KR102040224B1 - Method for manufacturing insulating film and multilayered printed circuit board - Google Patents

Abstract

The present invention, while improving the efficiency in terms of cost and productivity, it is possible to implement a uniform and fine pattern, a multilayer printed circuit using an insulating layer manufacturing method and an insulating layer obtained from the insulating layer manufacturing method to ensure excellent mechanical properties It relates to a substrate manufacturing method.

Description

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

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

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

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

Build-up PCBs used in these application areas must form via holes for connection between layers. Via holes, which correspond to interlayer electrical connection passages of multilayer printed circuit boards, are conventionally used as mechanical drills. As a result of the miniaturization of the circuit due to the miniaturization of the circuit, the laser processing method appeared as an alternative due to the increase in the processing cost and the limitation of the microhole processing.

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

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

Such a photosensitive insulating material or solder resist may be divided into a case where a developer different from that of using a sodium carbonate developer for pattern formation is used. In the case of using other developers, photosensitive insulating materials or solder resists are difficult to apply in actual processes due to environmental and cost reasons.

On the other hand, the use of sodium carbonate developer has an environmentally friendly advantage. In this case, acid-modified acrylate resins including a plurality of carboxylic acids and acrylate groups are used to impart photosensitivity. Since most acrylate groups and carboxyl groups are linked by ester bonds, polymerization inhibitors or the like are used to polymerize to a desired shape. It will include, in order to cause a radical reaction by ultraviolet irradiation will also include a photoinitiator and the like.

However, the polymerization inhibitor or photoinitiator may diffuse out of the resin under high temperature conditions, causing interfacial 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 and decreases the crosslinking density of the resin, thereby increasing the moisture absorption rate of the resin. When the moisture absorption rate is high, the polymerization inhibitor or the photoinitiator may be used at high temperature. It is possible to generate interfacial desorption with the insulating layer or the conductive layer after the semiconductor package process or after the conversion out of the resin, there was a limit to deteriorate HAST characteristics.

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

In order to improve the rigidity of the photosensitive insulating material or the solder resist, the ratio of the inorganic filler in the resin should be increased. However, in the case of the opaque inorganic filler, there is a problem that light does not pass. There was a limit that makes it difficult to form the opening pattern by using.

Accordingly, while preventing interfacial desorption with the insulating layer or the conductive layer, it is possible to implement a uniform and fine pattern at a low cost and to develop an insulating layer manufacturing method excellent in rigidity.

The present invention is to provide a method for producing an insulating layer that can be implemented in a uniform and fine pattern, while ensuring the efficiency in terms of cost and productivity, and excellent mechanical properties.

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

In the present specification, forming a polymer resin layer including an alkali-soluble resin and a thermosetting binder on the conductor wiring; Forming a photosensitive resin layer on the polymer resin layer; Exposing and alkali developing the photosensitive resin layer to form a photosensitive resin pattern, and at the same time, alkali developing the polymer resin layer exposed by the photosensitive resin pattern; Heat curing the polymer resin layer after the alkali development; And it is provided with an insulating layer manufacturing method comprising the step of peeling the photosensitive resin pattern.

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

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

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 chain, carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary 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, 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-methylhexyl, 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 an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, but may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto. The polycyclic aryl group may be naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

According to one embodiment of the invention, forming a polymer resin layer including an alkali-soluble resin and a thermosetting binder on the conductor wiring; Forming a photosensitive resin layer on the polymer resin layer; Exposing and alkali developing the photosensitive resin layer to form a photosensitive resin pattern, and at the same time, alkali developing the polymer resin layer exposed by the photosensitive resin pattern; Heat curing the polymer resin layer after the alkali development; And it may be provided an insulating layer manufacturing method comprising the step of peeling the photosensitive resin pattern.

According to the method of manufacturing the insulating layer of the present embodiment, the patterned photosensitive resin layer formed on the polymer resin layer having alkali solubility serves as a mask of the alkali developer, thereby exposing the polymer exposed by the photosensitive resin layer pattern. It was confirmed that the resin layer portion was removed through alkali development, and the polymer resin layer portion not exposed by the photosensitive resin layer pattern was protected from the alkaline developer.

By using this, more uniform and fine patterns can be quickly formed at a lower cost than the laser processing process, and the final insulating layer produced through experiments confirmed that the excellent physical properties through experiments and completed the invention.

Specifically, a fine and uniform pattern may be formed on the photosensitive resin layer by using photosensitive characteristics, and only a part of the polymer resin layer having a surface exposed through the pattern formed on the photosensitive resin layer selectively contacts the alkali developer. It is possible to form a fine and uniform pattern compared to the conventional laser processing process.

Furthermore, as the pattern formation through the development of the photosensitive resin layer and the pattern formation through the development of the polymer resin layer proceed simultaneously, the fine patterns formed on the photosensitive resin layer may be formed in the polymer resin layer in the same way, and the pattern formation process may be performed. It is easy and fast to improve the efficiency of the process when applied to mass production.

In addition, after the thermosetting of the patterned polymer resin layer is first performed, peeling is performed on the photosensitive resin layer pattern to easily remove the photosensitive resin layer while maintaining the pattern of the polymer resin layer. Can proceed.

In addition, since the final manufactured insulating layer includes a cured product of a thermosetting resin, which is a non-photosensitive insulating material, the content of the photoinitiator or polymerization inhibitor is greatly reduced or not used at all compared to the manufacturing of the insulating layer using a conventional photosensitive insulating material. Could. As a result, an insulating layer having excellent mechanical properties, such as reduced interfacial desorption with an insulating layer or a conductive layer which may be generated by a photoinitiator or a polymerization inhibitor, can be produced. In addition, since a non-photosensitive insulating material is included, a large amount of inorganic filler may be introduced regardless of the degree of transparency of the inorganic filler, so that a large amount of the inorganic filler may not affect the photosensitivity of the insulating layer.

