KR20210092100A - Insulation composition and method for manufacturing insulating film using the same, method for manufacturing multilayered printed circuit board - Google Patents

Abstract

The present invention relates to an insulating composition capable of forming an insulating layer having excellent adhesion to conductor wiring, a method for manufacturing an insulating film using the same, and a method for manufacturing a multilayered printed circuit board. The insulating composition comprises an imidazole-silane compound containing a carboxyl group represented by a chemical formula 1; an alkali-soluble resin; and a thermosetting binder.

Description

Insulation composition and insulating layer manufacturing method using same, multilayer printed circuit board manufacturing method

The present invention relates to an insulating composition, a method for manufacturing an insulating layer using the same, and a method for manufacturing a multilayer printed circuit board.

Recently, electronic devices are becoming smaller, lighter, and more functional. To this end, as the application field of the build-up printed circuit board (Build-up Printed Circuit Board) is rapidly expanding centering on small devices, the use of the multilayer printed circuit board is rapidly increasing.

Multilayer printed circuit boards are capable of three-dimensional wiring from flat wiring. In particular, in the field of industrial electronics, integration of functional devices such as IC (integrated circuit) and LSI (large scale integration) has been improved, and electronic devices are miniaturized, lightweight, highly functional, and structurally structured. It is an advantageous product for electrical function integration, shortening of assembly time and cost reduction.

The build-up method used in this application area forms a conductive layer on an insulating layer, and an insulating layer with excellent adhesion to the conductor wiring constituting the conductive layer is required to improve the quality of the multilayer printed circuit board.

The present invention relates to an insulating composition capable of forming an insulating layer having excellent adhesion to a conductor wiring, a method for manufacturing an insulating layer using the same, and a method for manufacturing a multilayer printed circuit board.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

An exemplary embodiment of the present invention is an imidazole-silane compound containing a carboxyl group represented by the following formula (1); alkali-soluble resin; and a thermosetting binder; provides an insulating composition comprising.

[Formula 1]

In Formula 1, R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

X is an alkylene group having 2 to 6 carbon atoms, wherein at least one -CH ₂ - group may be independently substituted with -O-,

R ₂ is an alkoxy group having 1 to 3 carbon atoms,

R ₃ is a nitro group or a carboxyl group.

In addition, one embodiment of the present invention, the step of applying the insulating composition on the conductor wiring having a metal protrusion formed on the surface; forming an insulating film by first curing the insulating composition; exposing the metal protrusions by etching the surface of the insulating film with an aqueous alkali solution; and secondary curing of the insulating film exposing the metal protrusion.

In addition, an exemplary embodiment of the present invention provides a method for manufacturing a multilayer printed circuit board comprising the step of forming a metal pattern layer on the insulating layer manufactured by the insulating layer manufacturing method.

The insulating composition according to an exemplary embodiment of the present invention may implement an insulating layer having excellent adhesion to the conductor wiring.

In addition, according to an exemplary embodiment of the present invention, it is possible to provide a method for manufacturing an insulating layer and a method for manufacturing a multilayer printed circuit board that is excellent in the efficiency of the manufacturing process and can prevent physical damage to the insulating layer.

Effects of the present invention are not limited to the above-described effects, and effects not mentioned will be clearly understood by those skilled in the art from the present specification and accompanying drawings.

Throughout this specification, when a part "includes" a certain element, it means that other elements may be further included, rather than excluding other elements, unless otherwise stated.

Throughout this specification, when a member is said to be “on” another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

Throughout this specification, the unit “part by weight” may mean a ratio of weight between each component.

Hereinafter, the present specification will be described in more detail.

An exemplary embodiment of the present invention provides an insulating composition comprising an imidazole-silane compound containing a carboxyl group represented by the following Chemical Formula 1, an alkali-soluble resin, and a thermosetting binder.

[Formula 1]

In Formula 1, R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is an alkylene group having 2 to 6 carbon atoms, in this case, one or more —CH ₂ —groups may be independently substituted with —O—, and , R ₂ is an alkoxy group having 1 to 3 carbon atoms, R ₃ is a nitro group or a carboxyl group.

The cured product of the insulating composition according to an exemplary embodiment of the present invention may implement an insulating layer having excellent adhesion to the conductor wiring. In addition, the insulating composition can be easily prepared by chemical etching with an aqueous alkali solution.

Since the insulating composition includes the imidazole-silane compound containing a carboxyl group represented by Chemical Formula 1, it is possible to implement an insulating layer having excellent adhesion to a conductor wiring having room temperature stability. Specifically, since the imidazole functional group in Formula 1 has a structure in which the carboxyl group is blocked by a carboxyl group, the imidazole functional group of the carboxyl group-containing imidazole-silane compound during the preparation and storage of the insulating layer with the insulating composition It is possible to suppress the progress of a side reaction between the alkali-soluble resin and the thermosetting binder.

According to an exemplary embodiment of the present invention, the carboxyl group-containing imidazole-silane compound is a mixture comprising an imidazole monomer represented by the following formula (2), a silane represented by the following formula (3), and phthalic anhydride represented by the following formula (4) may be a reaction product of

[Formula 2]

In Formula 2, R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[Formula 3]

In Formula 3, X is an alkylene group having 2 to 6 carbon atoms. In this case, one or more -CH ₂ -groups of X may be independently substituted with -O-.

[Formula 4]

In Formula 4, R ₃ is a nitro group or a carboxyl group.

That is, the carboxyl group-containing imidazole-silane compound is a unit derived from imidazole represented by Formula 2, a unit derived from silane represented by Formula 3, and a unit derived from phthalic anhydride represented by Formula 4 may include.

According to an exemplary embodiment of the present invention, the silane may contain at least an epoxy group. An epoxy group ring opening reaction of the silane by the imidazole may proceed to form an imidazole-silane compound.

The silane may include at least a reactant represented by the following Chemical Formula 3-1.

[Formula 3-1]

According to an exemplary embodiment of the present invention, the content of the silane in the mixture may be 250 parts by weight or more and 350 parts by weight or less based on 100 parts by weight of the imidazole. Specifically, the content of the silane is based on 100 parts by weight of the imidazole, 270 parts by weight or more and 330 parts by weight or less, 285 parts by weight or more and 300 parts by weight or less, 250 parts by weight or more and 300 parts by weight or less, 320 parts by weight or more and 350 parts by weight or more. parts by weight or less, or 275 parts by weight or more and 320 parts by weight or less.

