WO2020060265A1 - Multi-layer printed circuit board, method for manufacturing same, and semiconductor device using same - Google Patents

Abstract

The present invention relates to a multi-layer printed circuit board, which uses a resin coated-metal thin film and thus includes a thin insulation layer, a method for manufacturing same, and a semiconductor device using same.

Description

Multilayer printed circuit board, manufacturing method thereof and semiconductor device using the same

Cross-citation with relevant application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0113248 on September 20, 2018 and Korean Patent Application No. 10-2019-0115354 on September 19, 2019. All content disclosed in the literature is incorporated as part of this specification.

The present invention relates to a multilayer printed circuit board having a thin thickness and excellent durability, a method for manufacturing the same, and a semiconductor device using the same.

Recently, electronic devices are becoming smaller, lighter, and more functional. To this end, the use of multi-layer printed circuit boards is rapidly increasing as the application fields of build-up printed circuit boards (PCBs) are rapidly expanding, focusing on small devices.

Multi-layered printed circuit boards are capable of three-dimensional wiring from planar wiring. Especially in industrial electronics, the integration of functional devices such as integrated circuit (IC) and large scale integration (LSI) is improved, and the size, weight, high functionality, and structure of electronic devices are improved. It is a product that is advantageous for electrical function integration, assembly time reduction, and cost reduction.

Recently, a technology for realizing a thinner thickness through a coreless multilayer printed circuit board using a removable core film such as a carrier film has been actively researched. In particular, prepreg is mainly used as an insulating material used in the coreless multilayer printed circuit board.

However, when the prepreg is applied as an insulating material, there is a limitation that it is difficult to sufficiently reduce the thickness of the multilayer printed circuit board due to the fiber reinforcement inside the prepreg. In addition, when simply applying a polymer resin film excluding the fiber reinforcement to simply set the thickness as an insulating material, there was a limit to damage the multi-layer printed circuit board during the desorption process of the carrier film by increasing brittleness.

Accordingly, there is a need to develop a multilayer printed circuit board having a thinner thickness than the prepreg and having excellent durability.

The present invention relates to a multilayer printed circuit board having a thin thickness and excellent durability.

In addition, the present invention is to provide a method for manufacturing the above multilayer printed circuit board.

In addition, the present invention is to provide a semiconductor device including the multi-layer printed circuit board.

In order to solve the above problems, in the present specification, a resin laminate including a plurality of build-up layers including an insulating pattern and a metal pattern; And a resist pattern layer formed on upper and lower surfaces of the resin laminate, wherein the thickness of the insulating pattern included in the build-up layer is 15 μm or less.

In the present specification, a first step of laminating a metal layer on both sides of a carrier film and forming a pattern; A second step of stacking an insulating layer on the metal layer and forming a pattern; A third step of laminating a metal layer on the insulating layer and forming a pattern; A fourth step of forming a resist layer on the metal layer; The fifth step of peeling the carrier film and the metal layer of the first step, laminating a resist layer on the surface of the peeled metal layer and forming a pattern; including, the insulating layer is a resin coating metal thin film having a thickness of 15 ㎛ or less Provided is a multi-layer printed circuit board manufacturing method in which the second and third steps are repeated one or more times after the third step.

Also provided herein is a semiconductor device, comprising a multi-layer printed circuit board.

Hereinafter, a multilayer printed circuit board according to a specific embodiment of the present invention, a method of manufacturing the same, and a semiconductor device using the same will be described in more detail.

Ⅰ. Multilayer Printed Circuit Board

According to an embodiment of the present invention, a resin laminate including a plurality of build-up layers including an insulating pattern and a metal pattern; And a resist pattern layer formed on upper and lower surfaces of the resin laminate, and the thickness of the insulating pattern included in the build-up layer is 15 μm or less, and a multilayer printed circuit board may be provided.

According to the present inventors, as the multilayer printed circuit board of the above embodiment, the thickness of the insulating pattern included in each build-up layer included in the resin laminate is reduced to 15 µm or less, a total of 5 build-up layers are stacked. The thickness of the multi-layer printed circuit board was 75 µm or less, and the thickness of the multi-layer printed circuit board on which a total of seven build-up layers were stacked was reduced to 105 µm or less through experiments, and the invention was completed.

In particular, in the multilayer printed circuit board of the above embodiment, as the resist layer is formed on the upper and lower surfaces of the resin laminate, even when manufacturing an ultra-thin multilayer printed circuit board, product damage such as tearing can be prevented and excellent durability can be realized.

Conventionally, a multilayer printed circuit board has been mainly produced by using a prepreg impregnated with woven glass fiber as an insulating layer, but the thickness of the insulating pattern included in each build-up layer included in the resin laminate is 16. With the increase of more than µm, the limit of increasing the thickness of the multi-layer printed circuit board with a total of 5 layers of build-up layers to 80 µm or more and increasing the thickness of the multi-layer printed circuit board with a total of 7 layers of build-up layers to 112 µm or more have.

(1) Resin laminate

The multilayer printed circuit board may include a resin laminate including a plurality of build-up layers including an insulating pattern and a metal pattern. The resin laminate has a form in which 2 or more, and 2 to 20 to 20 build-up layers are stacked, and may be referred to as a panel. The build-up layer may include an insulating pattern and a metal pattern.

Specifically, each of the build-up layers may include an insulating pattern and a metal pattern, and metal patterns included in adjacent build-up layers may contact each other to transmit electrical signals.

The metal pattern refers to a metal block obtained through partial etching of a metal layer in a method of manufacturing a multilayer printed circuit board, which will be described later. Examples of metals included in the metal pattern include metals such as gold, silver, copper, tin, nickel aluminum, and titanium, or alloys containing a mixture of two or more thereof, and the thickness of the metal pattern is 1 μm to It may be 20 μm, or 5 μm to 15 μm, or 9 μm to 11 μm. When the thickness of the metal pattern is excessively increased, as an excessive amount of metal is required to form the metal pattern, the cost of raw materials may increase, resulting in reduced efficiency in economical efficiency, thinning and highly integrated semiconductor devices. Can be difficult to apply.

The insulating pattern refers to a polymer resin block obtained through partial etching of the insulating layer in the method of manufacturing a multilayer printed circuit board described later. More specifically, when using a resin coated metal thin film as an insulating layer in the method of manufacturing the multilayer printed circuit board, the insulating pattern means a resin coated layer included in the resin coated metal thin film.

The thickness of the insulating pattern may be 15 μm or less, or 10 μm or less, or 1 μm to 15 μm, or 1 μm to 10 μm, or 5 μm to 10 μm, or 6 μm to 8 μm. When the thickness of the insulating pattern is excessively increased, as an excessive amount of insulating material is required to form the insulating pattern, the cost of raw materials may increase, resulting in reduced efficiency in economical aspects, thinning, and highly integrated semiconductor device. It can be difficult to apply to.

Although the specific composition is not particularly limited to the insulating pattern, preferably, the insulating pattern includes: 1) carbon atoms having 1 to 20 carbon atoms substituted or unsubstituted with sulfone groups, carbonyl groups, halogen groups, nitro groups, cyano groups or halogen groups; An alkyl group, ii) an aryl group having 6 to 20 carbon atoms unsubstituted or substituted with a nitro group, a cyano group or a halogen group, iii) a heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with a nitro group, a cyano group or a halogen group, and iv) an amine compound containing at least one functional group selected from the group consisting of an alkylene group having 1 to 20 carbon atoms unsubstituted or substituted with a nitro group, a cyano group or a halogen group; Thermosetting resins; And a thermoplastic resin; may include a cured product of the liver, and an inorganic filler dispersed between the cured product.

More specifically, the insulating pattern, i) a sulfone group, a carbonyl group, a halogen group, a nitro group, a cyano group or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, ii) a nitro group, a cyano group or a halogen group A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, iii) a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, or iv) a nitro group, a cyano group, or a halogen group, or An amine compound containing at least one functional group selected from the group consisting of an unsubstituted alkylene group having 1 to 20 carbon atoms; Thermosetting resins; Thermoplastic resins; And an inorganic filler, containing 40 parts by weight to 90 parts by weight of the thermoplastic resin with respect to 100 parts by weight of the total of the amine compound and the thermosetting resin, and complexing up to 2000 Pa · s in the range of 120 ° C. to 180 ° C. It may include a cured product of a thermosetting resin composition for coating a thin metal film having a viscosity.

In the insulating pattern, a resin system composed of an epoxy and an amine curing agent and a certain amount of a thermoplastic resin are introduced to optimize the resin type and mixing ratio to secure the flowability of the resin.

More specifically, the curing reaction of the resin can be easily controlled by using a specific amine curing agent. More specifically, the modulus can be lowered by adjusting the functional group of the amine curing agent to control the number of bonds generated during the curing reaction of the resin. Through this, crack resistance is increased and it is possible to have more stability against the same tensile force or impact.

The i) a sulfone group, a carbonyl group, a halogen group, a nitro group, a cyano group or an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with a halogen group, ii) a nitro group, a cyano group or a 6 to 6 carbon atoms unsubstituted or substituted with a halogen group Aryl group of 20, iii) heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with nitro group, cyano group or halogen group, and iv) 1 to 20 carbon atoms unsubstituted or substituted with nitro group, cyano group or halogen group An amine compound containing at least one functional group selected from the group consisting of alkylene groups; Thermosetting resins; And a thermoplastic resin; the glass transition temperature (Tg) of the cured product of the liver or the cured product of the thermosetting resin composition for coating the metal thin film is 220 ° C to 240 ° C.

In addition, i) an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with a sulfone group, a carbonyl group, a halogen group, a nitro group, a cyano group or a halogen group, ii) a carbon number substituted or unsubstituted with a nitro group, a cyano group or a halogen group. Aryl groups of 6 to 20, iii) heteroaryl groups having 2 to 30 carbon atoms unsubstituted or substituted with a nitro group, cyano group or halogen group, and iv) 1 to 1 carbon atoms unsubstituted or substituted with a nitro group, cyano group or halogen group An amine compound containing at least one functional group selected from the group consisting of alkylene groups of 20; Thermosetting resins; And a thermoplastic resin; the cured product of the liver or the coating cured product of the thermosetting resin composition for coating the metal thin film according to IPC-TM-650 (2.4.18.3), in the MD direction measured using a Universal Testing Machine (Instron 3365) equipment. The tensile elongation may be 1% or more, or 1% to 10%, or 2% to 5%, or 3% to 4%, or 3.6% to 3.8%.