Specifically, the insulating layer manufacturing method comprises the steps of forming a polymer resin layer including an alkali-soluble resin and a thermosetting binder on the conductor wiring; Forming a photosensitive resin layer on the polymer resin layer; Exposing and alkali developing the photosensitive resin layer to form a photosensitive resin pattern, and at the same time, alkali developing the polymer resin layer exposed by the photosensitive resin pattern; Heat curing the polymer resin layer after the alkali development; And peeling the photosensitive resin pattern.

Hereinafter, specific contents will be described in each step.

On the conductor wiring Alkali  Forming a polymer resin layer comprising a soluble resin and a thermosetting binder

The polymer resin layer means a film formed through drying of a polymer resin composition including an alkali-soluble resin and a thermosetting binder.

The polymer resin layer may exist alone or in a state formed on a substrate including a semiconductor material such as a circuit board, a sheet, a multilayer printed wiring board, and an example of a method of forming the polymer resin layer on a substrate is greatly limited. However, for example, a method of directly coating the polymer resin composition on the substrate or in a state in which the polymer resin composition is applied on the carrier film may be used, and then a method of removing the carrier film may be used.

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

The polymer resin layer may include 1 part by weight to 150 parts by weight, or 10 parts by weight to 100 parts by weight, or 20 parts by weight to 50 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. When the content of the thermosetting binder is excessively high, the developability of the polymer resin layer may be lowered, and the strength may be lowered. On the contrary, when the content of the thermosetting binder is too low, not only the polymer resin layer is excessively developed, but also uniformity may be reduced during coating.

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

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

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

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

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

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

As a specific example of the said polyfunctional epoxy compound, bisphenol-A epoxy resin, hydrogenated bisphenol-A epoxy resin, brominated bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, novolak-type epoxy resin, for example , Phenol novolak type epoxy resin, cresol novolak type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolak type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, chelate type epoxy resin, glyc Oxal type epoxy resin, amino group containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenolic epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoyl ethane resin, silicone modified epoxy resin and (epsilon) -caprolactone modified epoxy resins. In addition, in order to impart flame retardancy, those in which atoms such as phosphorus are introduced into the structure may be used. By thermosetting these epoxy resins, characteristics, such as adhesiveness of a cured film, solder heat resistance, and electroless plating resistance, are improved.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [( 3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methylacrylic Latex, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or these In addition to polyfunctional oxetanes such as oligomers and copolymers, oxetane alcohols and novolac resins, poly (p-hydroxystyrenes), cardo-type bisphenols, charixarenes, carlixresolecinarenes, or silses And etherates with resins having hydroxy groups such as quoxane. In addition, the copolymer etc. of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate are mentioned.

Examples of the multifunctional cyanate ester compound include bisphenol A type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol M type cyanate ester resin, Novolac cyanate ester resins, phenol novolac cyanate ester resins, cresol novolac cyanate ester resins, novolac cyanate ester resins of bisphenol A, biphenol cyanate ester resins or oligomers or air thereof Coalescence, etc. are mentioned.

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

Examples of the multifunctional benzoxazine compounds include bisphenol A benzoxazine resins, bisphenol F benzoxazine resins, phenolphthalein benzoxazine resins, thiodiphenol type benzoxazine resins, dicyclopentadiene benzoxazine resins, and 3,3 '. -(Methylene-1,4-diphenylene) bis (3,4-dihydro-2H-1,3-benzoxazine (3,3 '-(methylene-1,4-diphenylene) bis (3,4- dihydro-2H-1,3-benzoxazine) resin and the like.

More specific examples of the multifunctional resin compound include YDCN-500-80P manufactured by Kukdo Chemical Co., Ltd., phenol novolak type cyanide ssene resin PT-30S from Lonza, phenylmethane type maleimide resin BMI-2300 from Daiwa Corporation, Pd type benzoxazine resin etc. are mentioned.

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

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

In addition, as the cyclic imide functional group is present in a large number in the alkali-soluble resin, the polarity is increased by the carbonyl group and the tertiary amine group included in the cyclic imide functional group, thereby increasing the interfacial adhesion of the alkali-soluble resin. Accordingly, the polymer resin layer containing the alkali-soluble resin may have high interfacial adhesion with the metal layer stacked on the upper portion, and specifically, may have higher adhesion than the interfacial adhesion between the carrier film and the metal layer laminated on the upper metal layer. Thus, as will be described later, physical peeling between the carrier film and the metal layer may be enabled.

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

[Formula 1]

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

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

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

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

[Formula 2]

In Formula 2, "*" means a bonding point.

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

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

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

The arylene group is a divalent functional group derived from arene, and may be, for example, a phenyl group or a naphthyl group as a cyclic type. One or more hydrogen atoms included in the arylene group may be substituted with another substituent, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and 6 carbon atoms Aryl group of 12 to 12 carbon atoms, heteroaryl group of 2 to 12 carbon atoms, arylalkyl group of 6 to 12 carbon atoms, halogen atom, cyano group, amino group, amidino group, nitro group, amide group, carbonyl group, hydroxy group, sulfonyl group, carba A mate group, a C1-C10 alkoxy group, etc. are mentioned.

Examples of the method for producing the alkali-soluble resin are not particularly limited, for example, a cyclic unsaturated imide compound; And amine compounds. At this time, the cyclic unsaturated imide compound; And at least one of the amine compounds may include an acidic functional group substituted at the terminal. That is, an acidic functional group may be substituted at the terminal of the cyclic unsaturated imide compound, the amine compound, or both of these two compounds. Details of the acidic functional group are as described above.