By adjusting the contents of the imidazole and the silane in the mixture to the above-described ranges, the imidazole-silane compound corresponding to the main chain of Formula 1 may be stably formed.

According to an exemplary embodiment of the present invention, an epoxy group ring-opening reaction of the imidazole and the silane proceeds to form an imidazole-silane compound, and then a ring-opening reaction of phthalic anhydride proceeds to a carboxyl group-containing imidazole-silane compound can be formed. In this case, the carboxyl group included in the imidazole-silane compound is a functional group formed by the ring opening reaction of the phthalic anhydride.

According to an exemplary embodiment of the present invention, at least one of the hydrogen atoms of the benzene ring of the phthalic anhydride may be substituted with a nitro group or a carboxyl group. At least one of the hydrogen atoms of the benzene ring of the phthalic anhydride is substituted with a nitro group or a carboxyl group, so that the ring opening reaction of the phthalic anhydride may be more easily performed. In addition, it is possible to effectively lower the pKa of the prepared imidazole-silane containing a carboxyl group.

The phthalic anhydride may include at least one of the reactants represented by the following Chemical Formulas 4-1 to 4-3.

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

According to an exemplary embodiment of the present invention, the content of the phthalic anhydride in the mixture may be 150 parts by weight or more and 300 parts by weight or less based on 100 parts by weight of the imidazole. Specifically, the content of the phthalic anhydride is based on 100 parts by weight of the imidazole, 160 parts by weight or more and 280 parts by weight or less, 165 parts by weight or more and 250 parts by weight or less, 170 parts by weight or more and 235 parts by weight or less, 150 parts by weight or more and 200 parts by weight or more. It may be no more than 215 parts by weight and no more than 250 parts by weight, or 175 parts by weight or more and 240 parts by weight or less.

By adjusting the content of the phthalic anhydride and the imidazole in the mixture to the above-mentioned range, the carboxyl group-containing imidazole-silane compound of Formula 1 having a structure in which a carboxyl group derived from phthalic anhydride blocks an imidazole functional group effectively can be formed

According to an exemplary embodiment of the present invention, the carboxyl group-containing imidazole-silane compound may include at least one of the carboxyl group-containing imidazole-silane compounds represented by Compounds 1 to 3 below.

[Compound 1]

[Compound 2]

[Compound 3]

Compound 1 may be prepared by reacting 2-methyl imidazole, silane represented by Formula 3-1, and phthalic anhydride represented by Formula 4-1. In addition, Compound 2 may be prepared by reacting 2-methyl imidazole, silane represented by Formula 3-1, and phthalic anhydride represented by Formula 4-2. In addition, Compound 3 may be prepared by reacting 2-methyl imidazole, silane represented by Formula 3-1, and phthalic anhydride represented by Formula 4-3.

An insulating layer having excellent adhesion to a conductor wiring may be provided by using an insulating composition including an alkali-soluble resin including at least one of Compounds 1 to 3.

According to an exemplary embodiment of the present invention, the pKa of the carboxyl group-containing imidazole-silane compound may be 1.5 or more and 3.5 or less. Specifically, the pKa of the carboxyl group-containing imidazole-silane compound may be 1.6 or more and 3.3 or less, 1.7 or more and 3.1 or less, 1.5 or more and 2.7 or less, or 2.5 or more and 3.5 or less. In this case, the pKa of the carboxyl group-containing imidazole-silane compound may mean the pKa of the carboxyl group formed by the ring opening reaction of the phthalic anhydride. When the pKa of the carboxyl group-containing imidazole-silane compound is within the above range, the effect of blocking the imidazole functional group by the carboxyl group may be further improved.

According to an exemplary embodiment of the present invention, the alkali-soluble resin has an acidic functional group; and at least 1 or more, or 2 or more, respectively, of a cyclic imide functional group substituted with an amino group. Examples of the acidic functional group are not particularly limited, but may include, for example, a carboxy group or a phenol group. The alkali-soluble resin includes at least one or more acidic functional groups, or two or more, so that the polymer resin layer exhibits higher alkali developability, and the development rate of the polymer resin layer can be controlled.

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

In addition, as a plurality of the cyclic imide functional group is present 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 a higher interfacial adhesion with the metal layer laminated thereon, and specifically, have higher adhesion than the interfacial adhesion between the carrier film and the metal layer laminated on the metal layer. Therefore, as will be described later, physical peeling between the carrier film and the metal layer may be possible.

More specifically, the cyclic imide functional group substituted with the amino group may include a functional group represented by the following Chemical Formula 5.

[Formula 5]

In Formula 5, R ₄ is an alkylene or alkenyl group having 1 to 10, or 1 to 5, or 1 to 3 carbon atoms, and “*” means a bonding point. The alkylene group is a divalent functional group derived from an alkane, for example, a straight-chain, branched or cyclic, methylene group, ethylene group, propylene group, isobutylene group, sec-butylene group, It may be a tert-butylene group, a pentylene group, a hexylene group, or the like. One or more hydrogen atoms included in the alkylene group may be substituted with other substituents, 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. A to 12 aryl group, a C2 to C12 heteroaryl group, an arylalkyl group having 6 to 12 carbon atoms, a halogen atom, a cyano group, an amino group, an amidino group, a nitro group, an amide group, a carbonyl group, a hydroxyl group, a sulfonyl group, a carba A mate group, a C1-C10 alkoxy group, etc. are mentioned.

The term "substituted" means that other functional groups are bonded instead of hydrogen atoms in the compound, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, the position where the substituent is substituted, is not limited, and when substituted by two or more, two or more The substituents may be the same as or different from each other.

The alkenyl group means one containing at least one carbon-carbon double bond in the middle or at the terminal of the above-described alkylene group, and examples include ethylene, propylene, butylene, hexylene, acetylene, and the like. . One or more hydrogen atoms in the alkenyl group may be substituted with the same substituents as in the case of the alkylene group.

Preferably, the cyclic imide functional group substituted with the amino group may be a functional group represented by the following formula (6).

[Formula 6]

In Formula 6, "*" 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 terminal of the cyclic imide functional group substituted with an amino group. can do. In this case, the cyclic imide functional group substituted with the amino group and the acidic functional group may be bonded via a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, for example, the cyclic imide functional group substituted with the amino group An acidic functional group may be bonded to the terminal of the amino group included in the imide functional group through a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and the amino group included in the cyclic imide functional group substituted with the amino group may be bonded to the terminal. An 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 terminus 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 5, and the amino group included in the cyclic imide functional group substituted with the amino group The terminus of the de functional group may mean a nitrogen atom included in the cyclic imide functional group in Formula 5 above.

