TW202018020A - Thermosetting resin composition for coating metal thin film, resin-coated metal thin film and metal clad laminate using the same - Google Patents

Abstract

The present invention relates to a thermosetting resin composition for coating a metal thin film including: an amine compound containing a specific functional group, a thermosetting resin, a thermoplastic resin, and an inorganic filler, wherein the thermoplastic resin is included in an amount of 40 parts by weight to 90 parts by weight based on 100 parts by weight of the total of the amine compound and the thermosetting resin, and wherein the thermosetting resin composition has a complex viscosity of 2000 Pa,s or less in the range of 120 DEG C to 180 DEG C, and to a resin-coated metal thin film and a metal clad laminate using the composition.

Description

Metal film-coated thermosetting resin composition, metal film-coated resin, and metal clad laminate using the same

The present invention relates to a metal film-coated thermosetting resin composition, a resin-coated metal film, and a metal cladding laminate, and more specifically, to a compound with excellent flow properties and improved For example, a thermosetting resin composition coated with a mechanical film such as crack resistance and tensile properties is related to a resin-coated metal film and a metal clad laminate using the same. [Cross-reference to related applications]

This application claims the priority or right of the Korean Patent Application No. 10-2018-0113252 filed on September 20, 2018 at the Korean Intellectual Property Office. The full content of the disclosure of the Korean patent application is incorporated in this case reference.

By impregnating a glass fabric substrate with a thermosetting resin varnish, semi-curing the substrate to form a prepreg, and then pressing and heating the prepreg and copper foil together to manufacture a copper clad used in a conventional printed circuit board Laminate. The prepreg is again used to configure and build circuit patterns on the copper clad laminate.

In recent years, as electronic devices, communication devices, personal computers, smart phones, etc. have increased efficiency, reduced thickness, and reduced weight, and semiconductor packages have become thinner, there has been an increasing demand for semiconductor package printing The circuit board is thinner.

In other words, as the form factor of electronic devices decreases, the thickness of semiconductor packages becomes thinner and thinner. However, since the prepreg as a laminate material in the conventional packaging component includes a woven glass fabric, it is difficult to reduce the thickness by more than a certain amount.

On the other hand, resin-coated copper (RCC), which is an alternative material to the prepreg, does not include glass fabric, so it can be made thinner than the prepreg.

However, the resin-coated copper foil, which is thinner than conventional prepregs, does not contain a glass fabric as a reinforcing substrate, so cracks may occur during the packaging process. If cracks occur during the manufacturing process, this can lead to a reduction in overall yield and adversely affect reliability. Therefore, there is a need to improve the crack resistance of the resin layer in the resin-coated copper foil.

In addition, the most important property of the laminate material is the filling property (embedability) of the pattern. That is, since the resin-coated copper foil as a laminate material must be filled with patterns, the flow properties of the resin are important characteristics. In particular, as the thickness of the resin copper clad laminate becomes thinner, the amount of resin decreases, so it is difficult to fill the pattern. If the pattern is not properly filled, empty voids will be generated, and the reliability and performance of the semiconductor substrate will be reduced. When the thickness of the resin-coated copper foil is thinner, the amount of resin is also reduced, thus making it possible that there are empty voids after the lamination and the pattern cannot be filled.

That is, if the thickness of the resin is reduced to make the substrate thinner, the filling properties of the pattern will deteriorate.

Therefore, in order to reduce the thickness while improving the pattern filling properties and preventing cracks, it is necessary to increase the flow properties and crack resistance of the resin at the same time.

The commonly used method is to use monomolecular resin. For resins with low molecular weight, since the viscosity before curing is low within the temperature window of the lamination process, the flow properties and pattern filling properties are excellent. However, since the monomolecular resin has surface viscosity before curing, a protective film is required. Since the curing reaction proceeds slowly when stored at room temperature, its disadvantage is that it easily changes with time.

In addition, the resin has problems of insufficient crack resistance and overall yield reduction.

[ technical problem ]

An object of the present invention is to provide a metal film-coated thermosetting resin composition having excellent flow properties and improved mechanical properties such as crack resistance and tensile properties.

Another object of the present invention is to provide a resin-coated metal film including a cured product of a metal film-coated thermosetting resin composition.