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

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

Examples of the weight ratio for reacting the cyclic unsaturated imide compound and the amine compound are not particularly limited. For example, 10 to 80 parts by weight of the amine compound, based on 100 parts by weight of the cyclic unsaturated imide compound, Or it may be reacted by mixing in 30 to 60 parts by weight.

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

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

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

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

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

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

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

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

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

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

In addition, the polyfunctional amine compound including two or more amino groups is a compound containing two or more amino groups (-NH ₂ ) in the molecule, and may include all aliphatic, alicyclic or aromatic polyfunctional amines depending on the type of hydrocarbon bonded to the amino group. have. Through the polyfunctional amine compound including two or more amino groups, flexibility, toughness, copper adhesion, etc. of the alkali-soluble resin may be improved.

Specific examples of the polyfunctional amine compound containing two or more amino groups include 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis (aminomethyl) -cyclohexane, and 1,4-bis (Aminomethyl) -cyclohexane, bis (aminomethyl) -norbornene, octahydro-4,7-methanoindene-1 (2), 5 (6) -dimethanamine, 4,4'-methylenebis ( Cyclohexylamine), 4,4'-methylenebis (2-methylcyclohexylamine), isophoronediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,5-dimethyl-1,4 -Phenylenediamine, 2,3,5,6, -tetramethyl-1,4-phenylenediamine, 2,4,5,6-tetrafluoro-1,3-phenylenediamine, 2,3,5 , 6-tetrafluoro-1,4-phenylenediamine, 4,6-diaminoresosinol, 2,5-diamino-1,4-benzenedithiol, 3-aminobenzylamine, 4-aminobenzyl Amines, m-xylenediamine, p-xylenediamine, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 2,6-diaminoanthraquinone, m-tolidine, o-tolidine, 3 , 3 ', 5,5'-tetramethylbenzidine (TMB), o-diazinidine, 4,4'-methylenebis (2-chloroaniline), 3,3'-diaminobenzidine, 2,2'- Bis (trifluoromethyl) -benzidine, 4,4'-diaminooctafluorobiphenyl, 4,4'-diamino-p-terphenyl, 3,3'-diaminodiphenylmethane, 3,4 ' -Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-methylenebis (2-ethyl-6- Methylaniline), 4,4'-methylenebis (2,6-diethylaniline), 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-ethylenedianiline, 4,4'-diamino-2,2'-dimethylbibenzyl, 2,2'-bis (3-amino-4-hydroxyphenyl) propane, 2,2'-bis (3-aminophenyl) -hexa Fluoropropane, 2,2'-bis (4-aminophenyl) -hexafluoropropane, 2,2'-bis (3-amino-4-methylphenyl) -hexafluoropropane, 2,2'-bis ( 3-amino-4-hydroxyphenyl) -hexafluoropropane, α, α'-bis (4-aminophenyl) -1,4- Diisopropylbenzene, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,1'-bis (4-aminophenyl) -cyclohexane, 9,9'-bis (4 -Aminophenyl) -fluorene, 9,9'-bis (4-amino-3-chlorophenyl) fluorene, 9,9'-bis (4-amino-3-fluorophenyl) fluorene, 9,9 '-Bis (4-amino-3-methylphenyl) fluorene, 3,4'-diaminodiphenylether, 4,4'-diaminodiphenylether, 1,3-bis (3-aminophenoxy ) -Benzene, 1,3-bis (4-aminophenoxy) -benzene, 1,4-bis (4-aminophenoxy) -benzene, 1,4-bis (4-amino-2-trifluoromethyl Phenoxy) -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-amino Phenyl) sulfone, bis (3-amino-4-hydroxy) sulfone, bis [4- (3-aminophenoxy) -phen ] Sulfone, bis [4- (4-aminophenoxy) -phenyl] sulfone, o-tolidine sulfone, 3,6-diaminocarbazole, 1,3,5-tris (4-aminophenyl) -benzene, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, 4,4'-diaminobenzanilide, 2- (3-aminophenyl) -5-aminobenzimidazole, 2- (4-aminophenyl ) -5-aminobenzoxazole, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 4,6-diaminoresosinol, 2,3,5,6-pyridinetetraamine, polyfunctional amines including siloxane structure of Shin-Etsu Silicone (PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008 , X-22-1660B-3, X-22-9409), polyfunctional amines including Dow Corning siloxane structure (Dow Corning 3055), polyfunctional amines including polyether structure (Huntsman, BASF), etc. Can be.

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

[Formula 3]

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

[Formula 4]

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

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

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

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

[Formula 5]

[Formula 6]

[Formula 7]

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

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

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

[Formula 8]

[Formula 9]

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

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

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

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

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

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

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

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

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

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

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

Although the example of the said phenol group containing resin is not restrict | limited greatly, For example, novolak resins, such as a phenol novolak resin, cresol novolak resin, bisphenol F (BPF) novolak resin, or 4,4 '-(1- (4 -(2- (4-hydroxyphenyl) propan-2-yl) phenyl) ethane-1,1-diyl) diphenol [4,4 '-(1- (4- (2- (4-Hydroxyphenyl) bisphenol A resins such as propan-2-yl) phenyl) ethane-1,1-diyl) diphenol] may be used alone or in combination.

The alkali soluble resin may have an acid value obtained by KOH titration of 50 mgKOH / g to 250 mgKOH / g, or 70 mgKOH / g to 200 mgKOH / g. Although the example of the method of measuring the acid value of the said alkali-soluble resin is not restrict | limited very much, For example, the following method can be used. Prepare a KOH solution (solvent: methanol) at a concentration of 0.1 N as a base solvent, and alpha-naphtholbenzein (pH: 0.8 to 8.2 yellow, 10.0 blue green) as an indicator. Was prepared. Subsequently, about 1 to 2 g of an alkali soluble resin as a sample was taken, dissolved in 50 g of dimethylformaldehyde (DMF) solvent, and then added with a marker, followed by titration with a base solvent. The acid value was determined in mg KOH / g by the amount of the base solvent used at the time of completion of the titration.