The alkylene group is a divalent functional group derived from an alkane, for example, a straight-chain, branched or cyclic, methylene group, ethylene group, propylene group, isobutylene group, sec-butylene group, It may be a tert-butylene group, a pentylene group, a hexylene group, or the like. One or more hydrogen atoms included in the alkylene group may be substituted with other substituents, 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. A to 12 aryl group, a C2 to C12 heteroaryl group, an arylalkyl group having 6 to 12 carbon atoms, a halogen atom, a cyano group, an amino group, an amidino group, a nitro group, an amide group, a carbonyl group, a hydroxyl group, a sulfonyl group, a carba A mate group, a C1-C10 alkoxy group, etc. are mentioned.

The arylene group is a divalent functional group derived from arene, for example, a cyclic group, and may be a phenyl group, a naphthyl group, or the like. One or more hydrogen atoms included in the arylene group may be substituted with other substituents, 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. A to 12 aryl group, a C2 to C12 heteroaryl group, an arylalkyl group having 6 to 12 carbon atoms, a halogen atom, a cyano group, an amino group, an amidino group, a nitro group, an amide group, a carbonyl group, a hydroxyl group, a sulfonyl group, a carba A mate group, a C1-C10 alkoxy group, etc. are mentioned.

Examples of the method for preparing the alkali-soluble resin are not particularly limited, but for example, a cyclic unsaturated imide compound; And it can be prepared through the reaction of an amine compound. In this case, the cyclic unsaturated imide compound; And at least one of the amine compound 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 compounds. The content of the acidic functional group is the same as described above.

The cyclic imide compound is a compound including the above-described cyclic imide functional group, and the cyclic unsaturated imide compound refers to a compound containing at least one unsaturated bond, that is, 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 with a double bond or a triple bond included in the cyclic unsaturated imide compound.

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

Examples of the cyclic unsaturated imide compound include N-substituted maleimide compounds. N-substituted means that a functional group is bonded instead of a hydrogen atom bonded to a nitrogen atom included in the maleimide compound, and the N-substituted maleimide compound is a 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 includes a nitrogen atom included in each of two or more maleimide compounds. It is a compound bound by a medium.

In the monofunctional N-substituted maleimide compound, the functional group substituted for the nitrogen atom included in the maleimide compound may include, without limitation, various known aliphatic, alicyclic or aromatic functional groups, and the functional group substituted for the nitrogen atom may include a functional group in which an acidic functional group is substituted with an aliphatic, alicyclic or aromatic functional group. The content of the acidic functional group is the same as described above.

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

In the polyfunctional N-substituted maleimide compound, the functional group mediating the bond between nitrogen atoms included in each of the two or more maleimide compounds may include various well-known aliphatic, alicyclic or aromatic functional groups without limitation, specific examples include , 4,4'-diphenylmethane functional group, etc. may be used. The functional group substituted for the nitrogen atom may include a functional group in which an acidic functional group is substituted with an aliphatic, alicyclic or aromatic functional group. The content of the acidic functional group is the same as described above.

Specific examples of the polyfunctional N-substituted maleimide compound include 4,4'-diphenylmethane bismaleimide (BMI-1000, BMI-1100, etc., manufactured by Daiwakasei), phenylmethane bismaleimide, and m-phenylenemethane bismaleimide. Mead, bisphenol A diphenylether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide imide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, and the like.

The amine compound may be a primary amine compound containing at least one amino group (-NH ₂ ) in its molecular structure, and more preferably a carboxylic acid compound substituted with an amino group, a polyfunctional amine compound containing two or more amino groups, or Mixtures thereof may 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 of aliphatic, alicyclic or aromatic carboxylic acids depending on the type of hydrocarbon bound to the carboxylic acid functional group. . As a plurality of carboxylic acid functional groups are included in the alkali-soluble resin through the carboxylic acid compound substituted with the amino group, the developability of the alkali-soluble resin may be improved.

The term "substitution" 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 substituted amino groups is 1 or more. can

Specific examples of the carboxylic acid compound substituted with the amino group include 20 kinds of α-amino acids, 4-aminobutanoic acid, 5-aminopentanoic acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8 -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 a molecule, and may include all of aliphatic, alicyclic or aromatic polyfunctional amines depending on the type of hydrocarbon bonded to the amino group. there is. Flexibility, toughness, copper foil adhesion, etc. of the alkali-soluble resin may be improved through the polyfunctional amine compound including 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-phenylenediamine, 2,3,5 ,6-Tetrafluoro-1,4-phenylenediamine, 4,6-diaminoresorcinol, 2,5-diamino-1,4-benzenedithiol, 3-aminobenzylamine, 4-aminobenzyl Amine, 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'-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)- 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- amino Phenyl)-2-propyl]benzene, 1,1'-bis(4-aminophenyl)-cyclohexane, 9,9'-bis(4-aminophenyl)-fluorene, 9,9'-bis(4- Amino-3-chlorophenyl) fluorene, 9,9'-bis (4-amino-3-fluorophenyl) fluorene, 9,9'-bis (4-amino-3-methylphenyl) fluorene, 3, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)-benzene, 1,3-bis(4-aminophenoxy)- Benzene, 1,4-bis(4-aminophenoxy)-benzene, 1,4-bis(4-amino-2-trifluoromethylphenoxy)-benzene, 4,4'-bis(4-aminophenoxy) Si)-biphenyl, 2,2'-bis[4-(4-aminophenoxy)-phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)-phenyl]hexafluoropropane , bis(2-aminophenyl)sulfide, bis(4-aminophenyl)sulfide, bis(3-aminophenyl)sulfone, bis(4-aminophenyl)sulfone, bis(3-amino-4-hydroxy)sulfone, Bis[4-(3-aminophenoxy)-phenyl]sulfone, bis[4-(4-aminophenoxy)-phenyl]sulfone, o-tolidine sulfone, 3,6-diaminocarbazole, 1,3 ,5-tris(4-aminophenyl)-benzene, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, 4,4'-diaminobenzanilide, 2-(3-aminophenyl)-5 -Aminobenzimidazole, 2-(4-aminophenyl)-5-aminobenzoxazole, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5 -amine, 4,6-diaminoresorcinol, 2,3,5,6-pyridinetetraamine, polyfunctional amine including the 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 amine containing Dow Corning siloxane structure (Dow Corning 3055), polyether structure containing polyfunctional amines (manufactured by Huntsman, BASF) and the like.