That is, as a result of a tensile test with a resin composition composed of a single molecule series, it can be observed that elongation is better until breakage when compared at the same thickness, and through this, it can be confirmed that the crack resistance is excellent.

Therefore, the present invention is excellent in crack resistance when compared at the same thickness compared to a resin-coated copper foil made of a conventional single-molecule series, thereby contributing to improving the performance of a semiconductor device.

In addition, the rheometer minimum viscosity window is widened, which is advantageous for flowability and pattern fillability. Preferably, within the temperature section of the metal foil lamination process, by increasing the window (window) to maintain the minimum viscosity, there is an effect of improving the flowability of the resin.

For example, assuming that the complex viscosity suitable for filling the pattern is 2000 Pa.s or less, in the case of the thermosetting resin composition for coating a metal thin film, a temperature range satisfying the viscosity condition is very wide from 120 ° C to 180 ° C. . That is, the flow resistance in the lamination process section is high and the pattern filling property is excellent, so that the crack resistance of the metal thin film coated with the thermosetting resin composition can be improved.

The thermosetting resin composition for coating a metal thin film may include an amine compound, a thermosetting resin, a thermoplastic resin, and an inorganic filler.

The content of the component is not limited significantly, but may include the above-mentioned components in consideration of physical properties of the final product prepared from the thermosetting resin composition for coating a metal thin film, and the content ratio between these components is as described below. .

Specifically, the thermosetting resin composition i) a sulfone group, a carbonyl group, a halogen group, a nitro group, a cyano group or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, ii) a nitro group, a cyano group or a halogen group Or an unsubstituted aryl group having 6 to 20 carbon atoms, iii) a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, or iv) a nitro group, a cyano group or a halogen group, and iv) a nitro group, a cyano group or a halogen group. It may include an amine compound containing at least one functional group selected from the group consisting of alkylene groups having 1 to 20 carbon atoms. The amine compound can be used as an amine curing agent.

In this case, the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, the heteroaryl group having 2 to 30 carbon atoms, and the alkylene group having 1 to 20 carbon atoms included in the amine compound are each independently a nitro group, a cyano group, and a halogen. It may be substituted with one or more functional groups selected from the group consisting of groups.

I) a sulfone group, a carbonyl group, a halogen group, a nitro group, a cyano group or an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with a halogen group, ii) substituted or unsubstituted with a nitro group, a cyano group or a halogen group A substituted aryl group having 6 to 20 carbon atoms, iii) a heteroaryl group having 2 to 30 carbon atoms substituted or unsubstituted with a nitro group, a cyano group or a halogen group, and iv) a substituted or unsubstituted nitro group, a cyano group or a halogen group At least one functional group selected from the group consisting of alkylene groups having 1 to 20 carbon atoms is a strong electron withdrawing group (EW), and the amine compound containing the electron withdrawing functional group is compared to an amine compound without an electron withdrawing functional group. Since the reactivity is reduced, it is possible to easily control the curing reaction of the resin composition.

Therefore, by adjusting the degree of curing reaction of the composition by the amine compound to improve the fluidity, the circuit pattern filling property can be improved.

The amine compound is i) an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with a sulfone group, carbonyl group, halogen group, nitro group, cyano group or halogen group, ii) substituted or unsubstituted with a nitro group, cyano group or halogen group An aryl group having 6 to 20 carbon atoms, iii) a heteroaryl group having 2 to 30 carbon atoms substituted or unsubstituted with a nitro group, a cyano group or a halogen group, and iv) a carbon number substituted or unsubstituted with a nitro group, a cyano group or a halogen group It may be an aromatic amine compound containing at least one functional group selected from the group consisting of alkylene groups of 20 to 1, and containing 2 to 5 amine groups.

More specifically, the amine compound may include one or more compounds selected from the group consisting of the following Chemical Formulas 1 to 3.

[Formula 1]

In Chemical Formula 1, A is a sulfone group, a carbonyl group, or an alkylene group having 1 to 10 carbon atoms, and X ₁ to X ₈ are each independently a nitro group, a cyano group, a hydrogen atom, a halogen group, or an alkyl group having 1 to 6 carbon atoms. , An aryl group having 6 to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, and R _1, R ₁ ′ _, R ₂ and R ₂ ′ are each independently a hydrogen atom, a halogen group, or an alkyl group having 1 to 6 carbon atoms, An aryl group having 6 to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, and n may be an integer of 1 to 10 carbon atoms.

The alkylene group having 1 to 10 carbon atoms, the alkyl group having 1 to 6 carbon atoms, the aryl group having 6 to 15 carbon atoms, and the heteroaryl group having 2 to 20 carbon atoms are each independently selected from the group consisting of a nitro group, a cyano group, and a halogen group. It may be substituted with the above functional groups.

[Formula 2]

In Chemical Formula 2, Y ₁ to Y ₈ are each independently a nitro group, a cyano group, a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms. R _3, R ₃ ′ _, R ₄ and R ₄ ′ are each independently a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms. , m is an integer of 1 to 10, the alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 15 carbon atoms, and heteroaryl group having 2 to 20 carbon atoms are each independently selected from the group consisting of a nitro group, a cyano group and a halogen group It may be substituted with one or more functional groups.

[Formula 3]

In Formula 3, Z ₁ to Z ₄ are each independently a nitro group, a cyano group, a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms. R _5, R ₅ ′ _, R ₆ and R ₆ ′ are each independently a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms. , The alkyl group having 1 to 6 carbon atoms, the aryl group having 6 to 15 carbon atoms, and the heteroaryl group having 2 to 20 carbon atoms may be independently substituted with one or more functional groups selected from the group consisting of a nitro group, a cyano group, and a halogen group. .

The alkyl group is a monovalent functional group derived from alkane, for example, as straight, branched or cyclic, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, Hexyl, and the like. Each of the one or more hydrogen atoms contained in the alkyl group may be substituted with a substituent.

The alkylene group is a divalent functional group derived from alkane, for example, as a straight chain, branched or cyclic, 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 contained in the alkylene group may be substituted with substituents similar to those of the alkyl group.

The aryl group is a monovalent functional group derived from arene, and may be, for example, monocyclic or polycyclic. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a stilbenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthryl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto. One or more hydrogen atoms among these aryl groups may be substituted with substituents similar to those of the alkyl group.

The heteroaryl group is a heteroatom, a heterocyclic group containing O, N, or S, and the number of carbon atoms is not particularly limited, but may be 2 to 30 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrol group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, triazine group, acridil group, pyridazine group , Quinolinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group and dibenzofuran Flags, etc., but are not limited to these. One or more hydrogen atoms of the heteroaryl group may be substituted with substituents similar to those of the alkyl group.

The term "substitution" means that other functional groups are bonded instead of the 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 the substituent is substitutable. The substituents can be the same or different from each other.

More specifically, Chemical Formula 1 may include a compound represented by Chemical Formula 1-1.

[Formula 1-1]

In Formula 1-1, the contents of A, X ₁ to X ₈ , R _1, R ₁ ′ _, R ₂ and R ₂ ′, n include the contents described in Formula 1 above.

A specific example of the above formula 1-1 is 4,4'-diaminodiphenyl sulfone (A in formula 1-1 is a sulfone group, X ₁ to X _8, R _1, R ₁ ' _, R ₂ and R ₂ ' are each independently A hydrogen atom, n is 1), bis (4-aminophenyl) methanone (A in Formula 1-1 is a carbonyl group, X ₁ , X _2, R _1, R ₁ ' _, R ₂ and R ₂ ' are each Independently, it is a hydrogen atom, n is 1), 4,4 '-(perfluoropropane-2,2-diyl) dianiline (A in formula 1-1 is perfluoropropane-2,2-diyl, X ₁ to X _8, R _1, R ₁ ′ _, R ₂ and R ₂ ′ are each independently a hydrogen atom, n is 1), 4,4 '-(2,2,2-trifluoroethane-1,1-diyl) dianiline ( In Formula 1-1, A is 2,2,2-trifluoroethane-1,1-diyl, X ₁ to X _8, R _1, R ₁ ′ _, R ₂ and R ₂ ′ are each independently a hydrogen atom, and n is 1).

In addition, Formula 2 may include a compound represented by Formula 2-1.

[Formula 2-1]

In Formula 2-1, the contents of Y ₁ to Y ₈ , R _3, R ₃ ′ _, R ₄ and R ₄ ′, m include the contents described in Formula 2 above.

A specific example of the above Chemical Formula 2-1 is 2,2 ', 3,3', 5,5 ', 6,6'-octafluorobiphenyl-4,4'-diamine (In Formula 2-1, Y ₁ to Y ₈ are halogen As fluorine group _, R _3, R ₃ ' _, R ₄ and R ₄ ' are each independently a hydrogen atom, m is 1.), 2,2'-bis (trifluoromethyl) biphenyl-4,4'-diamine ( Y ₂ and Y ₇ are each a trifluoromethyl group, Y ₁ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₈ are hydrogen atoms _, R _3, R ₃ ' _, R ₄ and R ₄ ' are each independently As a hydrogen atom, m is 1.) and the like.

In addition, Chemical Formula 3 may include a compound represented by Chemical Formula 3-1.

[Formula 3-1]

In Chemical Formula 3-1, contents of Z ₁ to Z ₄ , R _5, R ₅ ′ _, R ₆ and R ₆ ′ include the contents described in Chemical Formula 3 above.

Specific examples of the above Chemical Formula 3-1 are 2,3,5,6-tetrafluorobenzene-1,4-diamine (In Formula 3-1, Z ₁ to Z ₄ are halogen groups _, R _5, R ₅ ' _, R ₆ And R ₆ ′ are each independently a hydrogen atom.).