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

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

The thermosetting catalyst serves to promote thermosetting of the thermosetting binder. As said thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine compound; Hydrazine compounds such as adipic dihydrazide and sebacic acid dihydrazide; Phosphorus compounds, such as a triphenylphosphine, etc. are mentioned. Moreover, as what is marketed, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are brand names of an imidazole compound) by the Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N and UCAT3502T by San Apro Corporation (All are brand names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATS A102, U-CAT5002 (both bicyclic amidine compounds and salts thereof), and the like. It is not specifically limited to these, It may be the thing which accelerates reaction of the thermosetting catalyst of an epoxy resin or an oxetane compound, or an epoxy group and / or an oxetanyl group, and a carboxyl group, It can also be used individually or in mixture of 2 or more types. . Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine-isosaururic acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isosaanuric acid S-triazine derivatives, such as an adduct, can also be used, Preferably, the compound which also functions as these adhesive imparting agents can be used together with the said thermosetting catalyst.

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

Examples of the content of the inorganic filler are not particularly limited, but in order to achieve high rigidity of the polymer resin layer, the inorganic filler may be 100 parts by weight or more, based on 100 parts by weight of all the resin components included in the polymer resin layer, or 100 parts by weight to 600 parts by weight, or 150 parts by weight to 500 parts by weight, or 200 parts by weight to 500 parts by weight may be added.

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

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

The leveling agent serves to remove the popping or crater of the surface when the film coating, for example, BYK-380N, BYK-307, BYK-307, BYK-378, BYK-350 of BYK-Chemie GmbH may be used.

In addition, the polymer resin layer may further include a resin or an elastomer having a molecular weight of 5000 or more that can cause phase separation. Accordingly, the roughening treatment of the cured product of the polymer resin layer may be possible. The example of the molecular weight measuring method of the said resin of 5000 or more of molecular weights or an elastomer is not specifically limited, For example, the weight average molecular weight of polystyrene conversion measured by the GPC method is meant. In the process of measuring the weight average molecular weight of polystyrene conversion measured by the GPC method, a detector and an analytical column, such as a commonly known analytical device and a differential index detector (Refractive Index Detector) can be used, Conditions, solvents and flow rates can be applied. Specific examples of the measurement conditions include a temperature of 30, a chloroform solvent and a flow rate of 1 mL / min.

In addition, the polymer resin layer may further include an alkali-soluble resin including a thermosetting binder or a photoreactive unsaturated group and a photoinitiator to impart photocurable properties to the polymer resin layer. Specific examples of the thermosetting binder including the photoreactive unsaturated group, the alkali-soluble resin including the photoreactive unsaturated group and the photoinitiator are not particularly limited, and various compounds used in the art related to the photocurable resin composition may be used without limitation.

The content of the photoinitiator contained in the polymer resin layer may be 0.01% by weight or less based on the total weight of the polymer resin layer. When the content of the photoinitiator contained in the polymer resin layer is less than 0.01% by weight based on the total weight of the polymer resin layer, the content of the photoinitiator contained in the polymer resin layer may be very insignificant or may not include any photoinitiator. . Accordingly, the interface detachability with the insulating layer or the conductive layer which can be generated by the photoinitiator can be reduced, and the adhesion and durability of the insulating layer can be improved.

Forming a photosensitive resin layer on the polymer resin layer

The photosensitive resin layer includes a polymer in which a change in molecular structure occurs due to the action of light and a change in physical properties, and examples thereof include a photosensitive dry film resist (DFR), a liquid resist, and the like.

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

Examples of the method of forming the photosensitive resin layer on the polymer resin layer are not particularly limited. For example, a method of laminating a photosensitive resin in the form of a film, such as a photosensitive dry film resist, on a polymer resin layer, or by spraying or dipping. A method of coating the photosensitive resin composition on the polymer resin layer and compressing the same may be used.

The polymer resin layer may have a thickness of 1 μm to 500 μm, or 3 μm to 500 μm, or 3 μm to 200 μm, or 1 μm to 60 μm, or 5 μm to 30 μm, on the polymer resin layer. The formed photosensitive resin layer may have a thickness of 1 μm to 500 μm, or 3 μm to 500 μm, or 3 μm to 200 μm, or 1 μm to 60 μm, or 5 μm to 30 μm. When the thickness of the photosensitive resin layer is excessively increased, the resolution of the polymer resin layer may decrease.

Exposing the photosensitive resin layer and Alkali  The polymer resin layer exposed by the photosensitive resin pattern while being developed to form a photosensitive resin pattern Alkali  Developing steps

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

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

That is, for example, a method of exposing the photosensitive resin layer may include contacting a photomask formed with a predetermined pattern on the photosensitive resin layer and irradiating ultraviolet rays, or imaging a predetermined pattern included in the mask through a projection objective lens. Next, ultraviolet rays may be selectively exposed using a method such as directly irradiating ultraviolet rays or irradiating ultraviolet rays using a laser diode as a light source. Under the present circumstances, as an example of ultraviolet irradiation conditions, irradiation with the light quantity of 5mJ / cm <2> -600mJ / cm <2> is mentioned.

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

The ratio at which the photosensitive resin pattern is removed may be 0.01 wt% or less with respect to the total photosensitive resin pattern weight. When the ratio of the photosensitive resin pattern is removed is 0.01 wt% or less relative to the total weight of the photosensitive resin pattern, the ratio at which the photosensitive resin pattern is removed may be very insignificant or the photosensitive resin pattern may not be removed at all.