In addition, the alkali-soluble resin may include a repeating unit represented by the following Chemical Formula 7; and at least one repeating unit represented by the following Chemical Formula 8, respectively.

[Formula 7]

In Formula 7, R ₅ 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, "*" means a bonding point,

[Formula 8]

In Formula 8, R ₆ 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 ₇ is -H, -OH, -NR ₈ R ₉ , halogen, or an alkyl group having 1 to 20 carbon atoms, wherein R ₈ and R ₉ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, "*" is a bonding point it means.

Preferably, in Formula 7, R ₅ may be phenylene, in Formula 8, R ₆ may be phenylene, and R ₇ may be —OH.

On the other hand, the alkali-soluble resin may include a repeating unit represented by Chemical Formula 7; And it may further include a vinyl-based repeating unit in addition to the repeating unit represented by the formula (8). The vinyl-based repeating unit is a repeating unit included in a homopolymer of a vinyl-based monomer including at least one vinyl group in a molecule, and examples of the vinyl-based monomer are not particularly limited, for example, ethylene, propylene, isobutylene. , butadiene, styrene, acrylic acid, methacrylic acid, maleic anhydride, or maleimide.

a repeating unit represented by the above-described Chemical Formula 7; And the alkali-soluble resin each comprising at least one repeating unit represented by the formula (8) is a polymer including a repeating unit represented by the following formula (9), an amine represented by the following formula (10), and an amine represented by the following formula (11) can be manufactured.

[Formula 9]

[Formula 10]

[Formula 11]

In Formulas 9 to 11, R ₅ to R ₇ are the same as described above in Formulas 7 and 8, and “*” means a bonding point.

Specific examples of the polymer including the repeating unit represented by Formula 9 are not particularly limited, but for example, SMA of Cray valley, Xiran of Polyscope, Scripset of Solenis, Isobam of Kuraray, Polyanhydride resin of Chevron Phillips Chemical, Lindau Chemicals Maldene, Inc., etc. are mentioned.

In addition, the repeating unit represented by the above formula (7); And the alkali-soluble resin each comprising at least one repeating unit represented by Formula 8 may be prepared by reacting a compound represented by Formula 12 with a compound represented by Formula 13 below.

[Formula 12]

[Formula 13]

In Formulas 12 and 13, R ₅ to R ₇ are the same as described above in Formulas 7 and 8.

In addition, as the alkali-soluble resin, a known and usual carboxy group-containing resin or phenol group-containing resin containing a carboxy group or a phenol group in the molecule may be used. Preferably, the carboxyl group-containing resin or the carboxyl group-containing resin may be mixed with a phenol group-containing resin.

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

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

(2) a carboxyl group-containing resin obtained by reacting a bifunctional epoxy resin with a difunctional phenol and/or a dicarboxyl group and then reacting a polybasic acid anhydride;

(3) a carboxyl group-containing resin obtained by reacting a polyfunctional phenol resin with a compound having one epoxy group in a molecule and then reacting a polybasic acid anhydride;

(4) Carboxylic group-containing resin formed by reacting a polybasic acid anhydride with a compound having two or more alcoholic hydroxyl groups in the molecule

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

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

(7) A resin prepared by ring-opening an anhydride of a polymaleic anhydride resin and a polymaleic anhydride resin copolymer reacted with maleic anhydride with a weak acid, diamine, imidazole, or dimethyl sulfoxide; However, it is not limited to these.

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

Examples of the phenol group-containing resin are not particularly limited, but for example, novolak resins such as phenol novolac 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) propan-2-yl)phenyl)ethane-1,1-diyl)diphenol] can be used alone or mixed.

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. Examples of the method for measuring the acid value of the alkali-soluble resin are not particularly limited, but, for example, the following method may be used. Prepare a KOH solution (solvent: methanol) having a concentration of 0.1 N as a base solution, and alpha-naphtholbenzein (pH: 0.8 ~ 8.2 yellow, 10.0 blue green) as an indicator was prepared. Then, about 1 to 2 g of the alkali-soluble resin as a sample was taken, dissolved in 50 g of a dimethylformaldehyde (DMF) solvent, a marker was added, and then titrated with a base solvent. At the completion of the titration, the acid value was calculated as the amount of the base solvent used in units of mg KOH/g.

When the acid value of the alkali-soluble resin is excessively reduced to less than 50 mgKOH/g, the developability of the alkali-soluble resin may be lowered, and thus 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 from other resins may occur due to increased polarity.

According to an exemplary embodiment of the present invention, the thermosetting binder is 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 cyanide group, a maleimide group, and a benzo group. and an epoxy group. 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 thioether group, a cyanide group, a maleimide group, a benzoxazine group, or these groups It may include a mixture of two or more of. Such a thermosetting binder may form a cross-link with an alkali-soluble resin or the like by thermosetting to ensure heat resistance or mechanical properties of the insulating layer.

More specifically, as the thermosetting binder, a polyfunctional resin compound including two or more of the above-described functional groups in a molecule may be used. The polyfunctional resin compound may include a resin including 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 contains a compound having at least two or more groups of any one or two types of cyclic ether groups of 3, 4, or 5-membered rings or cyclic thioether groups in the molecule can do.

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

In addition, 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 or more oxetanyl groups in the molecule, or episul containing two or more thioether groups in the molecule It may include a feed resin, a polyfunctional cyanate ester compound containing at least two or more cyanide groups in a molecule, or a polyfunctional benzoxazine compound containing at least two or more benzoxazine groups in a molecule.

Specific examples of the polyfunctional epoxy compound include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, novolak epoxy resin , Phenol novolac 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, gly Oxal-type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenolic-type epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoylethane resin, silicone-modified epoxy resin , ε-caprolactone-modified epoxy resin and the like. In addition, for imparting flame retardancy, one 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, can be improved.

Examples of the polyfunctional oxetane compound include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, and 1,4-bis[( 3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methylacryl Late, (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 or copolymers of The etherified product with resin which has hydroxyl groups, such as quioxane, etc. are mentioned. In addition, the copolymer etc. of the unsaturated monomer which have an oxetane ring, and alkyl (meth)acrylate are mentioned.