Another object of the present invention is to provide a metal clad laminate including a resin-coated metal thin film. [ Technical Solution ]

An embodiment of the present invention provides a thermosetting resin composition coated with a metal film. The resin-coated thermosetting resin composition includes: an amine compound containing one or more functional groups, and the one or more functional groups are selected Free i) A sulfonyl group, a carbonyl group, a halogen group, an unsubstituted or substituted nitro, cyano or halogen-containing alkyl group having 1 to 20 carbon atoms, ii) an unsubstituted or substituted nitro, cyano or Aryl group having 6 to 20 carbon atoms substituted by halogen group, iii) heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted by nitro group, cyano group or halogen group, and iv) unsubstituted or A group consisting of an alkylene group having 1 to 20 carbon atoms substituted by a nitro group, a cyano group or a halogen group; a thermosetting resin; a thermoplastic resin; and an inorganic filler, wherein 100 parts by weight of the amine compound and the The total amount of the thermosetting resin includes the thermoplastic resin in an amount of 40 parts by weight to 90 parts by weight, and wherein the metal film-coated thermosetting resin composition has 2000 Pa·sec in the range of 120°C to 180°C Or a complex viscosity less than 2000 Pa·s (coompex viscosity).

Another embodiment of the present invention provides a resin-coated metal film including a cured product of a metal film-coated thermosetting resin composition.

Other embodiments of the present invention provide a metal clad laminate including a resin-coated metal thin film.

Hereinafter, a metal thin film-coated thermosetting resin composition, a resin-coated metal thin film, and a metal cladding laminate using the same according to specific embodiments of the present invention will be explained in more detail. I. Thermosetting resin composition coated with metal film

According to an embodiment of the present invention, a thermosetting resin composition coated with a metal thin film can be provided, the thermosetting resin composition comprising: an amine compound containing one or more functional groups selected from the group consisting of i) Alkyl, carbonyl, halogen, unsubstituted or substituted with nitro, cyano or halogen with 1 to 20 carbon atoms, ii) Unsubstituted or substituted with nitro, cyano or halogen Aryl group having 6 to 20 carbon atoms, iii) heteroaryl having 2 to 30 carbon atoms unsubstituted or substituted by nitro, cyano or halogen, and iv) unsubstituted or substituted A group consisting of an alkylene group having 1 to 20 carbon atoms substituted with a nitro group, a cyano group or a halogen group; a thermosetting resin; a thermoplastic resin; and an inorganic filler, wherein 100 parts by weight of the amine compound and the thermosetting The total amount of the resin includes the thermoplastic resin in an amount of 40 parts by weight to 90 parts by weight, and wherein the thermosetting resin composition has 2000 Pa·s or less in the range of 120° C. to 180° C. The complex viscosity.

Traditionally, metal cladding laminates have been mainly manufactured using a prepreg in which a resin composition is impregnated into a woven glass fabric. However, not only is there a limit to reducing the thickness, but if the thickness is reduced, there is a problem that the flow properties of the resin deteriorate during the lamination process of the copper foil, and therefore the pattern filling properties are poor. In addition, even if the copper foil in the form of resin coating can be made thin, there are many disadvantages in terms of storage and stability in the case of using a monomolecular resin.

On the other hand, the existing thermosetting resin composition has a high modulus after curing and is easily broken, which may cause a disadvantage of reduced crack resistance.

Therefore, the present invention not only aims to ensure the flow properties of the resin by introducing a resin system composed of an epoxy resin, an amine curing agent, etc., but also aims to improve the crack resistance of the metal thin film coated with the thermosetting resin composition. In addition, the composition of the present invention is characterized by optimizing the resin type and mixing ratio.

More specifically, according to the present invention, the curing reaction of the resin can be easily controlled by using a specific amine curing agent. More specifically, the modulus can be reduced by adjusting the functional group of the amine curing agent to adjust the number of bonds generated during the resin curing reaction. Therefore, the crack resistance is increased, and there can be greater stability against the same tensile force or impact.