The content of the amine compound with respect to the total weight of the amine compound and the resin component (specifically, the total of the thermosetting resin and the thermoplastic resin) may be 5% to 50% by weight, or 10% to 20% by weight. When the content of the amine compound is excessively reduced to less than 5% by weight, uncuring may occur, and when the content of the amine compound is excessively increased to more than 50 parts by weight, the curing rate is increased to decrease the fluidity of the thermosetting resin composition. In addition, the mechanical properties of a metal thin film using a thermosetting resin composition may be deteriorated by an unreacted amine compound.

Meanwhile, the thermosetting resin composition for coating a metal thin film may include a thermosetting resin.

The thermosetting resin may include dicyclopentadiene-based epoxy resin and biphenyl-based epoxy resin. Specifically, the content of the biphenyl-based epoxy resin compared to 100 parts by weight of the dicyclopentadiene-based epoxy resin is less than 100 parts by weight, or 1 part to 90 parts by weight, or 5 parts to 80 parts by weight, or 10 parts by weight Parts to 70 parts by weight, or 20 parts to 50 parts by weight.

More specifically, the biphenyl-based epoxy resin may be an epoxy resin represented by Formula 11 below, and the dicyclopentadiene-based epoxy resin may be an epoxy resin represented by Formula 12 below.

[Formula 11]

In Chemical Formula 11,

n is 0 or an integer from 1 to 50.

[Formula 12]

In Formula 12, n is 0 or an integer from 1 to 50.

As a specific example of the dicyclopentadiene-based epoxy resin, Nippon kayaku company XD-1000 may be mentioned, and a specific example of the biphenyl-based epoxy resin may include Nippon kayaku company NC-3000H.

In addition, the thermosetting resin may further include at least one resin selected from the group consisting of bismaleimide resin, cyanate ester resin, and bismaleimide-triazine resin.

The bismaleimide resin may be used without limitation, which is usually used in a thermosetting resin composition for coating a metal thin film, and the type is not limited. For a preferred example, the bismaleimide resin is a diphenylmethane type bismaleimide resin represented by the following Chemical Formula 13, a phenylene type bismaleimide resin represented by the following Chemical Formula 14, and a bisphenol A type diphenyl represented by the following Chemical Formula 15 It may be at least one selected from the group consisting of an ether bismaleimide resin, and a bismaleimide resin composed of oligomers of diphenylmethane type bismaleimide and phenylmethane type maleimide resin represented by Chemical Formula 16 below.

[Formula 13]

In Chemical Formula 13,

R ₁ and R ₂ are each independently H, CH ₃ or C ₂ H ₅ .

[Formula 14]

[Formula 15]

[Formula 16]

In Chemical Formula 16,

n is 0 or an integer from 1 to 50.

In addition, a specific example of the cyanate-based resin may include a cyanate ester resin, it can be used without limitation, usually used in the thermosetting resin composition for metal thin film coating, the type is not limited.

For a preferred example, the cyanate ester resin is a novolak-type cyanate resin represented by the following formula 17, a dicyclopentadiene-type cyanate resin represented by the following formula 18, a bisphenol-type cyanate resin represented by the following formula 19 And some of these triazine prepolymers, which may be used alone or in combination of two or more.

[Formula 17]

In Chemical Formula 17,

n is 0 or an integer from 1 to 50.

[Formula 18]

In Chemical Formula 18,

n is 0 or an integer from 1 to 50.

[Formula 19]

In Chemical Formula 19,

R is

or

to be.

More specifically, the cyanate resin of Chemical Formula 19 may be a bisphenol A cyanate resin, a bisphenol E cyanate resin, a bisphenol F type cyanate resin, or a bisphenol M type cyanate resin, depending on the type of R, respectively. .

And, the bismaleimide resin includes bismaleimide-triazine resin, and the like, and the bismaleimide-triazine resin can be used without limitation, which is usually used in a thermosetting resin composition for metal thin film coating. The type is not limited. Preferred examples of the bismaleimide resin include DAIWA KASEI BMI-2300.

In particular, the resin composition for coating a metal thin film contains the content of the thermosetting resin in an amount of 400 parts by weight or less based on 100 parts by weight of the amine compound, and prevents a change in physical properties of the thermosetting resin due to the filler injected at a high content, and the influence of the filler Without inducing the thermosetting resin to be uniformly curable to a more sufficient level, the reliability of the final product can be improved, mechanical properties such as toughness can also be increased, and the glass transition temperature can be sufficiently lowered. .

Conventionally, as the content of the thermosetting resin is contained in an amount of 400 parts by weight or less based on 100 parts by weight of the amine curing agent, there is a limit that the flowability and moldability decrease due to excessive curing of the thermosetting resin when a relatively large amount of the amine curing agent is added. there was. However, even if a specific amine curing agent having a reduced reactivity, including an electron withdrawing group (EWG), as described above, is added in excess, the curing rate of the thermosetting resin is suppressed from rapidly increasing due to a decrease in reactivity of the curing agent. It can exhibit a high flowability even during long-term storage in a metal thin film coating resin composition or a metal thin film obtained therefrom can have excellent fluidity.

Specifically, the thermosetting resin composition for coating a metal thin film has a content of the thermosetting resin of 400 parts by weight or less, or 150 parts by weight to 400 parts by weight, or 180 parts by weight to 300 parts by weight, or 180 parts by weight of the amine curing agent It may be parts by weight to 290 parts by weight, or 190 parts by weight to 290 parts by weight, or 240 parts by weight to 260 parts by weight. When the amine curing agent or the thermosetting resin is a mixture of two or more, the content of the thermosetting resin mixture with respect to 100 parts by weight of the amine curing agent mixture is also 400 parts by weight or less, or 150 parts by weight to 400 parts by weight, or 180 parts by weight to 300 parts by weight, Or it may be 180 parts by weight to 290 parts by weight, or 190 parts by weight to 290 parts by weight, or 240 parts by weight to 260 parts by weight.

When the content of the thermosetting resin is excessively increased to more than 400 parts by weight based on 100 parts by weight of the amine curing agent, it is difficult to uniformly cure the thermosetting resin to a more sufficient level under the influence of the filler injected at a high content, and the reliability of the final manufactured product This can be reduced, and mechanical properties such as toughness can also be reduced.

In addition, the content of the epoxy resin is 30% by weight to 80% by weight, and the content of bismaleimide resin is 1% by weight to 20% by weight based on the total weight of the amine compound and the resin component (specifically, the total of the thermosetting resin and the thermoplastic resin). It may be weight percent. Preferably, the content of the epoxy resin may be 35% to 70% by weight with respect to the sum of the amine compound and the resin component (specifically, the total of the thermosetting resin and the thermoplastic resin). In addition, the content of the bismaleimide resin may be 1% to 10% by weight relative to the sum of the amine compound and the resin component (specifically, the total of the thermosetting resin and the thermoplastic resin).

If the amount of the epoxy resin used is less than 30% by weight, there is a problem in that high Tg is difficult to implement, and when it exceeds 80% by weight, there is a problem in that flowability deteriorates.

If the use amount of the bismaleimide resin is less than 1% by weight, there is a problem that desired physical properties are not realized, and if it exceeds 20% by weight, there are many unreacted groups, which may adversely affect properties such as chemical resistance.

Meanwhile, the resin composition for coating a metal thin film has an equivalent ratio of 1.4 or more, or 1.4 to 2.5, or 1.45 to 2.5, or 1.45 to 2.1, or 1.45 to 1.8, or 1.49 to 1.75, or 1.6 to 1.7.

[Equation 1]

More specifically, in Equation 1, the total active hydrogen equivalent contained in the amine curing agent is the total weight (unit: g) of the amine curing agent divided by the active hydrogen unit equivalent (g / eq) of the amine curing agent Means

When the amine curing agent is a mixture of two or more types, the weight (unit: g) for each compound is determined by dividing it by the unit equivalent of active hydrogen (g / eq), and the sum thereof is included in the amine curing agent of Equation (1). The total amount of active hydrogen equivalent can be determined.

The active hydrogen contained in the amine curing agent means a hydrogen atom contained in the amino group (-NH ₂ ) present in the amine curing agent, and the active hydrogen can form a curing structure through reaction with the curable functional group of the thermosetting resin. have.

In addition, in Equation 1, the total curable functional group equivalent contained in the thermosetting resin means a value obtained by dividing the total weight of the thermosetting resin (unit: g) by the equivalent of the curable functional group of the thermosetting resin (g / eq) do.

When the thermosetting resin is a mixture of two or more types, a value obtained by dividing the weight (unit: g) for each compound by the unit equivalent weight of the curable functional group (g / eq) is obtained, and the sum thereof is included in the thermosetting resin of Equation (1). The total equivalent curable functional group equivalent can be obtained.

The curable functional group contained in the thermosetting resin means a functional group that forms a cured structure through reaction with the active hydrogen of the amine curing agent, and the type of the curable functional group may also vary depending on the type of the thermosetting resin.

For example, when an epoxy resin is used as the thermosetting resin, the curable functional group contained in the epoxy resin may be an epoxy group, and when using a bismaleimide resin as the thermosetting resin, the curability contained in the bismaleimide resin The functional group can be a maleimide group.

That is, the equivalent ratio of the resin composition for coating a thin metal film calculated by Equation 1 satisfies 1.4 or more. The amine curing agent is contained in a sufficient level so that the curable functional groups contained in all thermosetting resins can cause a curing reaction. It means there is. Therefore, when the equivalent ratio calculated by Equation 1 in the resin composition for coating a metal thin film decreases to less than 1.4, it is difficult for the thermosetting resin to be uniformly cured to a more sufficient level under the influence of the filler injected at a high content, resulting in final production There is a disadvantage that the reliability of the product can be reduced and the mechanical properties can also be reduced.

Meanwhile, the thermosetting resin composition for coating a metal thin film may include a thermoplastic resin.

After curing, the thermoplastic resin has an effect of increasing toughness, and may lower the thermal expansion coefficient and elastic modulus to alleviate warpage of the metal thin film. Specific examples of the thermoplastic resin include (meth) acrylate-based polymers.