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

Examples of the polyfunctional maleimide compound include 4,4'-diphenylmethane bismaleimide, 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-phenylene bismaleimide (4-methyl-1,3-phenylene bismaleimide), 1,6'- Bismaleimide-(2,2,4-trimethyl)hexane (1,6'-bismaleimide-(2,2,4-trimethyl)hexane) etc. are mentioned.

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

More specific examples of the polyfunctional resin compound include YDCN-500-80P of Kukdo Chemical, PT-30S of phenol novolac-type cyanite ester resin of Lonza, BMI-2300 of phenylmethane-type maleimide resin of Daiwa, Pd of Shikoku. A type benzoxazine resin etc. are mentioned.

According to an exemplary embodiment of the present invention, the content of the thermosetting binder in the insulating composition may be 1 part by weight or more and 150 parts by weight or less based on 100 parts by weight of the alkali-soluble resin. Specifically, the content of the thermosetting binder is based on 100 parts by weight of the alkali-soluble resin, 10 parts by weight or more and 100 parts by weight or less, 20 parts by weight or more and 50 parts by weight or less, 1 part by weight or more and 35 parts by weight or more, 40 parts by weight or more. 90 parts by weight or less, or 120 parts by weight or more and 150 parts by weight or less.

By adjusting the content of the alkali-soluble resin and the thermosetting binder to the above-mentioned ranges, it is possible to prevent deterioration of the developability and strength of the insulating layer, and it is possible to further improve the thermosetting uniformity of the insulating composition.

An exemplary embodiment of the present invention provides a method for manufacturing an insulating layer using the insulating composition. Specifically, the method for manufacturing an insulating layer according to an exemplary embodiment of the present invention includes the steps of: applying the insulating composition on a conductor wiring having a metal protrusion formed on the surface; forming an insulating film by first curing the insulating composition; The method may include exposing the metal protrusions by etching the surface of the insulating layer with an aqueous alkali solution, and secondary curing of the insulating layer exposing the metal protrusions.

In the method for manufacturing an insulating layer according to an exemplary embodiment of the present invention, an insulating layer having excellent adhesion to a conductor wiring can be easily formed by using the insulating composition.

According to an exemplary embodiment of the present invention, it is possible to prepare a conductor wiring having a metal protrusion formed on the surface. Examples of the method for forming the metal protrusions on the surface of the conductor wiring are not particularly limited, and for example, a plating process for the opening of the photosensitive resin layer pattern or an adhesion process using an adhesive may be used.

As a specific example of the plating process for the opening of the photosensitive resin layer pattern, forming a metal protrusion including laminating a photosensitive resin layer on a conductor wiring, forming a pattern on the photosensitive resin layer, and electroplating method can be used.

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

Accordingly, when a portion of the photosensitive resin layer is selectively exposed and then alkali-developed, the exposed portion is not developed, and only the unexposed portion may be selectively etched and removed. As described above, the portion of the photosensitive resin layer that remains intact without being alkali-developed by exposure is referred to as a photosensitive resin pattern.

That is, as an example of a method of exposing the photosensitive resin layer, a photomask formed in a predetermined pattern on the photosensitive resin layer is contacted and irradiated with ultraviolet rays, or a predetermined pattern included in the mask is imaged through a projection objective lens. Then, it can be selectively exposed through a method such as irradiating ultraviolet rays or directly imaging using a laser diode as a light source and then irradiating ultraviolet rays. At this time, examples of the ultraviolet irradiation condition include irradiation with a light quantity of ^{5 mJ/cm 2} to 600 mJ/cm ^{2 .}

In addition, an example of a method of performing alkali development 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, the concentration and temperature of an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, amines, etc. can be used by adjusting the temperature, and alkali developer sold as a commercial product can also be used. The specific amount of the alkali developer is not particularly limited, but it is necessary to adjust the concentration and temperature not to damage the photosensitive resin pattern, for example, 0.5% to 3% sodium carbonate aqueous solution at 25 ° C. to 35 ° C. can be used. .

Meanwhile, in the electroplating step, examples of the plating method include a dry deposition process or a wet deposition process, and specific examples of the dry deposition process include vacuum deposition, ion plating, sputtering, and the like. Meanwhile, specific examples of the wet deposition process include electroless plating of various metals, and electroless copper plating is common, and may further include a roughening process before or after deposition.

In the roughening process, there are dry and wet methods depending on conditions. Examples of the dry method include vacuum, atmospheric pressure, plasma treatment for each gas, Excimer UV treatment for each gas, and the like, and examples of the wet method include desmear. processing can be used. Through this roughening process, it is possible to increase the surface roughness of the metal thin film to improve adhesion to the metal deposited on the metal thin film.

In addition, in order to leave only the metal protrusion, after the electroplating step, the step of removing the photosensitive resin layer may be further included. 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 conductor wiring and metal protrusion as much as possible.

As a specific example of the method for stripping the photosensitive resin pattern, a photoresist stripper may be treated, a desmear process or plasma etching may be performed, and the above methods may be mixed.

On the other hand, as a specific example of the bonding process using the adhesive, a metal protrusion is formed on the surface of a passive device such as micc or an active device such as a semiconductor chip, and then the opposite side of the formed metal protrusion is applied to the surface of the conductor wiring using an insulating adhesive. Adhesive method can be used. In this case, as the method of forming the metal protrusion on the surface of the passive element or the active element, the method of the plating process for the opening of the photosensitive resin layer pattern described above may be used as it is. For example, a method may be used in which a photosensitive resin layer pattern is formed on the surface of a passive element or an active element, and then metal is plated on the opening portion of the pattern.

According to an exemplary embodiment of the present invention, the metal protrusion may have a height of 1 μm or more and 20 μm or less, and a cross-sectional diameter of 5 μm or more and 30 μm or less. The cross-sectional diameter may mean a diameter or a maximum diameter of a cross-section in which the metal projection is cut in a direction perpendicular to the height direction of the metal projection. For example, the shape of the metal protrusion may include a cylinder, a truncated cone, a polygonal prism, a polygonal truncated pyramid, an inverted truncated cone, or an inverted polygonal truncated cone. Examples of the metal component included in the metal protrusion are also not particularly limited, and for example, a conductive metal such as copper or aluminum may be used.

According to an exemplary embodiment of the present invention, the insulating composition may be applied on the conductor wiring having the metal protrusion formed on the surface, thereby sealing the conductor wiring having the metal protrusion formed on the surface. The insulating composition may be applied to a thickness of 1 μm or more and 500 μm or less, 3 μm or more and 500 μm or less, 3 μm or more and 200 μm or less, 1 μm or more and 60 μm or less, or 5 μm or more and 30 μm or less.