In addition, the metal film-coated thermosetting resin composition used in the present invention controls the curing reaction, and at the same time, a specific thermoplastic resin is added to the composition to control the flow properties. Therefore, the minimum viscosity window of the rheometer becomes wider, which is beneficial to the flow properties and pattern filling properties. Preferably, according to the present invention, within the temperature window of the metal foil lamination process, the window that maintains the lowest viscosity is widened, thereby achieving the effect of improving the flow properties 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 resin composition proposed in the present invention, the temperature window satisfying the viscosity conditions is as wide as 120°C to 180°C. That is, the flow property in the part of the lamination process 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 is improved.

The thermosetting resin composition coated with a metal film according to an embodiment of the present invention includes an amine compound, a thermosetting resin, a thermoplastic resin, and an inorganic filler.

The content of the above components is not particularly limited, but considering the physical properties of the final product manufactured from the thermosetting resin composition coated with a metal thin film, the above components may be included, and the content ratio between these components is as follows .

Specifically, the thermosetting resin composition according to an embodiment of the present invention may include an amine compound containing one or more functional groups selected from the group consisting of i) a sulfonyl group, a carbonyl group, a halogen group, and an Substituted or substituted with nitro, cyano or halogen groups, alkyl groups having 1 to 20 carbon atoms, ii) Unsubstituted or substituted with nitro, cyano or halogen groups, aromatic groups having 6 to 20 carbon atoms Group, iii) unsubstituted or substituted by a nitro, cyano or halogen group having 2 to 30 carbon atoms and iv) unsubstituted or substituted by a nitro, cyano or halogen group having 1 Group consisting of alkylene groups up to 20 carbon atoms. Amine compounds can be used as amine curing agents.

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

The amine compound contains an alkyl group having 1 to 20 carbon atoms selected from i) a sulfonyl group, a carbonyl group, a halogen group, unsubstituted or substituted by a nitro group, a cyano group or a halogen group, ii) unsubstituted or substituted Aryl group having 6 to 20 carbon atoms substituted by nitro, cyano or halogen, iii) heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted by nitro, cyano or halogen, and iv) The one or more functional groups in the group consisting of alkylene groups having 1 to 20 carbon atoms which are unsubstituted or substituted by nitro, cyano or halogen groups are strong electron-withdrawing groups (electron withdrawing group (EWG), and compared to amine compounds without electron withdrawing groups, amine compounds with electron withdrawing groups have reduced reactivity, so it is easy to control the curing reaction of the resin composition.

Therefore, the degree of curing reaction of the composition can be adjusted by the amine compound to improve the flow property, thereby improving the filling property of the circuit pattern.

The amine compound contains an alkyl group having 1 to 20 carbon atoms selected from i) a sulfonyl group, a carbonyl group, a halogen group, an unsubstituted or substituted by a nitro group, a cyano group or a halogen group, ii) an unsubstituted or substituted nitro group , Cyano or halogen substituted aryl groups having 6 to 20 carbon atoms, iii) unsubstituted or substituted by nitro, cyano or halogen groups having 2 to 30 carbon atom heteroaryl groups and iv) One or more functional groups in the group consisting of alkylene groups having 1 to 20 carbon atoms that are unsubstituted or substituted with nitro, cyano, or halogen groups, and the amine compound may contain 2 to 5 amines Based aromatic amine compounds.

More specifically, the amine compound may include one or more compounds selected from the group consisting of Chemical Formula 1 to Chemical Formula 3 below. [Chemical Formula 1]

In Chemical Formula 1, A is an alkyl 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, and have 1 to 6 An alkyl group of carbon atoms, an aryl group having 6 to 15 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, R ₁ , R ₁ ′, R ₂ and R ₂ ′ are each independently a hydrogen atom, 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, n is an integer of 1 to 10, and has 1 to 10 The alkylene group having a carbon atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, and a heteroaryl group having 2 to 20 carbon atoms can each be independently selected from the group consisting of nitro, One or more functional groups in the group consisting of cyano group and halogen group are substituted. [Chemical 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 having 2 Heteroaryl groups of up 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, having 6 to 15 carbons Aromatic aryl group or heteroaryl group having 2 to 20 carbon atoms, m is an integer of 1 to 10, and an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms and having 2 The heteroaryl groups of up to 20 carbon atoms may each be independently substituted with one or more functional groups selected from the group consisting of nitro, cyano, and halogen groups. [Chemical Formula 3]

In Chemical 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 having 2 Heteroaryl groups of up 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, and having 6 to 15 carbons Aromatic aryl groups or heteroaryl groups having 2 to 20 carbon atoms, and alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 15 carbon atoms, and heteroaryl groups having 2 to 20 carbon atoms The groups may each be independently substituted with one or more functional groups selected from the group consisting of nitro, cyano, and halogen groups.

