examples>
The physical properties of the insulating layers obtained in the examples and comparative examples were measured by the following methods, and the results are shown in Table 1.

1. Diameter of Via Hole The diameter of the upper opening surface (via hole) was measured through an optical microscope for the insulating layers obtained in Examples 1, 3, 5-8 and Comparative Examples 1, 2, 4, 5, and 6.

2. Metal adhesion due to moisture absorption The multilayer printed circuit boards obtained in Examples 2 and 4 and Comparative Example 3 were allowed to stand at 135 ° C. and 85% moisture absorption for 48 hours, and then according to the IPC-TM-650 standard. The metal peel strength was measured, and the metal adhesion strength was determined from this.

3. HAST (Highly Accelerated Temp & Humidity Stress Test) Characteristics HAST characteristics were confirmed for the multilayer printed circuit boards obtained in Examples 2 and 4 and Comparative Example 3 according to JESD22-A101 standards. Specifically, a voltage of 3 V is applied to a specimen circuit board having a width, interval, and thickness of 50 μm, 50 μm, and 12 μm, respectively, and the specimen circuit board is left for 168 hours. The above abnormality was confirmed.
OK: No abnormality is observed in the coating appearance NG: Water bubbles or peeling is observed in the coating

As shown in Table 1, in the case of the insulating layers of Comparative Examples 1, 4, and 5 in which the via hole is formed in the thermosetting resin layer by etching using a CO ₂ laser drill, the diameter of the via hole is 62 μm or 60 μm. On the other hand, the diameter of the via hole included in the insulating layer manufactured in Examples 1, 3, and 5-8 is reduced to 46 μm or less, and a finer pattern can be realized than in the case of the above example. Was confirmed.

  On the other hand, in the insulating layer manufactured in Comparative Example 6, light is scattered due to the refractive index difference between the inorganic filler and the resin, and a fine via hole is not formed by exposure and development of the photosensitive resin layer, thereby realizing a fine pattern. It was confirmed that it was impossible.

  Further, in the case of the multilayer printed circuit board of Comparative Example 3 manufactured through exposure and development of the resin composition of Comparative Example 2 containing a photoinitiator, the metal adhesion was measured to 0 kgf / cm, and the insulating layer and the conductive layer It was confirmed that interfacial desorption occurred between and the HAST characteristics.

  On the other hand, in the case of the multilayer printed circuit board of Example 2 manufactured through thermosetting without the photoinitiator, the metal adhesion force is measured as high as 0.3 kgf / cm, and the gap between the insulating layer and the conductive layer is measured. It was confirmed that the interfacial bonding was maintained and excellent HAST characteristics were exhibited.

  In addition, when the insulating layers obtained in Examples 1 and 3 were compared with the insulating layers obtained in Examples 5 and 7, the resin component 100 parts by weight was more than 200 parts by weight. In the case of the insulating layers obtained in Examples 5 and 7 to which an inorganic filler was added, compared to the insulating layer obtained in Example 1 in which the content of the inorganic filler relative to 100 parts by weight of the resin component is less than 200 parts by weight, It was confirmed that a finer via hole diameter could be secured.

  This is because when the content of the inorganic filler relative to the resin is increased as in Examples 5 to 8, the inorganic filler remains without being removed during alkali development for forming the insulating layer, and a sufficient residue is formed. It is understood that this is due to the suppression of via hole diameter expansion during subsequent resist stripping.

1: Polymer resin layer 2: Copper line 3: Copper foil laminate 4: Photosensitive dry film resist (DFR)
5: Via hole 6: Metal layer 7: Insulating layer 8: Seed layer 9: Photosensitive resin pattern 10: Metal substrate
<1> to <6>: Process progress order

Claims (20)