The conductor wiring may exist in a state formed on a substrate including a semiconductor material such as a circuit board, a sheet, and a multilayer printed wiring board underneath. As such, in a state in which the conductor wiring is present on the substrate, the conductor wiring may be sealed through a method of applying the insulating composition on the substrate. Meanwhile, the conductor wiring may be sealed by applying an insulating composition on a carrier film, drying the insulating composition to form a resin layer, and then laminating the substrate and the resin layer.

According to an exemplary embodiment of the present invention, an insulating film may be formed by first curing the insulating composition. Through the step of first curing the insulating composition, the thermosetting binder and the alkali-soluble resin may be cross-linked. By crosslinking the thermosetting binder and the alkali-soluble resin, heat resistance and mechanical properties of the insulating film may be secured.

According to an exemplary embodiment of the present invention, the primary curing may be performed at a temperature of 50° C. or more and 150° C. or less, for 0.1 hours or more and 2 hours or less. By controlling the temperature and time for performing the primary curing in the above-described ranges, crosslinking of the thermosetting binder and the alkali-soluble resin may be more stably performed. In addition, it is possible to prevent excessive damage to the formed insulating film.

According to an exemplary embodiment of the present invention, the metal protrusion may be exposed by etching the surface of the insulating layer with an aqueous alkali solution. By exposing the metal protrusions sealed by the insulating layer through chemical etching with an aqueous alkali solution, physical damage to the insulating layer can be prevented.

As the surface of the insulating layer is etched with an aqueous alkali solution to expose the metal protrusions, an electrical signal may be connected to the conductor wiring sealed inside the insulating layer through the exposed metal protrusions.

The metal protrusion may be exposed using an aqueous alkali solution. The aqueous alkali solution may have a temperature of 10 ℃ to 100 ℃ or 25 ℃ to 60 ℃, and a concentration of 1% to 10%, or 1% to 5%, more specifically, a photoresist stripper may be used. By the aqueous alkali solution, the bonding of the polymer matrix in the insulating film formed through the primary curing may be broken, and the insulating film may be removed by etching.

At this time, by adjusting the concentration and temperature of the aqueous alkali solution, the etching rate of the insulating film by the aqueous alkali solution can be controlled, and the thickness of the insulating film can be easily maintained while maintaining the etching rate at an appropriate level within the above-described range to secure process efficiency. can be adjusted.

As the aqueous alkali solution, aqueous solutions of metal hydroxides such as potassium hydroxide and sodium hydroxide can be used, and commercially sold products such as Resistrip products from Atotech, ORC-731, ORC-723K, ORC-740, SLF-6000 from ORChem, etc. can also be used

The etching by the aqueous alkali solution may proceed from the surface of the insulating layer. The surface of the insulating film means an area in which the insulating film sealing the conductor wiring having the metal protrusion formed on the surface contacts the air, and as etching proceeds from the surface of the insulating film to the inside, the metal protrusion may be exposed.

In order for the etching by the aqueous alkali solution to proceed from the surface of the insulating layer, the aqueous alkali solution may be in contact with the surface of the insulating layer. At this time, in order to secure thickness uniformity through uniform removal without physical damage to the insulating film, the aqueous alkali solution may be brought into contact with the surface of the insulating film by spraying or the like.

According to an exemplary embodiment of the present invention, the insulating layer may be formed by secondary curing of the insulating film exposing the metal protrusion. By secondary curing the insulating film, the bonding of the polymer matrix in the insulating film broken by the aqueous alkali solution can be repaired, and finally, an insulating layer having excellent chemical resistance can be formed.

According to an exemplary embodiment of the present invention, the secondary curing may be performed at a temperature of 150° C. or more and 250° C. or less, for 0.1 hours or more and 10 hours or less. By controlling the temperature and time for performing the secondary curing within the above-described ranges, the insulating layer having excellent adhesion to the conductor wiring can be easily formed.

Meanwhile, after the secondary curing step, if necessary, the method may further include removing the substrate formed under the conductor wiring. As described above, the conductor wiring may exist in a state formed on a substrate including a semiconductor material such as a circuit board, a sheet, and a multilayer printed wiring board underneath. In order to form a multilayer circuit board having a finer structure, the substrate under the conductor wiring may be removed, if necessary.

An exemplary embodiment of the present invention provides a method for manufacturing a multilayer printed circuit board comprising the step of forming a metal pattern layer on the insulating layer manufactured by the insulating layer manufacturing method.

According to an exemplary embodiment of the present invention, a conductor wiring is included in the insulating layer, and a metal protrusion formed on the surface of the conductor wiring is exposed to the outside of the insulating layer, and a metal pattern layer is newly laminated on the insulating layer. In this case, the metal pattern layer may transmit and receive electrical signals to and from the conductor wiring inside the insulating layer through the metal protrusions.

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

According to an exemplary embodiment of the present invention, the forming of the metal pattern layer on the insulating layer includes forming a metal thin film on the insulating layer, forming a photosensitive resin layer having a pattern 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 the metal thin film on the insulating layer, examples of the method for forming the metal thin film include a dry deposition process or a wet deposition process, and specific examples of the dry deposition process include vacuum deposition, ion plating, and sputtering. and the like.

Meanwhile, specific examples of the wet deposition process include electroless plating of various metals, and electroless copper plating is common, and may further include a roughening process before or after deposition. In the roughening process, there are dry and wet methods depending on conditions. Examples of the dry method include vacuum, atmospheric pressure, plasma treatment for each gas, Excimer UV treatment for each gas, and the like, and examples of the wet method include desmear. processing can be used. Through this roughening process, it is possible to increase the surface roughness of the metal thin film to improve adhesion to the metal deposited on the metal thin film.

According to an exemplary embodiment of the present invention, 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 adhesive force between the metal thin film and the insulating layer may be improved.

Specifically, as an example of a method of forming the 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 may be used. The plasma processing method may include any one of an atmospheric pressure plasma processing method, a DC plasma processing method, and an RF plasma processing method. As a result of the surface treatment process, a surface treatment layer including a reactive functional group may be formed on the surface of the insulating layer. Another example of the method of forming the surface treatment layer on the insulating layer may include a method of depositing a chromium (Cr) or titanium (Ti) metal having a thickness of 50 nm to 300 nm on the surface of the insulating layer.