The alkyl group is a monovalent functional group derived from an alkane, and examples thereof include linear, branched, or cyclic groups such as methyl, ethyl, propyl, isobutyl, second butyl, third butyl, Amyl, hexyl, etc. The one or more hydrogen atoms contained in the alkyl group may each be substituted with a substituent.

Alkyl groups are divalent functional groups derived from alkanes, and examples thereof include linear, branched, or cyclic groups, such as methyl groups, ethyl groups, propyl groups, isobutyl groups, and dibutyl groups. Radical, tertiary butyl, pentyl, hexyl, etc. Similar to the alkyl group, the one or more hydrogen atoms contained in the alkylene group may each be substituted with a substituent.

An aryl group is a monovalent functional group derived from an aromatic hydrocarbon, which may be, for example, a monocyclic or polycyclic group. Specific examples of monocyclic aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, distyryl, and the like. Examples of polycyclic aryl groups include, but are not limited to, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, perylene, benzyl, and fluorenyl. Similar to alkyl groups, one or more hydrogen atoms of these aryl groups may each be substituted with a substituent.

The heteroaryl group is a heterocyclic group containing O, N, or S as a hetero atom, and its carbon number is not particularly limited, but may be 2 to 30. Examples of heterocyclic groups include, but are not limited to, thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, triazinyl, acryl Pyridinyl, pyridazinyl, quinolinyl, isoquinolinyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl , Dibenzothienyl, benzofuranyl, dibenzofuranyl, etc. Similar to alkyl, one or more hydrogen atoms of these heteroaryl groups may each be substituted with a substituent.

The term "substituted" means that a hydrogen atom bonded to a carbon atom of a compound becomes another functional group, and the position to be substituted is not limited as long as the position is a position where a hydrogen atom is substituted, that is, the substituent can be substituted Is sufficient, and when two or more are substituted, the two or more substituents may be the same or different from each other.

More specifically, Chemical Formula 1 may include a compound represented by the following Chemical Formula 1-1. [Chemical Formula 1-1]

In Chemical Formula 1-1, A, X ₁ to X ₈ , R ₁ , R ₁ ′, R ₂ , R ₂ ′, and n have the same meanings as defined in Chemical Formula 1.

Specific examples of formula 1-1 include 4,4'-diaminodiphenyl sulfone (in formula 1-1, A is sulfhydryl, X ₁ to X ₈ , R ₁ , R ₁ ′, R ₂ and R ₂ 'are each independently a hydrogen atom, and n is 1), bis (4-aminophenyl) methanone (formula 1-1, A is a carbonyl _{group, X 1, X 2, R} 1, R 1' , R ₂ and R ₂ 'are each independently a hydrogen atom, and n is 1), 4,4'-(perfluoropropane-2,2-diyl) diphenylamine (in formula 1-1, A is a full Fluoropropane-2,2-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), 4,4′-(2,2 ,2-trifluoroethane-1,1-diyl)diphenylamine (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) and the like.

In addition, Chemical Formula 2 may include a compound represented by the following Chemical Formula 2-1. [Chemical Formula 2-1]

In Chemical Formula 2-1, Y ₁ to Y ₈ , R ₃ , R ₃ ′, R ₄ , R ₄ ′, and m have the same meanings as defined in Chemical Formula 2.

Specific examples of formula 2-1 include 2,2',3,3',5,5',6,6'-octafluorobiphenyl-4,4'-diamine (in formula 2-1, Y ₁ To Y ₈ is a halogen group, such as fluorine, R ₃ , R ₃ ′, R ₄ and R ₄ ′ are each independently a hydrogen atom, and m is 1), 2,2′-bis(trifluoromethyl)biphenyl -4,4'-diamine (wherein Y ₂ and Y ₇ are each independently trifluoromethyl, Y ₁ , Y ₃ , Y ₄ , Y ₅ , Y ₆ and Y ₈ are hydrogen atoms, R ₃ and R ₃ ', R ₄ and R ₄ 'are each independently a hydrogen atom, and m is 1) and so on.