Forming a polymer resin layer containing an alkali-soluble resin and a thermosetting binder on the conductor wiring;
Forming a photosensitive resin layer on the polymer resin layer;
Exposure and alkali development of the photosensitive resin layer to form a photosensitive resin pattern, and the polymer resin layer exposed by the photosensitive resin pattern is alkali-developed;
A method for producing an insulating layer, comprising: a step of thermally curing the polymer resin layer after the alkali development; and a step of peeling the photosensitive resin pattern.   The method for producing an insulating layer according to claim 1, wherein the alkali-soluble resin includes at least one acidic functional group; and at least one cyclic imide functional group substituted with an amino group. The method for producing an insulating layer according to claim 2, wherein the cyclic imide functional group substituted with the amino group includes a functional group represented by the following chemical formula 1:

In the chemical formula 1, R ₁ is an alkylene group or alkenyl group having 1 to 10 carbon atoms, and “ ^* ” means a point of attachment.   The alkali-soluble resin is produced through a reaction of a cyclic unsaturated imide compound; and an amine compound, and at least one of the cyclic unsaturated imide compound and the amine compound includes an acidic functional group substituted at a terminal. Item 3. A method for producing an insulating layer according to Item 2.   5. The insulating layer according to claim 4, wherein the amine compound includes one or more selected from the group consisting of a carboxylic acid compound substituted with an amino group, and a polyfunctional amine compound containing two or more amino groups. Production method. The method for producing an insulating layer according to claim 1, wherein the alkali-soluble resin includes at least one repeating unit represented by the following chemical formula 3; and at least one repeating unit represented by the following chemical formula 4:

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

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

In the chemical formulas 5 to 7, R _{2 to} R ₄ are as defined in claim 6 and “ ^* ” means a point of attachment. The method for producing an insulating layer according to claim 6, 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 6.   2. The method for manufacturing an insulating layer according to claim 1, wherein the alkali-soluble resin has an acid value determined by KOH titration of 50 mgKOH / g to 250 mgKOH / g.   The method for producing an insulating layer according to claim 1, wherein the polymer resin layer includes 1 part by weight to 150 parts by weight of a thermosetting binder with respect to 100 parts by weight of the alkali-soluble resin.   The thermosetting binder comprises at least one functional group selected from the group consisting of an oxetanyl group, a cyclic ether group, a cyclic thioether group, a cyano group, a maleimide group, and a benzoxazine group, and an epoxy group. The manufacturing method of the insulating layer of description.   The method for producing an insulating layer according to claim 1, wherein 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 entire polymer resin layer. The photosensitive resin layer is exposed and alkali developed to form a photosensitive resin pattern, and the polymer resin layer exposed by the photosensitive resin pattern is also alkali developed,
The method for manufacturing an insulating layer according to claim 1, wherein a ratio at which the photosensitive resin pattern is removed is 0.01% by weight or less with respect to a weight of the entire photosensitive resin pattern. After the photosensitive resin layer is exposed and alkali developed to form a photosensitive resin pattern, and the polymer resin layer exposed by the photosensitive resin pattern is also alkali developed,
The method for manufacturing an insulating layer according to claim 1, wherein 0.1 wt% to 85 wt% remains based on the total weight of the polymer resin layer exposed by the photosensitive resin pattern. In the step of peeling the photosensitive resin pattern,
The method for producing an insulating layer according to claim 1, wherein a ratio at which the polymer resin layer is removed is 10% by weight or less based on the weight of the entire polymer resin layer.   The said polymeric resin layer is a manufacturing method of the insulating layer of Claim 1 containing 100 weight part or more of inorganic fillers 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 polymer resin layer or the photosensitive resin layer has a thickness of 1 μm to 500 μm.   A method for manufacturing a multilayer printed circuit board, comprising: forming a metal substrate having a pattern formed on an insulating layer manufactured by the method according to claim 1.   The method for manufacturing a multilayer printed circuit board according to claim 18, wherein the insulating layer includes a thermosetting product of an alkali-soluble resin and a thermosetting binder. Forming a metal substrate having a pattern formed on the insulating layer;
Forming a metal foil film on the insulating layer;
Forming a photosensitive resin layer having a pattern formed on the metal foil film; and depositing a metal on the metal foil film exposed by the photosensitive resin layer pattern; and removing the photosensitive resin layer. The method of manufacturing a multilayer printed circuit board according to claim 18, comprising removing the exposed metal foil film.

Images