Accordingly, in the method of manufacturing the insulating layer, the photosensitive resin layer may be exposed and alkali developed to form a photosensitive resin pattern, and at the same time, the polymer resin layer exposed by the photosensitive resin pattern may be alkali developed. As described above, the photosensitive resin layer may be formed with a fine and uniform pattern by using photosensitivity, and only a part of the surface of the polymer resin layer exposed through the pattern formed on the photosensitive resin layer selectively contacts the alkali developer. Through this process, the conventional laser etching process may be replaced, but more accurate and equivalent process economics may be obtained.

That is, in the step of alkali developing the polymer resin layer exposed by the photosensitive resin pattern, the photosensitive resin pattern is used as a resist mask as it is, because it is not removed by the alkaline developer, it is used as an alkali through the opening of the photosensitive resin pattern The developing solution may contact the polymer resin layer located under the photosensitive resin layer. At this time, since the polymer resin layer includes an alkali-soluble resin, since the polymer resin layer has alkali solubility dissolved by an alkali developer, a portion of the polymer resin layer in contact with the alkali developer may be dissolved and removed.

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

By alkali developing the polymer resin layer exposed by the photosensitive resin pattern, a polymer resin pattern having the same form as the photosensitive resin pattern may be formed on the polymer resin layer as shown in FIG. 1. Like the photosensitive resin pattern, a part of the polymer resin layer that remains as it is without alkali development may be referred to as a polymer resin pattern.

In this way, as the pattern formation through the development of the photosensitive resin layer and the pattern formation through the development of the polymer resin layer are simultaneously performed in one alkaline developer, mass production can be performed quickly, thereby improving the efficiency of the process. The 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.

On the other hand, after the step of exposing and alkali developing the photosensitive resin layer to form a photosensitive resin pattern and at the same time also alkali developing the polymer resin layer exposed by the photosensitive resin pattern, the entire polymer resin layer exposed by the photosensitive resin pattern 0.1 to 85 weight percent, or 0.1 to 50 weight percent, or 0.1 to 10 weight percent, based on weight, may remain. This is because the alkali-soluble resin contained in the polymer resin layer was removed by the alkaline developer, but the thermosetting binder or the inorganic filler, which has little alkali developability, seems to remain without being removed.

In particular, in order to control the extent to which the inorganic filler and the thermosetting binder remain, the weight ratio of the thermosetting binder and the inorganic filler to the alkali soluble resin, the ratio of the acidic functional groups on the surface of the inorganic filler, and the like, and preferably the alkali soluble resin 100 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 filler may be added, and an acid value of the surface of the inorganic filler may be 0 mgKOH / g to 5 mgKOH / g, or 0.01 mgKOH / g to 5 mgKOH / g. The content of the acid value is the same as the method for measuring the acid value of the alkali-soluble resin.

As described above, in the process 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 polymer resin pattern is removed during the subsequent process of removing the photosensitive resin pattern. Instead, while the remaining polymer resin layer is removed, it is possible to prevent via hole expansion due to the removal of the polymer resin pattern.

After the alkali development, thermosetting the polymer resin layer

In addition, the insulating layer manufacturing method may include a step of thermosetting the polymer resin layer after the alkali development. As the polymer resin layer may be thermally cured, damage to the polymer resin layer may be minimized during the subsequent photosensitive resin pattern peeling process.

At this time, the specific thermosetting conditions are not limited, and according to the peeling method of the photosensitive resin pattern, the preferable conditions may be adjusted. For example, when the photoresist stripper is removed to remove the photosensitive resin pattern, the step of thermosetting the polymer resin layer may be performed 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 short, the polymer resin pattern may be damaged by the stripping solution, and the thermosetting temperature of the polymer resin layer is high, or the thermosetting time is long. In this case, it may be difficult to remove the photosensitive resin pattern by the stripping solution.

As another example, when the resist mask is peeled off through a desmear process, the thermosetting of the polymer resin layer may be performed for 1 hour to 4 hours at a temperature of 150 to 230 ° C.

Peeling off the photosensitive resin pattern

The insulating layer manufacturing method may include peeling the photosensitive resin pattern after the thermosetting. When removing the photosensitive resin pattern, it is preferable to use a method capable of removing only the photosensitive resin layer without removing the lower polymer resin layer as much as possible. In addition, a portion of the polymer resin layer may be removed to control the shape of the opening pattern or to remove residues of the polymer resin layer that may remain on the bottom surface of the opening pattern.

That is, the ratio of removing the polymer resin layer in the step of peeling the photosensitive resin pattern may be 10% by weight or less, or 1% by weight or less, or 0.01% by weight or less with respect to the total weight of the polymer resin layer. When the ratio of the polymer resin layer is removed is less than 0.01% by weight based on the total weight of the polymer resin layer, the ratio of removing the polymer resin layer may be very insignificant or may not mean that the polymer resin layer is not removed at all.

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

Although the example of the peeling method using the photoresist stripping solution is not particularly limited, for example, it can be used by adjusting the concentration and temperature of alkaline aqueous solution such as potassium hydroxide and sodium hydroxide, Atotech's Resistrip product range, Oalchem's ORC-731 Commercially available products such as ORC-723K, ORC-740, and SLF-6000 are also available. Although the specific amount of the photoresist stripping solution is not particularly limited, it needs to be adjusted to a concentration and temperature that does not damage the lower polymer resin layer pattern. For example, a 1 to 5% aqueous solution of sodium hydroxide of 25 to 60 may be used. Can be.