Examples of the (meth) acrylate-based polymer are not particularly limited, and include, for example, an acrylic ester copolymer containing a repeating unit derived from a (meth) acrylate monomer and a repeating unit derived from (meth) acrylonitrile; Or it may be an acrylic acid ester copolymer containing a repeating unit derived from butadiene. For example, the (meth) acrylate-based polymer is a monomer such as butyl acrylate, ethyl acrylate, acrylonitrile, methyl methacrylate, glycidyl methacrylate, respectively, in the range of 1% by weight to 40% by weight It may be a copolymer that is used in (in comparison to the total weight of the whole monomer) copolymerized.

The (meth) acrylate-based polymer may have a weight average molecular weight of 500,000 to 1,000,000. If the weight-average molecular weight of the (meth) acrylate-based polymer is too small, the effect may be technically disadvantageous due to an increase in toughness after curing or a decrease in thermal expansion and elastic modulus. In addition, if the weight average molecular weight of the (meth) acrylate-based polymer is too large, fluidity may be reduced.

In this specification, the weight average molecular weight means the weight average molecular weight of polystyrene conversion measured by GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, detectors and analytical columns, such as a commonly known analytical device and a differential index detector, can be used, and the temperature is usually applied. Conditions, solvents and flow rates can be applied. For a specific example of the above measurement conditions, using a Waters PL-GPC220 instrument using a Polymer Laboratories PLgel MIX-B 300 mm length column, the evaluation temperature is 160 ° C. and 1,2,4-trichlorobenzene is used as a solvent. The flow rate was 1 mL / min, the sample was prepared at a concentration of 10 mg / 10 mL, and then supplied in an amount of 200 μL, and the value of Mw can be obtained by using an assay curve formed using a polystyrene standard. The molecular weight of the polystyrene standard was 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.

Preferred examples of the thermoplastic resin include Negami chemical industrial Co., LTD. PARACRON KG-3015P.

On the other hand, with respect to 100 parts by weight of the total of the amine compound and the thermosetting resin, the thermoplastic resin may include 40 parts by weight to 90 parts by weight. Preferably, the thermoplastic resin may include 41 parts by weight to 80 parts by weight, or 42 parts by weight to 70 parts by weight, or 42.7 parts by weight to 67 parts by weight based on 100 parts by weight of the total of the amine compound and the thermosetting resin. When the content of the thermoplastic resin is less than 40 parts by weight, there is a problem in that the flowability of the resin is too large, resulting in an increase in thickness variation.

In addition, the thermosetting resin composition for coating a metal thin film may include an inorganic filler.

The inorganic filler may be used without limitation that is usually used in a thermosetting resin composition for metal thin film coating, and specific examples include silica, aluminum trihydroxide, magnesium hydroxide, molybdenum oxide, zinc molybdate, and zinc Borate, zinc stannate, alumina, clay, kaolin, talc, calcined kaolin, calcined talc, mica, short glass fibers, glass fine powder and hollow glass may be one or more selected from the group consisting of these.

The thermosetting resin composition for coating a metal thin film has an inorganic filler content of 200 parts by weight to 500 parts by weight, or 205 parts by weight to 450 parts by weight, or 210 parts by weight to 400 parts by weight based on a total of 100 parts by weight of the amine compound and the thermosetting resin It may include parts by weight. If the content of the inorganic filler is too small, the thermal expansion coefficient increases, which increases the warpage during the reflow process, and there is a problem that the rigidity of the printed circuit board decreases.

In addition, when using the surface-treated filler, the packing density can be increased by using a small size of the nanoparticle size and a large size of the microparticle size to increase the packing density.

The inorganic filler may include two or more inorganic fillers having different average particle diameters. Specifically, at least one of the two or more inorganic fillers may be an inorganic filler having an average particle diameter of 0.1 μm to 100 μm, and another one may be an inorganic filler having an average particle diameter of 1 nm to 90 nm.

The inorganic filler content of the average particle diameter of 1 nm to 90 nm with respect to 100 parts by weight of the inorganic filler having an average particle diameter of 0.1 μm to 100 μm may be 1 part by weight to 30 parts by weight.

The inorganic filler may use silica surface-treated with a silane coupling agent from the viewpoint of improving moisture resistance and dispersibility.

As a method of surface-treating the inorganic filler, a method of treating silica particles by dry or wet using a silane coupling agent as a surface treatment agent may be used. For example, silica may be surface-treated by a wet method using 0.01 to 1 part by weight of a silane coupling agent based on 100 parts by weight of silica particles.

Specifically, as the silane coupling agent, 3-aminopropyl triethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane and N-2- (aminoethyl) -3-aminopropyl trimethoxysilane. Aminosilane coupling agents, epoxy silane coupling agents such as 3-glycidoxypropyl trimethoxysilane, vinyl silane coupling agents such as 3-methacryloxypropyl trimethoxysilane, N-2- (N-vinylbenzylaminoethyl ) -3-aminopropyltrimethoxysilane hydrochloride, and cationic silane coupling agents such as phenyl silane coupling agents, and silane coupling agents may be used alone, or at least two silane coupling agents may be combined as necessary. Can be used.

More specifically, the silane compound may include an aromatic amino silane or (meth) acrylic silane, and as the inorganic filler having an average particle diameter of 0.1 μm to 100 μm, silica treated with an aromatic amino silane may be used. As the inorganic filler having an average particle diameter of 1 nm to 90 nm, (meth) acrylic silane-treated silica may be used. Specific examples of the aromatic amino silane-treated silica include SC2050MTO (Admantechs), and specific examples of the (meth) acrylsilane-treated silica include AC4130Y (Nissan chemical). The (meth) acrylic was used to mean both acrylic or methacrylic.

In addition, the thermosetting resin composition for coating a metal thin film may be used as a solution by adding a solvent if necessary. The solvent is not particularly limited as long as it exhibits good solubility with respect to the resin component, and alcohols, ethers, ketones, amides, aromatic hydrocarbons, esters, nitriles, etc. can be used. Alternatively, a mixed solvent used in combination of two or more kinds can also be used.

In addition, the thermosetting resin composition for coating a thin metal film may further include various polymer compounds such as other thermosetting resins, thermoplastic resins, and oligomers and elastomers, and other flame retardant compounds or additives, as long as the properties of the resin composition are not impaired. have. These are not particularly limited as long as they are selected from those commonly used. For example, additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, pigments, dyes, thickeners, lubricants, antifoaming agents, dispersants, There are leveling agents, varnishes, etc., and it is also possible to mix and use them to meet the purpose.

Examples of the other thermosetting resins include epoxy resins, and the epoxy resins are not limited in their types, but bisphenol A type epoxy resins, phenol novolac epoxy resins, phenyl aralkyl epoxy resins, and tetraphenyl ethane epoxy resins. , Naphthalene-based epoxy resins, or mixtures thereof.

Specifically, the epoxy resin is a bisphenol-type epoxy resin represented by the following formula (5), a novolac-type epoxy resin represented by the following formula (6), a phenyl aralkyl epoxy resin represented by the following formula (7), tetraphenyl represented by the following formula (8) Ethane type epoxy resin, one or more selected from the group consisting of naphthalene type epoxy resins represented by the following formulas 9 and 10 may be used.

[Formula 5]

In Chemical Formula 5,

R is

or

ego,

n is 0 or an integer from 1 to 50.

More specifically, the epoxy resin of Formula 5 may be a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol M type epoxy resin, or a bisphenol S type epoxy resin, depending on the type of R.

[Formula 6]

In Chemical Formula 2,

R is H or CH ₃ ,

n is 0 or an integer from 1 to 50.

More specifically, the novolac-type epoxy resin of Chemical Formula 3 may be a phenol novolac-type epoxy resin or a cresol novolac-type epoxy resin, depending on the type of R, respectively.

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

Meanwhile, the thermosetting resin composition for coating a metal thin film may include the amine compound described above, and may further include an additional curing agent other than the amine compound.

By mixing each of the above-described components to prepare a varnish for coating, and coating it on a metal foil, a resin coating metal thin film can be produced by a simple method through curing and drying.

The thermosetting resin composition for coating a metal thin film having such a configuration may satisfy a complex viscosity condition of 2000 Pa · s or less in a range of 120 ° C. to 180 ° C. for a rheometer minimum viscosity section.

That is, assuming that the complex viscosity suitable for filling the pattern is 2000 Pa · s or less, in the case of the resin composition presented in the present invention, the temperature range satisfying the viscosity condition is very wide from 120 ° C. to 180 ° C. That is, since the flowability in the lamination process section is high, no empty space is generated after lamination of the resin, so that the pattern filling property is excellent.

As the thermosetting resin composition for coating a metal thin film has excellent resin flow properties as described above, it is possible to make a metal thin film and a metal laminated plate using the same or secure flowability in a build-up process to easily fill a fine pattern. Also, the crack resistance of the thin film can be improved.

The thickness of the cured product used as the insulating pattern may be 15 μm or less, or 10 μm or less, or 1 μm to 15 μm, or 1 μm to 10 μm, or 5 μm to 10 μm, or 6 μm to 8 μm.

(2) resist pattern layer

The multilayer printed circuit board may include a resist pattern layer formed on upper and lower surfaces of the resin laminate. The resist pattern layer may include a resist pattern having an opening pattern. The resist pattern refers to a resist block obtained through partial etching of the resist layer in the method of manufacturing a multilayer printed circuit board described later.

The resist pattern layer is formed on the upper and lower surfaces of the resin laminate to prevent product damage such as tearing and to realize excellent durability even when manufacturing an ultra-thin multilayer printed circuit board.

Examples of the resist included in the resist pattern layer include an alkali-soluble or non-thermosetting photosensitive dry film resist (DFR). The thickness of the resist pattern layer may be 1 μm to 20 μm, or 5 μm to 15 μm, or 9 μm to 10 μm.

Ⅱ. Manufacturing method of multilayer printed circuit board

According to another embodiment of the present invention, a first step of laminating a metal layer on both sides of a carrier film and forming a pattern; A second step of stacking an insulating layer on the metal layer and forming a pattern; A third step of laminating a metal layer on the insulating layer and forming a pattern; A fourth step of forming a resist layer on the metal layer; The fifth step of peeling the carrier film and the metal layer of the first step, laminating a resist layer on the surface of the peeled metal layer and forming a pattern; including, the insulating layer is a resin coating metal thin film having a thickness of 15 ㎛ or less Provides a method for manufacturing a multilayer printed circuit board in which the second and third steps are repeated one or more times after the third step.