According to an exemplary embodiment of the present invention, the step of forming the photosensitive resin layer having a pattern formed thereon on the metal thin film may include exposing and developing the photosensitive resin layer formed on the metal thin film. It may be the same as the contents of the above-described exposure and development of the photosensitive resin layer.

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

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

At this time, the metal deposited on the metal thin film exposed by the photosensitive resin layer pattern may form the above-described metal pattern layer, and more specifically, the metal pattern layer is connected to the conductor wiring through the metal protrusion. can be formed. Through this, the metal pattern layer may transmit and receive electrical signals to and from the conductor wiring included in the insulating layer. More specifically, one end of the metal protrusion may contact the conductor wiring, and the other end of the metal protrusion may contact the metal pattern layer to electrically connect the conductor wiring and the metal pattern layer.

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

The multilayer printed circuit board manufactured by the method of manufacturing the multilayer printed circuit board can be used again as a build-up 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 process of forming a metal substrate on the insulating layer and the second process of forming a metal substrate on the insulating layer according to the method for 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 method for manufacturing the multilayer printed circuit board is also not significantly limited, and for example, one or more layers, or 1 to 20 layers, depending on the purpose and purpose of use. can have

Hereinafter, examples will be given to describe the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present invention to those of ordinary skill in the art.

Preparation of alkali-soluble resin and insulating composition

alkali Preparation of Soluble Resins

manufacturing example

543 g of dimethylacetamide (DMAc) as a solvent was placed in a reaction vessel with a heating and cooling volume of 2 liters equipped with a thermometer, stirring device, reflux condenser, and moisture meter, 350 g of Cray Valley’s SMA1000, 4-aminobenzo Ik acid (4-aminobenzoic acid, PABA) 144g, 4-aminophenol (4-aminophenol, PAP) 49g was added and mixed. In a nitrogen atmosphere, the temperature of the reactor was set to 80 ° C, and the acid anhydride and the aniline derivative reacted for 24 hours to form amic acid. Then, the temperature of the reactor was set to 150 ° C. and the imidization reaction was continued for 24 hours. , an alkali-soluble resin solution having a solid content of 50% was prepared.

first insulating composition

In a 1L reactor, 82 g of 2-methyl imidazole as imidazole, 236 g of KBM-403 as silane, and 466 g of DMAc as solvent were added and stirred, and the temperature was raised to 90 ° C. and maintained for 6 hours to obtain a reactant.

Then, 148 g of phthalic anhydride was further added to the reactant, and the mixture was maintained at 90° C. for 6 hours to prepare an imidazole-silane compound containing a carboxyl group of Compound 1.

[Compound 1]

The prepared carboxyl group-containing imidazole-silane compound had a pKa of about 3.07.

Then, 16 g of the alkali-soluble resin prepared in Preparation Example, 1 g of the prepared imidazole-silane compound containing a carboxyl group, 5 g of MY-510 (manufactured by Huntsman) as a thermosetting binder, SC2050 MTO (70% solid content, manufactured by Adamatech) as an inorganic filler 35 g was mixed to prepare a first insulating composition.

second insulating composition

In a 1L reactor, 82 g of 2-methyl imidazole as imidazole, 236 g of KBM-403 as silane, and 466 g of DMAc as solvent were added and stirred, and the temperature was raised to 90 ° C. and maintained for 6 hours to obtain a reactant.

Thereafter, 192 g of trimellitic anhydride as phthalic anhydride was further added to the reaction product, and the mixture was maintained at 90° C. for 6 hours to prepare an imidazole-silane compound containing a carboxyl group of Compound 2.

[Compound 2]

The pKa of the prepared imidazole-silane compound containing a carboxyl group was about 2.65 and 3.61.

Thereafter, a second insulation composition was prepared in the same manner as the method for preparing the first insulation composition.

Third Insulation Composition

In a 1L reactor, 82 g of 2-methyl imidazole as imidazole, 236 g of KBM-403 as silane, and 466 g of DMAc as solvent were added and stirred, and the temperature was raised to 90 ° C. and maintained for 6 hours to obtain a reactant.

Thereafter, 193 g of 3-nitrophthalic anhydride as phthalic anhydride was further added to the reaction product, and the mixture was maintained at 90° C. for 6 hours to prepare an imidazole-silane compound containing a carboxyl group of Compound 3.

[Compound 3]

The prepared carboxyl group-containing imidazole-silane compound had a pKa of about 1.76.

Thereafter, a third insulation composition was prepared in the same manner as the method for preparing the first insulation composition.

Fourth Insulation Composition

In a 1L reactor, 82 g of 2-methyl imidazole as imidazole, 236 g of KBM-403 as silane, and 318 g of DMAc as solvent were put and stirred, and the temperature was raised to 90 ° C. and maintained for 6 hours to imidazole-silane compound. was prepared.

Thereafter, a fourth insulation composition was prepared in the same manner as the method for preparing the first insulation composition.

insulating layer manufacturing

Example One

The first insulating composition prepared above was applied to an untreated PET film having a thickness of 25 µm and dried to prepare a resin layer having a thickness of 18 µm.

Example 2

An insulating layer was prepared in the same manner as in Example 1, except that the second insulating composition was used instead of the first insulating composition in Example 1.

Example 3

An insulating layer was prepared in the same manner as in Example 1, except that the third insulating composition was used instead of the first insulating composition in Example 1.

comparative example One

An insulating layer was prepared in the same manner as in Example 1, except that the fourth insulating composition was used instead of the first insulating composition in Example 1.

comparative example 2

An insulating layer was prepared in the same manner as in Example 1, except that an insulating material composition excluding the imidazole-silane compound of the first insulating composition was used in Example 1.

Manufacturing of multilayer printed circuit boards

A dry film (RY-5319, Hitachi Chemical) was laminated on a copper clad laminate (LG-500GA VB/VB, LG Chem) to which an ultra-thin copper foil was adhered, to form a pattern, and electroplating to form a circuit using the MSAP method. Thereafter, a dry film (RY-5319, Hitachi Chemical) was laminated on the circuit to form a pattern, and electroplating was performed to form copper bumps with a height of 15 μm and a diameter of 20 μm.