Examples of the peeling method using the desmear process are not limited to, for example, Atotech's desmear process chemicals, such as Securiganth E, Securiganth HP, Securiganth BLG, Securiganth MV SWELLER, Securiganth SAP SWELLER, Securiganth P Reagents such as 500, Securiganth MV ETCH P, Securiganth SAP ETCH P, Securiganth E Reduction Cleaner, Securiganth HP Reduction Cleaner, Securiganth BLG Reduction Cleaner, Securiganth MV Reduction Cleaner, Securiganth SAP Reduction Cleaner As a process chemical, commercially available products such as swellers such as ORC-310A, ORC-315A, ORC-315H and ORC-312, permanganic acid such as ORC-340B, and reducing agents such as ORC-370 and ORC-372 Can be used according to the conditions.

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

The present inventors, as the insulating layer manufactured in the embodiment includes a predetermined opening pattern, in the process of newly laminating a metal substrate on the insulating layer, as the inside of the opening pattern is filled with metal, based on the insulating layer As a result, it was confirmed that the upper and lower metal substrates were connected to each other to manufacture a multilayer printed circuit board.

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

The forming of the metal substrate having the pattern formed on the insulating layer is a microcircuit pattern forming process known in the art as a semi additive process (SAP), and the SAP process forms a microcircuit pattern in a state where nothing exists on the insulating layer. It may mean a case of forming.

For example, forming a metal substrate having a pattern formed on the insulating layer more specifically, forming a metal thin film on the insulating layer; Forming a photosensitive resin layer having a pattern formed on the metal thin film; Depositing a metal on the metal thin film exposed by the photosensitive resin layer pattern; And removing the photosensitive resin layer and removing the exposed metal thin film.

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

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

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

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

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

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

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

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

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

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

According to the present invention, while improving the efficiency in terms of cost and productivity, it is possible to implement a uniform and fine pattern, multi-layer printing using the insulating layer manufacturing method and the insulating layer obtained from the insulating layer manufacturing method to ensure excellent mechanical properties A circuit board manufacturing method may be provided.

Figure 1 schematically shows a manufacturing process of the insulating layer of Example 1.
2 schematically shows a manufacturing process of a multilayer printed circuit board of Example 2. FIG.

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

Preparation Example: Production of Alkali Soluble Resin

Preparation Example 1

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

Preparation Example 2

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

Preparation Example 3

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

Preparation Example 4

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

<Example>

Example 1 Fabrication of Insulation Layer

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

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

At this time, the photosensitive dry film resist 4 having the pattern formed serves as a protective layer of the polymer resin layer 1, so that the same pattern as the photosensitive dry film resist 4 is formed in the polymer resin layer 1, Via holes 5 were formed. At this time, white residues derived from the polymer resin layer 1 remained in the via holes 5.

Thereafter, thermal curing was performed at a temperature of 100 for 1 hour, and then the residue and the photosensitive dry film resist 4 were removed using a 3% sodium hydroxide resist stripping solution at a temperature of 50 ° C., and thermoset for 1 hour at a temperature of 200 ° C. To proceed further to prepare an insulating layer having a via hole diameter of Table 1 below.

Example 2 Fabrication of Multilayer Printed Circuit Board

Referring to the contents of FIG. 2, titanium (Ti) metal 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 via hole 5 prepared in Example 1 to a deposition apparatus. 50 nm and a copper (Cu) metal were deposited to a thickness of 0.5 μm to form a seed layer (8).

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 electroplating. Next, the photosensitive resin pattern 9 was removed using a photosensitive resin stripper, and thus the exposed seed layer 8 was removed by etching to prepare a multilayer printed circuit board.

Example 3: Fabrication of Insulation Layer

16 g of the alkali-soluble resin synthesized in Preparation Example 3, 6 g of MY-510 (manufactured by Huntsman) as a thermosetting binder, and 35 g of SC2050 MTO (70% solids, manufactured by Adamatech) as an inorganic filler when the polymer resin layer was prepared. Except for using, an insulating layer having a via hole diameter of Table 1 was prepared in the same manner as in Example 1.

Example 4 Fabrication 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 prepared in Example 3 was used instead of the insulating layer prepared in Example 1.

Example 5 Fabrication of Insulation Layer

16g of the alkali-soluble resin synthesized in Preparation Example 1, 5g of MY-510 (manufactured by Huntsman) as a thermosetting binder, and 43g of SC2050 MTO (70% solids, Adamatech) as an inorganic filler when the polymer resin layer was prepared. Except for using, an insulating layer having a via hole diameter of Table 1 was prepared in the same manner as in Example 1.

Example 6 Fabrication of Insulation Layer

16 g of the alkali-soluble resin synthesized in Preparation Example 2, 5 g of MY-510 (manufactured by Huntsman) as a thermosetting binder, and 43 g of SC2050 MTO (70% solids, manufactured by Adamatech) as an inorganic filler when the polymer resin layer was prepared. Except for using, an insulating layer having a via hole diameter of Table 1 was prepared in the same manner as in Example 1.

Example 7 Fabrication of Insulation Layer

16 g of the alkali-soluble resin synthesized in Preparation Example 3, 5 g of MY-510 (manufactured by Huntsman) as a thermosetting binder, and 43 g of SC2050 MTO (70% solids, manufactured by Adamatech) as an inorganic filler when the polymer resin layer was prepared. Except for using, an insulating layer having a via hole diameter of Table 1 was prepared in the same manner as in Example 1.

Example 8 Fabrication of Insulation Layer

In preparing the polymer resin layer, 16 g of an alkali-soluble resin synthesized in Preparation Example 4, 5 g of MY-510 (manufactured by Huntsman) as a thermosetting binder, and 43 g of SC2050 MTO (70% solids, manufactured by Adamatech) as an inorganic filler were mixed. Except for using, an insulating layer having a via hole diameter of Table 1 was prepared in the same manner as in Example 1.