The multilayer printed circuit board of the one embodiment can be obtained by the method of manufacturing the multilayer printed circuit board of the other embodiment.

The method of manufacturing the multi-layer printed circuit board, using the carrier film as a temporary core layer, repeats the lamination / pattern formation of the metal layer and the insulating layer on the upper and lower surfaces of the carrier film, respectively, and then removing the carrier film to remove the two in a single process. A resin laminate (panel) can be formed.

In particular, as a resin coating metal thin film having a thickness of 15 µm or less is applied as an insulating layer used in manufacturing a resin laminate, the total thickness of the resin laminate is significantly reduced, thereby increasing the applicability to thinner and highly integrated semiconductor devices. You can. In addition, the resin-coated metal thin film includes a metal thin film on the surface of the resin layer together with a resin layer having insulating properties, and thus, the metal layer can be easily stacked without introducing a separate seed layer in the process of forming the metal layer after forming the insulating layer. You can.

In addition, in order to prevent the resin laminate from being damaged in the process of removing the carrier film, a resist layer is formed on the top of the resin laminate prior to the removal of the carrier film, and after removing the carrier film, the remaining top of the resin laminate is removed. The durability of the resin laminate can be improved through two coatings of the resist layer, which further forms a resist layer.

Specifically, the first step is a step of laminating a metal layer on both sides of the carrier film and forming a pattern. The carrier film is a base film that serves as a support for lamination of a metal layer and an insulating layer, and a metal layer may be laminated on each side of the carrier film and opposite sides facing the carrier film.

Examples of metals included in the metal layer include metals such as gold, silver, copper, tin, nickel aluminum, and titanium, or alloys containing two or more mixtures thereof, and the thickness of the metal layer is 1 μm to 20 μm. , Or 5 μm to 15 μm, or 7 μm to 9 μm. When the thickness of the metal layer is excessively increased to more than 20 μm, as an excessive amount of metal is required to form the metal layer, the cost of raw materials may increase, resulting in reduced efficiency in terms of economy, thinning, and highly integrated semiconductor Application to the device can be difficult.

The specific example of the carrier film is not particularly limited, and various organic and inorganic materials such as polymer, metal, and rubber may be applied. As a specific example, plastic films such as polyethylene terephthalate (PET), polyester film, polyimide film, polyamideimide film, polypropylene film, and polystyrene film can be used. The thickness of the carrier film may be 10 μm to 100 μm.

Examples of a method of laminating a metal layer on both sides of the carrier film include forming a metal thin film on both sides of the carrier film; And depositing metal on the metal thin film.

Specifically, in the step of forming a metal thin film on both sides of the carrier film, metal, such as gold, silver, copper, tin, nickel aluminum, titanium, or an alloy containing a mixture of two or more thereof, is deposited on the surface of the carrier film. And a method.

Examples of the deposition 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. On the other hand, specific examples of the wet deposition process include electroless plating of various metals, and more specifically electroless copper plating. In addition, a roughening treatment process may be further included before or after the deposition.

In the step of depositing the metal on the metal thin film, the above-described deposition method may be applied in the same way.

An example of a method of forming a pattern on the metal layer is not particularly limited, for example, forming a patterned photosensitive resin layer on the metal layer; And removing the metal layer exposed by the patterned photosensitive resin layer.

In the step of forming a patterned photosensitive resin layer on the metal layer, the photosensitive resin layer may be laminated on the metal layer in a state in which a pattern is formed, or a pattern may be formed after being laminated, more preferably on the metal layer. After being stacked on, a pattern may be formed. Examples of the photosensitive resin layer include an alkali-soluble or non-thermosetting photosensitive dry film resist (DFR).

The method of forming the photosensitive resin layer on the metal layer is 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 carrier film, or spraying or dipping the photosensitive resin composition. A method of coating on a carrier film and pressing it can be used.

The step of forming a patterned photosensitive resin layer on the metal layer may include exposing and alkali developing the photosensitive resin layer formed on the metal layer. In this case, the photosensitive resin layer may be used as a protective layer or patterning mask for the metal layer.

In the step of exposing and alkali developing the photosensitive resin layer formed on the metal layer, the thickness of the photosensitive resin layer formed on the metal layer may be 3 μm to 60 μm, or 5 μm to 30 μm. When the thickness of the photosensitive resin layer is excessively increased to more than 60 μm, resolution may decrease.

An example of a method of exposing the photosensitive resin layer is not particularly limited. For example, a photomask formed of a predetermined pattern is contacted with the photosensitive resin layer and irradiated with ultraviolet rays, or a predetermined pattern included in the mask is projected. It can be selectively exposed through a method such as irradiating ultraviolet rays after imaging through a lens, or directly using a laser diode as a light source, and then irradiating ultraviolet rays. At this time, examples of the ultraviolet irradiation conditions include irradiation with a light amount of 5 mJ / cm 2 to 600 mJ / cm 2.

In addition, an example of a method of developing the photosensitive resin layer may include a method of treating an alkali developer. Examples of the alkali developer are not particularly limited. For example, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, and amines can be used. , Preferably, 30 ° C 1% sodium carbonate developer may be used. The specific amount of the alkali developer is not particularly limited.

In the step of removing the metal layer exposed by the photosensitive resin layer pattern, the photosensitive resin pattern is used as a resist for forming a pattern in the metal layer. Therefore, the metal layer exposed by the photosensitive resin layer pattern means a portion of the metal layer that is not in contact with the photosensitive resin layer on the surface.

Specifically, the step of removing the metal layer exposed by the photosensitive resin layer pattern may include a step in which the etching solution passes through the photosensitive resin layer on which the pattern is formed and contacts the metal layer.

The etchant may be selected according to the type of metal layer, and it is preferable to use a material that does not affect the photosensitive resin layer.

The second step is a step of laminating an insulating layer on the metal layer and forming a pattern. The metal layer in the second step refers to a metal layer on which a pattern is formed after the first step.

The insulating layer formed on the metal layer may include a resin-coated metal thin film having a thickness of 15 μm or less. Specifically, the thickness of the resin-coated metal thin film may be 15 μm or less, or 10 μm or less, or 1 μm to 15 μm, or 1 μm to 10 μm, or 5 μm to 10 μm, or 8 μm to 10 μm. . When the thickness of the resin-coated metal thin film is excessively increased, as an excessive amount of insulating material is required to form the insulating layer, the cost of raw materials may increase, resulting in reduced efficiency in economical efficiency, thinning and high integration. Applications to semiconductor devices can be difficult.

The resin-coated metal thin film includes a metal foil, a resin cured product formed on at least one surface of the metal foil, and an inorganic filler dispersed between the resin cured products, wherein the cured resin product is i) sulfone group, carbonyl group, halogen group , An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with a nitro group, a cyano group or a halogen group, ii) a nitro group, an aryl group having 6 to 20 carbon atoms unsubstituted or substituted with a cyano group or a halogen group, iii) a nitro group, a cyano group Heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with no or halogen group, and iv) at least one functional group selected from the group consisting of a alkylene group having 1 to 20 carbon atoms unsubstituted or substituted with nitro group, cyano group or halogen group. An amine compound containing at least one; Thermosetting resins; And thermoplastic resin; may be a cured product of the liver.

In addition, the resin-coated metal thin film includes a metal foil and a cured resin formed on at least one surface of the metal foil, and the cured resin is i) substituted with a sulfone group, a carbonyl group, a halogen group, a nitro group, a cyano group, or a halogen group. Or an unsubstituted alkyl group having 1 to 20 carbon atoms, ii) an aryl group having 6 to 20 carbon atoms substituted or unsubstituted with a nitro group, a cyano group or a halogen group, iii) a carbon number substituted or unsubstituted with a nitro group, a cyano group or a halogen group 2 to 30 heteroaryl groups, and iv) an amine compound containing at least one functional group selected from the group consisting of an alkylene group having 1 to 20 carbon atoms unsubstituted or substituted with a nitro group, a cyano group, or a halogen group; Thermosetting resins; Thermoplastic resins; And an inorganic filler, containing 40 parts by weight to 90 parts by weight of the thermoplastic resin with respect to 100 parts by weight of the total of the amine compound and the thermosetting resin, and complexing up to 2000 Pa · s in the range of 120 ° C. to 180 ° C. It may be a cured product of a thermosetting resin composition for coating a thin metal film having a viscosity.

The metal foil is copper foil; Aluminum foil; A composite foil of a three-layer structure comprising nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead or lead-tin alloy as an intermediate layer, and including copper layers of different thicknesses on both sides; Or it includes a composite foil of a two-layer structure in which aluminum and copper foil are combined.

According to one preferred embodiment, the metal foil used in the present invention is a copper foil or an aluminum foil is used, it can be used having a thickness of about 2 ㎛ to 200 ㎛, the thickness is preferably about 2 ㎛ to 35 ㎛. Preferably, copper foil is used as the metal foil. In addition, according to the present invention, as a metal foil, nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, or lead-tin alloy, etc. are used as an intermediate layer, and copper layers having a thickness of 0.5 μm to 15 μm on both sides thereof and 10 It is also possible to use a three-layer structured composite foil provided with a copper layer of µm to 300 µm or a two-layer structure composite foil obtained by combining aluminum and copper foil.

The cured resin may have a thickness of 15 μm or less, or 10 μm or less, or 1 μm to 15 μm, or 1 μm to 10 μm, or 5 μm to 10 μm, or 6 μm to 8 μm. Even if the cured product has a thin thickness on the metal foil, it is possible to exhibit excellent thermal and mechanical properties with respect to the metal foil. When the thickness of the cured product increases or decreases by a specific value, physical properties measured in the resin-coated metal thin film may also change by a certain value.

On the other hand, the contents of the cured resin include all the contents described above in one embodiment.

The resin coating metal thin film, coating a thermosetting resin composition for metal thin film coating on a metal thin film; And curing the thermosetting resin composition coated on the metal thin film.

In one embodiment, the above-mentioned components for the thermosetting resin composition for metal thin film coating are mixed to prepare a coating varnish, and after coating it on a metal foil, curing and drying the resin coating metal thin film by a simple method. can do.