Then, each of the insulating layers of Examples 1 to 3 and Comparative Examples 1 and 2 were vacuum laminated on the copper clad laminate to seal the circuit and the copper bump, and the PET film was removed from the insulating layer. The laminated resin layer was first thermally cured at a temperature of 100° C. for 1 hour to form an insulating film. Thereafter, a 3% sodium hydroxide resist stripper at a temperature of 50° C. was sprayed onto the surface of the insulating film, removed to a depth of about 3 μm from the surface of the insulating film, the copper bumps were exposed on the surface, and washed and dried. At this time, the process of exposing the copper bumps was performed for 10 to 60 seconds per panel as a continuous process.

Then, an insulating layer was prepared by secondary thermal curing of the insulating film on which the copper bumps were exposed at a temperature of 200° C. for 1 hour.

A copper thin film is deposited on the insulating layer using electroless copper plating, heated at 100 ° C for 30 minutes to improve adhesion with electroless copper plating, and then a dry film (RY-5319, Hitachi Chemical Co., Ltd.) is laminated. Then, a pattern was formed and a circuit was formed by the SAP method by electroplating. Then, the copper clad laminate and the ultra-thin foil were separated and removed from the insulating layer to complete a multilayer printed circuit board.

Experimental example 1: Room temperature stability evaluation experiment

The insulating layers of Examples 1 to 3 and Comparative Examples 1 and 2 were prepared, and then left at room temperature of 25° C. for one week, and then multilayer printed circuit boards were manufactured.

Examples 1 to 3 and Comparative Example 2 produced multilayer printed circuit boards, but there was no significant change at room temperature. In Comparative Example 1, an insulating layer was vacuum laminated on a copper clad laminate. Due to the reaction, there was a problem that the circuit and the copper bump could not be sealed and separated.

Experimental example 2: Copper foil adhesion measurement experiment

All of the copper foil on the copper clad laminate (LG-500GA VB/VB, LG Chem) was removed, and the insulating layer prepared using the first insulating composition was vacuum laminated to remove the PET film from the insulating layer. The laminated resin layer was first thermally cured at a temperature of 100° C. for 1 hour to form an insulating film. Thereafter, a 3% sodium hydroxide resist stripper at a temperature of 50° C. was sprayed onto the surface of the insulating film, removed to a depth of about 3 μm from the surface of the insulating film, washed with water and dried. At this time, the insulating film removal process was performed as a continuous process for 10 to 60 seconds per panel.

Then, the insulating layer was prepared by secondary heat curing at a temperature of 200° C. for 1 hour.

A copper thin film was deposited on the insulating layer using electroless copper plating, heated at 100 ° C. for 30 minutes to improve adhesion with electroless copper plating, and then electroplating to manufacture a 25 μm thick copper foil. Evaluation samples were prepared. The second, third, and fourth insulating compositions were prepared in the same manner, respectively.

As a result of comparing the adhesion of the copper foil adhesion evaluation samples according to the IPC-TM-650 standard, Examples 1 to 3 and Comparative Example 1 secured copper foil adhesion of 0.3 kgf/cm or more, but Comparative Example 2 secured 0.3 kgf/cm or more couldn't

Claims (14)

an imidazole-silane compound containing a carboxyl group represented by the following formula (1); alkali-soluble resin; and a thermosetting binder; an insulating composition comprising:
[Formula 1]

In Formula 1, R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
X is an alkylene group having 2 to 6 carbon atoms, wherein at least one -CH ₂ - group may be independently substituted with -O-,
R ₂ is an alkoxy group having 1 to 3 carbon atoms,
R ₃ is a nitro group or a carboxyl group.
The method according to claim 1,
The carboxyl group-containing imidazole-silane compound,
imidazole represented by the following formula (2);
silane represented by the following formula (3); and
An insulating composition which is a reaction product of a mixture containing phthalic anhydride represented by the following formula (4):
[Formula 2]

[Formula 3]

[Formula 4]

In Formula 1, R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
In Formula 2, X is an alkylene group having 2 to 6 carbon atoms, in this case, one or more -CH ₂ -groups may be independently substituted with -O-, R ₂ is an alkoxy group having 1 to 3 carbon atoms,
In Formula 3, R ₃ is a nitro group or a carboxyl group.
3. The method according to claim 2,
The content of the silane is 250 parts by weight or more and 350 parts by weight or less based on 100 parts by weight of the imidazole insulation composition.
3. The method according to claim 2,
The content of the phthalic anhydride is 150 parts by weight or more and 300 parts by weight or less based on 100 parts by weight of the imidazole.
The method according to claim 1,
The carboxyl group-containing imidazole-silane compound,
An insulating composition comprising at least one of the carboxyl group-containing imidazole-silane compounds represented by the following compounds 1 to 3:
[Compound 1]

[Compound 2]

[Compound 3]

.
The method according to claim 1,
The pKa of the carboxyl group-containing imidazole-silane compound is 1.5 or more and 3.5 or less.
The method according to claim 1,
The content of the thermosetting binder is 1 part by weight or more and 150 parts by weight or less based on 100 parts by weight of the alkali-soluble resin.
The method according to claim 1,
The thermosetting binder is an insulating composition comprising at least one functional group of an oxetanyl group, a cyclic ether group, a cyclic thioether group, a cyanide group, a maleimide group, and a benzo group and an epoxy group.
applying the insulating composition according to claim 1 on the conductor wiring having the metal protrusion formed on the surface;
forming an insulating film by first curing the insulating composition;
exposing the metal protrusions by etching the surface of the insulating layer with an aqueous alkali solution; and
and secondary curing of the insulating film exposing the metal protrusion.
10. The method of claim 9,
The primary curing is at a temperature of 50 ℃ or more and 150 ℃ or less, and the insulating layer manufacturing method is carried out for 0.1 hours or more and 2 hours or less.
10. The method of claim 9,
The secondary curing is carried out at a temperature of 150 ℃ or more and 250 ℃ or less, for 0.1 hours or more and 10 hours or less.
A method of manufacturing a multilayer printed circuit board comprising forming a metal pattern layer on the insulating layer manufactured according to claim 9 .
13. The method of claim 12,
The step of forming a metal pattern layer on the insulating layer,
forming a metal thin film on the insulating layer;
forming a photosensitive resin layer having a pattern formed thereon on the metal thin film;
depositing a metal on the metal thin film exposed by the photosensitive resin layer pattern; and
and removing the photosensitive resin layer and removing the exposed metal thin film.
13. The method of claim 12,
The method of manufacturing a multilayer printed circuit board in which the metal pattern layer is connected to a conductor wiring through a metal protrusion.