Comparative Example

Comparative Example 1: Fabrication of Insulation Layer

As in Example 1, 16 g of the alkali-soluble resin synthesized in Preparation Example 1, 5 g of MY-510 (manufactured by Huntsman) as a thermosetting binder, and 35 g of SC2050 MTO (70% solids, Adamatech) as an inorganic filler were mixed. The composition was applied to a PET film and dried to prepare a polymer resin layer 1 having a thickness of 15 μm. And. The polymer resin layer 1 was vacuum laminated at 85 on a circuit board on which copper lines 2 were formed on the copper-clad 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 prepare an insulating layer having a via hole diameter shown in Table 1 below.

Comparative Example 2: Fabrication of Insulation Layer

30 g of CCR-1291H (manufactured by Nippon Kayaku) with acid-modified acrylate resin, 5 g of TMPTA (manufactured by ETNIS) with polyfunctional acrylate monomer, 2 g of Irgacure TPO-L (manufactured by BASF) with photoinitiator, YDCN-500-8P with polyfunctional epoxy (Kukdo Chemical Co., Ltd.) The photosensitive resin composition which mixed 6 g and 2 g of 2E4MZ (made by Shikoku Chem) with the thermosetting catalyst was apply | coated on a circuit board, and it dried and manufactured the photosensitive resin layer.

A circular negative photomask having a diameter of 30 μm was contacted on the photosensitive resin layer, irradiated with ultraviolet rays (light amount of 400 mJ / cm 2), and developed through 30 1% sodium carbonate developer to prepare an insulating layer.

Comparative Example 3: Fabrication 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 prepared in Comparative Example 2 was used instead of the insulating layer prepared in Example 1.

Comparative Example 4: Fabrication of Insulation Layer

As in Example 5, 16g of the alkali-soluble resin synthesized in Preparation Example 1, 6g of MY-510 (manufactured by Huntsman) as a thermosetting binder, 43g of SC2050 MTO (70% solids, Adamatech) as an inorganic filler was mixed Was applied to a PET film and dried to prepare a polymer resin layer (1) having a thickness of 15 μm. And. The polymer resin layer 1 was vacuum laminated at 85 on a circuit board on which copper lines 2 were formed on the copper-clad 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 prepare an insulating layer having a via hole diameter shown in Table 1 below.

Comparative Example 5: Fabrication of Insulation Layer

As in Example 7, the polymer resin composition was mixed with 16 g of the alkali-soluble resin synthesized in Preparation Example 3, 5 g of MY-510 (manufactured by Huntsman) with a thermosetting binder, and 43 g of SC2050 MTO (70% solids, manufactured by Adamatech) with an inorganic filler. Was applied to a PET film and dried to prepare a polymer resin layer (1) having a thickness of 15 μm. And. The polymer resin layer 1 was vacuum laminated at 85 on a circuit board on which copper lines 2 were formed on the copper-clad 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 prepare an insulating layer having a via hole diameter shown in Table 1 below.

Comparative Example 6: Fabrication of Insulation Layer

30 g of CCR-1291H (manufactured by Nippon Kayaku) with acid-modified acrylate resin, 5 g of TMPTA (manufactured by ETNIS) with polyfunctional acrylate monomer, 2 g of Irgacure TPO-L (manufactured by BASF) with photoinitiator, YDCN-500-8P with polyfunctional epoxy (Preparation of Kukdo Chemical Co., Ltd.) A photosensitive resin composition obtained by mixing 6 g, 0.2 g of 2E4MZ (manufactured by Shikoku Chem) with a thermosetting catalyst, and 49 g of SC2050 MTO (70% solids, manufactured by Adamatech) with an inorganic filler was applied on a circuit board, dried, and then photosensitive. The resin layer was produced.

A circular negative photomask having a diameter of 30 μm was contacted on the photosensitive resin layer, irradiated with ultraviolet light (light amount of 400 mJ / cm 2), and developed through 30 ° C. 1% sodium carbonate developer to prepare an insulating layer. .

Experimental Example: Measurement of Physical Properties of Insulation Layer Obtained in Examples and Comparative Examples

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

1. Via hole diameter

The diameters of the upper opening surfaces (via holes) of the insulating layers obtained in Examples 1, 3, 5-8 and Comparative Examples 1, 2, 4, 5, and 6 were measured through an optical microscope.

2. Metal adhesion by moisture absorption

After leaving the multilayer printed circuit boards obtained in Examples 2, 4 and Comparative Example 3 for 48 hours at 135 ° C. and 85% moisture absorption, the peel strength of the metal was measured according to the IPC-TM-650 standard. Metal adhesion was obtained.

3.HAST (Highly Accelerated Temp & Humidity Stress Test) Resistance

The HAST resistance of the multilayer printed circuit boards obtained in Examples 2, 4 and Comparative Example 3 was confirmed according to the JESD22-A101 standard. Specifically, after applying a voltage of 3V to the specimen circuit board having a width, an interval, and a thickness of 50 μm, 50 μm, and 12 μm, respectively, and leaving it for 168 hours, the sample circuit board was inspected under the following criteria. It was.

OK: No abnormality observed in the appearance of the coating

NG: blisters or peelings are observed on the film

Experimental Example Results of Examples and Comparative Examples division Via hole diameter (㎛) Metal adhesion (kgf / cm) HAST characteristic (㎛) Example 1 46 - - Example 2 - 0.3 OK Example 3 46 - - Example 4 - 0.3 OK Example 5 41 - - Example 6 42 - - Example 7 42 - - Example 8 42 - - Comparative Example 1 62 - - Comparative Example 2 28 - - Comparative Example 3 - 0 (complete peel) NG Comparative Example 4 62 - - Comparative Example 5 60 - - Comparative Example 6 Not formed - -

As shown in Table 1, in the case of Comparative Examples 1, 4, and 5 insulating layers in which the via holes were formed by etching the thermosetting resin layer using a CO 2 laser drill, the diameter of the via holes was 62 μm or 60 μm, The diameter of the via hole included in the insulating layers prepared in Examples 1, 3, and 5-8 was reduced to 46 μm or less, and thus, it was confirmed that a finer pattern could be implemented in the case of the above embodiment.