In addition, the curing reaction of the resin is adjusted to lengthen the section at which the minimum viscosity is maintained in the lamination process temperature section. Preferably, the curing conditions may be performed for 1 hour to 4 hours at a temperature of 180 ° C to 250 ° C.

In addition, the method of coating the metal thin film coating thermosetting resin composition on the metal foil is not particularly limited, and a coating method well known in the art may be used.

As an example, a method of coating a metal foil with a thermosetting resin composition for coating a thin film in a coater device and coating it with a predetermined thickness may be used. The coater device may use a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater or spray coater.

In addition, a carrier film may be used for evaluation of flowability, and the carrier film may include plastic films such as polyethylene terephthalate (PET), polyester film, polyimide film, polyamideimide film, polypropylene film, and polystyrene film. Can be used.

Meanwhile, the varnish used for the coating may be in a state in which a solvent is added to the thermosetting resin composition. The solvent for the resin varnish is not particularly limited as long as it can be mixed with the resin component and has good solubility. Specific examples of these include ketones such as acetone, methyl ethyl ketone, methylisobutyl ketone and cyclohexanone, aromatic hydrocarbons such as benzene, toluene and xylene, and amides such as dimethylformamide and dimethylacetamide, methylcello And alcohol alcohols such as sorb and butyl cellosolve.

Meanwhile, an example of a method of forming a pattern on the insulating layer is not particularly limited. For example, a CO ₂ or YAG laser drill may be used as a processing method using a laser.

The third step is a step of laminating a metal layer on the insulating layer and forming a pattern. In the third step, the insulating layer means an insulating layer having a pattern formed after the second step.

The specific method of forming a metal layer and forming a pattern on the insulating layer is the same as in the first step.

Meanwhile, after the third step, the second and third steps may be repeated one or more times. That is, after the third step is performed, the second step may be performed again, and then one repeating process of the third step may be performed. As the second and third steps are repeated a plurality of times, a multi-layer build-up film may be laminated in the resin laminate.

The fourth step is a step of forming a resist layer on the metal layer. As described above, in order to prevent damage to the resin laminate occurring in the fifth step of removing the carrier film, a resist layer is formed on the top of the resin laminate in the fourth step prior to the removal of the carrier film to improve the durability of the resin laminate. Can be improved.

Examples of the resist layer include alkali-soluble or non-thermosetting photosensitive dry film resist (DFR). The resist layer may have a thickness of 1 μm to 20 μm, or 5 μm to 15 μm, or 9 μm to 10 μm.

The fifth step is a step of peeling the carrier film and the metal layer of the first step, laminating a resist layer on the surface of the peeled metal layer and forming a pattern.

In particular, the bonding force between the carrier film and the metal layer in the first step is smaller than the bonding force between the metal layer and the insulating layer in the second step, and even after the metal layer is adhered to one surface of the carrier film, physical separation between them is possible, thereby making the carrier film. It can be easily removed. This seems to be because the adhesion to the metal of the insulating layer was improved by the characteristic of the components of the insulating material used in the insulating layer.

A resist layer may be stacked on the surface of the peeled metal layer, and examples of the resist layer include an alkali-soluble or non-thermosetting photosensitive dry film resist (DFR). The resist layer may have a thickness of 1 μm to 20 μm, or 5 μm to 15 μm, or 9 μm to 10 μm.

After laminating the resist layer, a pattern can be formed on the resist layer. The resist layer forming the pattern may be all of the resist layers included in the upper and lower surfaces of the resin laminate or at least one of them.

Examples of a method of forming a pattern on the resist layer include exposure and alkali development. An example of a method of exposing the resist layer is not particularly limited. For example, a photo mask formed of a predetermined pattern is contacted with the resist layer and irradiated with ultraviolet rays, or a predetermined objective included in the mask is projected. It can be selectively exposed through imaging such as irradiating ultraviolet rays after imaging, or directly using a laser diode as a light source and then irradiating ultraviolet rays. At this time, examples of the ultraviolet irradiation conditions include irradiation with a light amount of 5 mJ / cm 2 to 600 mJ / cm 2.

In addition, an example of a method for developing the resist layer is a method for treating an alkali developer. Examples of the alkali developer are not particularly limited. For example, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, and amines can be used. , Preferably, 30 ° C 1% sodium carbonate developer may be used. The specific amount of the alkali developer is not particularly limited.

Ⅲ. Semiconductor device

According to another embodiment of the present invention, there is provided a semiconductor device including the multilayer printed circuit board of the one embodiment. The contents of the multilayer printed circuit board included in the semiconductor device include all of the contents described above in one embodiment.

The multi-layer printed circuit board can be introduced into a semiconductor device by a known method, and since the multi-layer printed circuit board has ultra-thin and strong durability, it can be applied to a thinned and highly integrated semiconductor device.

According to the present invention, a multilayer printed circuit board having a thin thickness and excellent durability, a method for manufacturing the same, and a semiconductor device using the same can be provided.

1 schematically shows a manufacturing process of a multilayer printed circuit board of Example 1.

The invention is described in more detail in the following examples. However, the following examples are only illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

<Production Example: Preparation of insulating layer>

Production Example 1: Resin coated copper foil

(1) Preparation of a thermosetting resin composition for metal thin film coating

According to the composition of Table 1, each component was added to methyl ethyl ketone in accordance with 40% of solid content and mixed, followed by stirring at room temperature at a rate of 400 rpm for 1 day and viscosity adjustment and defoaming using a rotary evaporator. By proceeding, a resin composition (resin varnish) for coating a metal thin film was prepared.

(2) Preparation of resin coated copper foil

After coating the metal thin film coating resin composition with a comma coater on a copper foil (2 µm thick, manufactured by Mitsui) (coating thickness: 6 µm), it was cured for 100 minutes under conditions of 220 ° C. and 35 kg / cm 2. Subsequently, a resin coated copper foil of Preparation Example 2 was produced by cutting to a size of 17 cm x 15 cm.

Production Example 2: Resin coated copper foil

(1) Preparation of a thermosetting resin composition for metal thin film coating

According to the composition of Table 1, each component was added to methyl ethyl ketone in accordance with 40% of solid content and mixed, followed by stirring at room temperature at a rate of 400 rpm for 1 day and viscosity adjustment and defoaming using a rotary evaporator. By proceeding, a resin composition (resin varnish) for coating a metal thin film was prepared.

(2) Preparation of resin coated copper foil

After coating the resin composition for metal thin film coating with a comma coater (2 µm thick, manufactured by Mitsui) (coating thickness: 8 µm), it was cured for 100 minutes under conditions of 220 ° C. and 35 kg / cm 2. Subsequently, a resin coated copper foil of Preparation Example 1 was produced by cutting to a size of 17 cm x 15 cm.

Preparation Example 3: Prepreg

(1) Preparation of thermosetting resin composition

According to the composition of Table 1, each component was added to methyl ethyl ketone in accordance with 40% of solid content and mixed, followed by stirring at room temperature at a rate of 400 rpm for 1 day and viscosity adjustment and defoaming using a rotary evaporator. By proceeding, a resin composition (resin varnish) for coating a metal thin film was prepared.

 (2) Preparation of prepreg

The impregnated varnish was impregnated into a woven glass fiber (12 µm thick, manufactured by Asahi Glass), followed by hot air drying at a temperature of 180 ° C. for 2 to 5 minutes to prepare a 16 µm thick prepreg.

Preparation Example 4: Prepreg

(1) Preparation of thermosetting resin composition

According to the composition of Table 1, each component was added to methyl ethyl ketone in accordance with 40% of solid content and mixed, followed by stirring at room temperature at a rate of 400 rpm for 1 day and viscosity adjustment and defoaming using a rotary evaporator. By proceeding, a resin composition (resin varnish) for coating a metal thin film was prepared.

 (2) Preparation of prepreg

The impregnated varnish was impregnated into a woven glass fiber (12 µm thick, manufactured by Asahi Glass), followed by hot air drying at a temperature of 180 ° C. for 2 to 5 minutes to prepare an 18 µm thick prepreg.

* XD-1000: Epoxy resin (Nippon kayaku; epoxy equivalent 253 g / eq) * NC-3000H: Epoxy resin (Nippon kayaku; epoxy equivalent 290 g / eq)

* BMI-2300: bismaleimide resin (DAIWA KASEI, maleimide equivalent 179 g / eq)

* DDS: 4,4'-diaminodiphenyl sulfone (active hydrogen equivalent 62g / eq)

* Acrylic rubber (Mw 800,000): PARACRON KG-3015P (Negami chemical industrial Co., LTD)

Production Example 5 and Production Example 6: Resin coated copper foil

(1) Preparation of a thermosetting resin composition for metal thin film coating

According to the composition of Table 2, each component was added to methyl ethyl ketone according to 40% of solid content and mixed, followed by stirring at room temperature at a rate of 400 rpm for 1 day and viscosity adjustment and defoaming using a rotary evaporator. By proceeding, a resin composition (resin varnish) for coating a metal thin film was prepared.

(2) Preparation of resin coated copper foil

After coating the metal thin film coating resin composition with a comma coater on a copper foil (2 µm thick, manufactured by Mitsui) (coating thickness: 6 µm), it was cured for 100 minutes under conditions of 220 ° C. and 35 kg / cm 2. Subsequently, the resin coated copper foils of Production Example 5 and Production Example 6 were prepared by cutting them to a size of 17 cm x 15 cm.

After the copper foil was etched and removed from the resin coated copper foils of Preparation Example 1 and Preparation Example 5, rheometer viscosity was measured (viscosity measurement conditions according to temperature, heating rate 5 ° C./min, frequency: 10 Hz).

As a result, in the resin layer of Production Example 1, the temperature range of the complex viscosity of 2000 Pa · s or less was 120 to 180 ° C., whereas the resin layer of Production Example 5 had no temperature section of the complex viscosity of 2000 Pa · s or less.

In addition, after the copper foil was etched and removed from the resin coated copper foils of Preparation Examples 1 and 6, according to IPC-TM-650 (2.4.18.3), tensile elongation in the MD direction using Universal Testing Machine (Instron 3365) equipment. Was measured.

As a result, it was confirmed that the resin layer of Production Example 1 had a tensile elongation of 3.8%, whereas the resin layer of Production Example 6 had a tensile elongation of 0.9%, which was measured very low compared to the Example.

<Example: Preparation of a multilayer printed circuit board>

Example 1

As shown in FIG. 1, a multilayer printed circuit board was manufactured according to the following process sequence.

<1> An ultra-thin copper foil (M0, MO ') having a thickness of 5 μm was laminated on both sides of a carrier film (C) having a thickness of 50 to 100 μm.

<2> After that, while supplying a mixed gas of argon and oxygen to the surface of the ultra-thin copper foil (M0) as a deposition equipment, a seed layer was deposited by depositing copper (Cu) metal to a thickness of 0.5 μm through sputtering. Formation, and formed a copper foil layer (M1) of 9 ㎛ thickness through electroplating.

A 15 μm thick photosensitive dry film resist KL1015 (manufactured by Kolon Industries) was laminated at 110 ° C. on the copper foil layer (M1), and a circular negative photomask having a diameter of 30 μm was contacted on the photosensitive dry film resist. , Irradiated with ultraviolet light (25 mJ / cm 2 light amount), and then developed the photosensitive dry film resist through a 30 ° C. 1% sodium carbonate developer. At this time, the exposed copper foil layer M1 was removed through etching to form a pattern. Thereafter, the remaining photosensitive dry film resist was removed using a 3% sodium hydroxide resist stripper at a temperature of 50 ° C.

On the copper foil layer M1, an 8 μm thick resin coated copper foil obtained in Preparation Example 1 was laminated as an insulating layer D12. At this time, the resin layer of the resin coated copper foil was adhered to the copper foil layer (M1).

Thereafter, the insulating layer (D12) was thermally cured at a temperature of 200 ° C. for 1 hour, and then etched using a CO ₂ laser drill to form a via hole.

Thereafter, while supplying a mixed gas of argon and oxygen to the via hole surface as a deposition equipment, a copper (Cu) metal is deposited to a thickness of 0.5 μm through a sputtering method to form a seed layer, and 7 through electroplating. A copper foil layer (M2) having a thickness of μm was formed.

A 15 μm thick photosensitive dry film resist KL1015 (manufactured by Kolon Industries) was laminated at 110 ° C. on the copper foil layer M2, and a circular negative photomask having a diameter of 30 μm was contacted on the photosensitive dry film resist, , Irradiated with ultraviolet light (25 mJ / cm 2 light amount), and then developed the photosensitive dry film resist through a 30 ° C. 1% sodium carbonate developer. At this time, the exposed copper foil layer M2 was removed through etching to form a pattern. Thereafter, the remaining photosensitive dry film resist was removed using a 3% sodium hydroxide resist stripper at a temperature of 50 ° C.

Thereafter, a resin coated copper foil having a thickness of 10 μm obtained in Production Example 2 was laminated on the copper foil layer M2 as an insulating layer D23. At this time, the resin layer of the resin coated copper foil was adhered to the copper foil layer (M2).

Thereafter, the insulating layer D23 was thermally cured at a temperature of 200 ° C. for 1 hour, and then etched using a CO ₂ laser drill to form a via hole.

Thereafter, while supplying a mixed gas of argon and oxygen to the via hole surface as a deposition equipment, a titanium (Ti) metal was deposited to a thickness of 50 nm and a copper (Cu) metal to a thickness of 0.5 µm through a sputtering method to form a seed layer. Was formed, and a copper foil layer (M3) having a thickness of 9 μm was formed through electroplating.

A 15 μm thick photosensitive dry film resist KL1015 (manufactured by Kolon Industries) was laminated at 110 ° C. on the copper foil layer (M3), and a circular negative photomask having a diameter of 30 μm was brought into contact with the photosensitive dry film resist. , Irradiated with ultraviolet light (25 mJ / cm 2 light amount), and then developed the photosensitive dry film resist through a 30 ° C. 1% sodium carbonate developer. At this time, the exposed copper foil layer (M3) was removed through etching to form a pattern. Thereafter, the remaining photosensitive dry film resist was removed using a 3% sodium hydroxide resist stripper at a temperature of 50 ° C. to prepare a first panel (PN-1).

On the surface of the ultra-thin copper foil (MO '), copper foil layer (M1'), insulating layer (D12 '), copper foil layer (M2'), insulating layer (D23 '), and copper foil layer (M3') in the same manner as the first panel. ) To form a second panel (PN-2) sequentially stacked.

<3> A photosensitive dry film resist KL1015 (manufactured by Kolon Industries) (SR BTM) having a thickness of 9 μm was laminated on the surface of the first panel (PN-1) at 110 ° C. On the surface of the second panel (PN-2), a photosensitive dry film resist KL1015 (manufactured by Kolon Industries) (SR BTM ') having a thickness of 9 µm was laminated at 110 ° C.

<4> The ultra-thin copper foil (M0) and the carrier film (C) were separated to remove the carrier film.

<5> The ultra-thin copper foil (MO) on the surface of the first panel (PN-1) was removed by etching, and a 9 μm thick photosensitive dry film resist KL1015 (manufactured by Kolon Industries) (SR TOP) was laminated at 110 ° C.

<6> A circular negative photomask having a diameter of 30 µm is brought into contact with the photosensitive dry film resist (SR TOP), irradiated with ultraviolet rays (light amount of 25 mJ / cm 2), and then through 30% 1% sodium carbonate developer The photosensitive dry film resist (SR TOP) was developed to form a constant pattern.

In the same way as the photosensitive dry film resist (SR BTM), a constant pattern was formed to produce a multilayer printed circuit board.

<7> Also for the second panel (PN-2), the steps of <5> to <6> were performed to prepare a multilayer printed circuit board.

Example 2

A multilayer printed circuit board was manufactured according to the following process sequence.

<1> The same procedure as in <1> in Example 1 was performed.

<2> On the surface of the ultra-thin copper foil (M0), while supplying a mixed gas of argon and oxygen to the deposition equipment, a copper (Cu) metal is deposited to a thickness of 0.5 μm through a sputtering method to form a seed layer, A copper foil layer (M1) having a thickness of 9 μm was formed through electroplating.

A 15 μm thick photosensitive dry film resist KL1015 (manufactured by Kolon Industries) was laminated at 110 ° C. on the copper foil layer (M1), and a circular negative photomask having a diameter of 30 μm was contacted on the photosensitive dry film resist. , Irradiated with ultraviolet light (25 mJ / cm 2 light amount), and then developed the photosensitive dry film resist through a 30 ° C. 1% sodium carbonate developer. At this time, the exposed copper foil layer M1 was removed through etching to form a pattern. Thereafter, the remaining photosensitive dry film resist was removed using a 3% sodium hydroxide resist stripper at a temperature of 50 ° C.

On the copper foil layer M1, an 8 μm thick resin coated copper foil obtained in Preparation Example 1 was laminated as an insulating layer D12. At this time, the resin layer of the resin coated copper foil was adhered to the copper foil layer (M1).

Thereafter, the insulating layer (D12) was thermally cured at a temperature of 200 ° C. for 1 hour, and then etched using a CO ₂ laser drill to form a via hole.

Thereafter, while supplying a mixed gas of argon and oxygen to the via hole surface as a deposition equipment, a copper (Cu) metal is deposited to a thickness of 0.5 μm through a sputtering method to form a seed layer, and through electroplating, 8 A copper foil layer (M2) having a thickness of μm was formed.

A 15 μm thick photosensitive dry film resist KL1015 (manufactured by Kolon Industries) was laminated at 110 ° C. on the copper foil layer M2, and a circular negative photomask having a diameter of 30 μm was contacted on the photosensitive dry film resist, , Irradiated with ultraviolet light (25 mJ / cm 2 light amount), and then developed the photosensitive dry film resist through a 30 ° C. 1% sodium carbonate developer. At this time, the exposed copper foil layer M2 was removed through etching to form a pattern. Thereafter, the remaining photosensitive dry film resist was removed using a 3% sodium hydroxide resist stripper at a temperature of 50 ° C.

On the copper foil layer M2, an 8 μm-thick resin-coated copper foil obtained in Preparation Example 1 was laminated as an insulating layer (D23). At this time, the resin layer of the resin coated copper foil was adhered to the copper foil layer (M2).

Thereafter, the insulating layer (D23) was thermally cured at a temperature of 200 ° C. for 1 hour, and then etched using a CO ₂ laser drill to form a via hole.

Thereafter, while supplying a mixed gas of argon and oxygen to the via hole surface as a deposition equipment, a copper (Cu) metal is deposited to a thickness of 0.5 μm through a sputtering method to form a seed layer, and through electroplating, 8 A copper foil layer (M3) having a thickness of μm was formed.

A 15 μm thick photosensitive dry film resist KL1015 (manufactured by Kolon Industries) was laminated at 110 ° C. on the copper foil layer (M3), and a circular negative photomask having a diameter of 30 μm was brought into contact with the photosensitive dry film resist. , Irradiated with ultraviolet light (25 mJ / cm 2 light amount), and then developed the photosensitive dry film resist through a 30 ° C. 1% sodium carbonate developer. At this time, the exposed copper foil layer M2 was removed through etching to form a pattern. Thereafter, the remaining photosensitive dry film resist was removed using a 3% sodium hydroxide resist stripper at a temperature of 50 ° C.

Thereafter, a resin coated copper foil having a thickness of 10 μm obtained in Production Example 2 was laminated on the copper foil layer M3 as an insulating layer D34. At this time, the resin layer of the resin coated copper foil was adhered to the copper foil layer (M3).

Thereafter, the insulating layer D34 was thermally cured at a temperature of 200 ° C. for 1 hour, and then etched using a CO ₂ laser drill to form a via hole.

Thereafter, while supplying a mixed gas of argon and oxygen to the via hole surface as a deposition equipment, a titanium (Ti) metal was deposited to a thickness of 50 nm and a copper (Cu) metal to a thickness of 0.5 µm through a sputtering method to form a seed layer. Was formed, and a copper foil layer (M4) having a thickness of 9 μm was formed through electroplating.