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

In addition, in the Comparative Example 3 multilayer printed circuit board manufactured by exposure and development of the Comparative Example 2 resin composition including the photoinitiator, the adhesion of the metal was measured at 0 kgf / cm, indicating that interface desorption between the insulating layer and the conductive layer occurred. It was confirmed that the HAST resistance was also poor.

On the other hand, in the case of the multilayer printed circuit board of Example 2 manufactured by thermal curing without the photoinitiator, the metal adhesion is measured as 0.3 kgf / ㎝ high, maintaining the interface bonding between the insulating layer and the conductive layer, excellent HAST It could be confirmed that the resistance was shown.

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

When the inorganic filler content is higher than that of the resin as in Examples 5 to 8, the inorganic filler is not removed during alkali development for forming the insulating layer, so that a sufficient residue is formed, and the residue has a via hole diameter during subsequent resist stripping. It is believed that the expansion is suppressed.

1: polymer resin layer
2: copper circuit
3: copper clad laminate
4: Photosensitive Dry Film Resist (DFR)
5: via hole
6: metal layer
7: insulation layer
8: seed layer
9: photosensitive resin pattern
10: metal substrate
<1> to <6>: Process sequence of a process

Claims (20)

Forming a polymer resin layer including an alkali-soluble resin and a thermosetting binder on the conductor wiring;
Forming a photosensitive resin layer on the polymer resin layer;
Exposing and alkali developing the photosensitive resin layer to form a photosensitive resin pattern, and at the same time, alkali developing the polymer resin layer exposed by the photosensitive resin pattern;
Heat curing the polymer resin layer after the alkali development; And
Peeling the photosensitive resin pattern;
1) The alkali soluble resin is an acidic functional group; And at least one or more cyclic imide functional groups each substituted with an amino group, or
2) the alkali-soluble resin is a repeating unit represented by the following formula (3); And at least one or more repeating units represented by the following formula (4):
[Formula 3]

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

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

In Formula 1, R ₁ is an alkylene group or alkenyl group having 1 to 10 carbon atoms, and "*" means a point of attachment.
The method of claim 1,
1) The alkali soluble resin is a cyclic unsaturated imide compound; And an amine compound, wherein at least one or more of the cyclic unsaturated imide compound and the amine compound include an acidic functional group substituted at an end thereof.
The method of claim 4, wherein
The amine compound comprises at least one member selected from the group consisting of a carboxylic acid compound substituted with an amino group and a polyfunctional amine compound containing two or more amino groups, insulating layer manufacturing method.
delete The method of claim 1,
2) The alkali-soluble resin is prepared by the reaction of a polymer comprising a repeating unit represented by the following formula (5), an amine represented by the formula (6), and an amine represented by the formula (7):
[Formula 5]

[Formula 6]

[Formula 7]

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

[Formula 9]

In Chemical Formulas 8 to 9, R ₂ to R ₄ are as defined in claim 1.
The method of claim 1,
The alkali-soluble resin has an acid value (50 mgKOH / g to 250 mgKOH / g) obtained by KOH titration, insulating layer manufacturing method.
The method of claim 1,
The polymer resin layer comprises 1 part by weight to 150 parts by weight of the thermosetting binder with respect to 100 parts by weight of the alkali-soluble resin, the insulating layer manufacturing method.
The method of claim 1,
The thermosetting binder includes at least one functional group and an epoxy group selected from the group consisting of oxetanyl group, cyclic ether group, cyclic thio ether group, cyanide group, maleimide group and benzoxazine group.
The method of claim 1,
The content of the photoinitiator contained in the polymer resin layer is 0.01 wt% or less relative to the total weight of the polymer resin layer, insulating layer manufacturing method.
The method of claim 1,
Exposing and alkali developing the photosensitive resin layer to form a photosensitive resin pattern, and at the same time, alkali developing the polymer resin layer exposed by the photosensitive resin pattern,
The ratio of removing the photosensitive resin pattern is 0.01% by weight or less based on the total weight of the photosensitive resin pattern, the insulating layer manufacturing method.
The method of claim 1,
After exposing and alkali developing the photosensitive resin layer to form a photosensitive resin pattern, the polymer resin layer exposed by the photosensitive resin pattern is also alkali developed.
0.1 wt% to 85 wt% based on the total weight of the polymer resin layer exposed by the photosensitive resin pattern, the insulating layer manufacturing method.
The method of claim 1,
In the step of peeling the photosensitive resin pattern,
The insulating layer manufacturing method, wherein the ratio of the polymer resin layer is removed is 10% by weight or less relative to the total weight of the polymer resin layer.
The method of claim 1,
The said polymeric resin layer contains an inorganic filler at 100 weight part or more with respect to a total of 100 weight part of alkali-soluble resin and a thermosetting binder.
The method of claim 1,
The polymer resin layer or the photosensitive resin layer has a thickness of 1 μm to 500 μm, the insulating layer manufacturing method.
A method of manufacturing a multilayer printed circuit board, comprising the step of forming a metal substrate having a pattern formed on the insulating layer prepared by claim 1.
The method of claim 18,
The insulating layer is a multilayer printed circuit board manufacturing method comprising a thermosetting of an alkali-soluble resin and a thermosetting binder.
The method of claim 18,
Forming a metal substrate having a pattern formed on the insulating layer,
Forming a metal thin film on the insulating layer;
Forming a photosensitive resin layer having a pattern formed on the metal thin film; And
Depositing a metal on the metal thin film exposed by the photosensitive resin layer pattern; And
Removing the photosensitive resin layer and removing the exposed metal thin film.

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