A 15 μm thick photosensitive dry film resist KL1015 (manufactured by Kolon Industries) was laminated at 110 ° C. on the copper foil layer (M4), and a circular negative photomask having a diameter of 30 μm was contacted on the photosensitive dry film resist. , Irradiated with ultraviolet light (25 mJ / cm 2 light amount), and then developed the photosensitive dry film resist through a 30 ° C. 1% sodium carbonate developer. At this time, the exposed copper foil layer (M4) was removed through etching to form a pattern. Thereafter, the remaining photosensitive dry film resist was removed using a 3% sodium hydroxide resist stripper at a temperature of 50 ° C. to prepare a first panel (PN-1).

Copper foil layer M1 ', insulating layer D12', copper foil layer M2 ', insulating layer D23', copper foil layer M3 'on the surface of the ultra-thin copper foil MO' in the same manner as the first panel. ), A second panel (PN-2) in which the insulating layer (D34 ') and the copper foil layer (M4') were sequentially stacked.

<3> to <7> The same procedure as in <3> to <7> in Example 1 was performed.

<Comparative Example: Manufacturing of a multi-layer printed circuit board>

Comparative Example 1

In the step <2> of Example 1, instead of the 8 μm thick resin coated copper foil obtained in Production Example 1 as the insulating layer (D12), a 16 μm thick prepreg (PPG) obtained in Production Example 3 was used and insulated. As the layer (D23), instead of the 10 μm thick resin coated copper foil obtained in Production Example 2, the 18 μm thick prepreg (PPG) obtained in Production Example 4 was used, and the thickness of each layer of the multi-layer laminate was as shown in Table 3 below. A multilayer printed circuit board was manufactured in the same manner as in Example 1, except that it was changed.

Comparative Example 2

In the step <2> of Example 2, instead of the 8 μm thick resin coated copper foil obtained in Production Example 1 as the insulating layer (D12) and the insulating layer (D23), the 18 μm thick prepreg (PPG) obtained in Production Example 4 ), And instead of the 10 μm thick resin coated copper foil obtained in Production Example 2 as the insulating layer (D34), the 18 μm thick prepreg (PPG) obtained in Production Example 4 was used, and the thickness of each layer of the multi-layer laminate A multi-layer printed circuit board was manufactured in the same manner as in Example 2, except that Table 3 was changed.

As shown in Table 3, in the case of using the resin-coated copper foils obtained in Production Example 1 and Production Example 2 as the insulating layer, the multilayer printed circuit board of Example 1 containing 3 layers of copper foil layers had a thickness of 61 µm and copper foil. Although the multi-layer printed circuit board of Example 2, which contained four layers, had a very thin thickness of 80 µm, there was no problem of breakage or tearing. On the other hand, in the case of the comparative example using the prepreg obtained in Production Example 3 and Production Example 4 as the insulating layer, the multilayer printed circuit board thickness of Comparative Example 1 containing 3 layers of copper foil layers was 81 µm, and the comparison of four layers of copper foil layers was included. The thickness of the multi-layer printed circuit board of Example 2 was 120 µm, so there was a limitation in that it was measured very thickly compared to the example.

[Description of codes]

C: Carrier film

M0, MO ': Ultra-thin copper foil

SR TOP, SR TOP ': Resist

M1, M1 ': Copper foil layer

D12, D12 ': insulating layer

M2, M2 ': Copper foil layer

D23, D23 ': insulating layer

M3, M3 ': Copper foil layer

D34, D34 ': insulating layer

M4, M4 ': Copper foil layer

SR BTM, SR BTM ': resist

PN-1: 1st panel

PN-2: 2nd panel

<1> to <6>: the order of progress of the process

Claims (19)

1. A resin laminate including a plurality of build-up layers including an insulating pattern and a metal pattern; And

   Including; a resist pattern layer formed on the upper and lower surfaces of the resin laminate;

   A multilayer printed circuit board having a thickness of 15 µm or less of an insulating pattern included in the build-up layer.
2. The method of claim 1

   The insulating pattern,

   i) an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with a sulfone group, carbonyl group, halogen group, nitro group, cyano group or halogen group, ii) 6 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group or halogen group Aryl group of iii) a heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with a nitro group, cyano group or halogen group, and iv) alkyl having 1 to 20 carbon atoms substituted or unsubstituted with a nitro group, cyano group or halogen group An amine compound containing at least one functional group selected from the group consisting of len groups; Thermosetting resins; And a thermoplastic resin; comprising a cured product of the liver and an inorganic filler dispersed between the cured products.
3. The method of claim 1

   The insulating pattern,

   i) an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with a sulfone group, carbonyl group, halogen group, nitro group, cyano group or halogen group, ii) 6 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group or halogen group Aryl group of iii) a heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with a nitro group, cyano group or halogen group, and iv) alkyl having 1 to 20 carbon atoms substituted or unsubstituted with a nitro group, cyano group or halogen group An amine compound containing at least one functional group selected from the group consisting of len groups; Thermosetting resins; Thermoplastic resins; And an inorganic filler, containing 40 parts by weight to 90 parts by weight of the thermoplastic resin with respect to 100 parts by weight of the total of the amine compound and the thermosetting resin, and complexing up to 2000 Pa · s in the range of 120 ° C. to 180 ° C. A multilayer printed circuit board comprising a cured product of a thermosetting resin composition for coating a metal thin film having a viscosity.
4. According to any one of claims 2 or 3,

   The thermosetting resin comprises a dicyclopentadiene-based epoxy resin and a biphenyl-based epoxy resin, a multilayer printed circuit board.
5. According to claim 4,

   The content of the biphenyl-based epoxy resin compared to 100 parts by weight of the dicyclopentadiene-based epoxy resin is less than 100 parts by weight, a multilayer printed circuit board.
6. According to any one of claims 2 or 3,

   The thermosetting resin further comprises at least one resin selected from the group consisting of bismaleimide resin, cyanate ester resin, and bismaleimide-triazine resin, a multilayer printed circuit board.
7. According to any one of claims 2 or 3,

   A multi-layer printed circuit board comprising less than 400 parts by weight of the thermosetting resin with respect to 100 parts by weight of the amine compound.
8. According to any one of claims 2 or 3,

   A multilayer printed circuit board having an equivalent ratio calculated by Equation 1 below of 1.4 or more:

   [Equation 1]

   
9. According to any one of claims 2 or 3,

   The amine compound comprises an aromatic amine compound containing 2 to 5 amino groups, a multilayer printed circuit board.
10. According to any one of claims 2 or 3,

    The thermoplastic resin includes a (meth) acrylate-based polymer, a multilayer printed circuit board.
11. The method of claim 10,

    The (meth) acrylate-based polymer,

    Acrylic ester copolymers containing repeat units derived from (meth) acrylate monomers and repeat units derived from (meth) acrylonitrile; Or an acrylic acid ester copolymer containing a repeating unit derived from butadiene, a multilayer printed circuit board.
12. The method of claim 10,

    The (meth) acrylate-based polymer has a weight average molecular weight of 500000 to 1000000, a multilayer printed circuit board.
13. According to any one of claims 2 or 3,

    The inorganic filler content is 200 parts by weight to 500 parts by weight based on 100 parts by weight of the total of the amine compound and the thermosetting resin, the multilayer printed circuit board.
14. According to any one of claims 2 or 3,

    The inorganic filler may include two or more inorganic fillers having different average particle diameters,

    A multilayer printed circuit board, wherein at least one of the two or more inorganic fillers is an inorganic filler having an average particle diameter of 0.1 μm to 100 μm, and another is an inorganic filler having an average particle diameter of 1 nm to 90 nm.
15. A first step of laminating a metal layer on both sides of the carrier film and forming a pattern;

    A second step of stacking an insulating layer on the metal layer and forming a pattern;

    A third step of laminating a metal layer on the insulating layer and forming a pattern;

    A fourth step of depositing a resist layer on the metal layer and forming a pattern;

    Including the fifth step of peeling the carrier film and the metal layer of the first step, and forming a resist layer on the surface of the peeled metal layer;

    The insulating layer includes a resin-coated metal thin film having a thickness of 15 μm or less,

    After the third step, the second and third steps are repeated one or more times, and a multi-layer printed circuit board manufacturing method.
16. The method of claim 15

    The bonding force between the carrier film and the metal layer in the first step is less than the bonding force between the metal layer and the insulating layer in the second step, a method for manufacturing a multilayer printed circuit board.
17. The method of claim 15

    The resin coating metal thin film,

    Metal foil, and

    It includes a cured resin formed on at least one surface of the metal foil, and an inorganic filler dispersed between the cured resin,

    The cured resin is i) a sulfone group, a carbonyl group, a halogen group, a nitro group, a cyano group or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, ii) a nitro group, a cyano group or a halogen group substituted or unsubstituted An aryl group having 6 to 20 carbon atoms, iii) a heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with a nitro group, a cyano group or a halogen group, and iv) a carbon number substituted or unsubstituted with a nitro group, a cyano group or a halogen group An amine compound containing at least one functional group selected from the group consisting of 1 to 20 alkylene groups; Thermosetting resins; And a thermoplastic resin; a method for manufacturing a multilayer printed circuit board which is a cured product of the liver.
18. The method of claim 15

    The resin coating metal thin film,

    Metal foil, and

    It includes a cured resin formed on at least one surface of the metal foil,

    The cured resin is i) a sulfone group, a carbonyl group, a halogen group, a nitro group, a cyano group or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, ii) a nitro group, a cyano group or a halogen group substituted or unsubstituted An aryl group having 6 to 20 carbon atoms, iii) a heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with a nitro group, a cyano group or a halogen group, and iv) a carbon number substituted or unsubstituted with a nitro group, a cyano group or a halogen group An amine compound containing at least one functional group selected from the group consisting of 1 to 20 alkylene groups; Thermosetting resins; Thermoplastic resins; And an inorganic filler, containing 40 parts by weight to 90 parts by weight of the thermoplastic resin with respect to 100 parts by weight of the total of the amine compound and the thermosetting resin, and complexing up to 2000 Pa · s in the range of 120 ° C. to 180 ° C. A method of manufacturing a multilayer printed circuit board, which is a cured product of a thermosetting resin composition for coating a thin metal film having a viscosity.
19. A semiconductor device comprising the multilayer printed circuit board of claim 1.

Images