In addition, Chemical Formula 3 may include a compound represented by the following Chemical Formula 3-1. [Chemical Formula 3-1]

In Chemical Formula 3-1, Z ₁ to Z ₄ , R ₅ , R ₅ ′, R ₆ and R ₆ ′ have the same meaning as defined in Chemical Formula 3.

Specific examples of Formula 3-1 include 2,3,5,6-tetrafluorobenzene-1,4-diamine (In Formula 3-1, Z ₁ to Z ₄ are halogen groups, such as fluorine, and R ₅ , R ₅ ', R ₆ and R ₆ 'are each independently a hydrogen atom) and the like.

Based on the total weight of the amine compound and the resin component (specifically, the total amount of the thermosetting resin and the thermoplastic resin), the content of the amine compound may be 5 to 50% by weight or 10 to 20% by weight. If the content of the amine compound is excessively reduced to less than 5% by weight, it may cause non-curing. If the content of the amine compound is excessively increased to more than 50% by weight, the curing rate may be increased, so that the flow properties of the thermosetting resin composition may be reduced, and further the mechanical properties of the metal thin film using the thermosetting resin composition may be due to unreacted The amine compound is lowered.

Meanwhile, the metal film-coated thermosetting resin composition according to an embodiment of the present invention may include a thermosetting resin.

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

More specifically, the biphenyl type epoxy resin may be an epoxy resin represented by the following Chemical Formula 11, and the dicyclopentadiene type epoxy resin may be an epoxy resin represented by the following Chemical Formula 12. [Chemical Formula 11]

In Chemical Formula 11, n is 0 or an integer of 1 to 50. [Chemical Formula 12]

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

Specific examples of the dicyclopentadiene type epoxy resin may include XD-1000 (purchased from Nippon Kayaku), and specific examples of the biphenyl type epoxy resin may include NC-3000H (purchased from Nippon Kayaku) Pharmaceutical companies).

In addition, the thermosetting resin may include one or more resins selected from the group consisting of bismaleimide resin, cyanate ester resin, and bismaleimide-triazine resin.

As the bismaleimide resin, those resins commonly used for thermosetting resin compositions coated with metal thin films can be used without limitation, and the types thereof are not limited. As a preferred example, the bismaleimide resin may be selected from diphenylmethane bismaleimide resin represented by the following chemical formula 13, phenylene type bismaleimide represented by the following chemical formula 14 Resin, bisphenol A type diphenyl ether bismaleimide resin represented by the following chemical formula 15 and diphenylmethane type bismaleimide resin represented by the following chemical formula 16 and phenylmethane type bismaleimide One or more of the group consisting of oligomers of imine resins. [Chemical Formula 13]

[化學式15]

[化學式16]

In Chemical Formula 13, R ₁ and R ₂ are each independently H, CH ₃ or C ₂ H ₅ . [Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

In Chemical Formula 16, n is 0 or an integer from 1 to 50.

In addition, specific examples of the cyanate ester-based resin include cyanate ester resins, and those resins commonly used for thermosetting resin compositions coated with metal thin films can be used without limitation, and the types thereof are not limited.

As a preferred example, the cyanate resin may be a novolac type cyanate resin represented by the following chemical formula 17, a dicyclopentadiene type cyanate resin represented by the following chemical formula 18, and a bisphenol represented by the following chemical formula 19 Type cyanate resin and its partially triazineated prepolymer. These resins may be used alone or in combination of two or more types. [Chemical Formula 17]

In Chemical Formula 17, n is 0 or an integer of 1 to 50. [Chemical Formula 18]

In Chemical Formula 18, n is 0 or an integer of 1 to 50. [Chemical Formula 19]

或

。In Chemical Formula 19, R is

or

.

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

The bismaleimide resin may include bismaleimide-triazine resin and the like. As the bismaleimide-triazine resin, those resins commonly used for thermosetting resin compositions coated with metal thin films can be used without limitation, and the types thereof are not limited. Preferred examples of the bismaleimide resin include BMI-2300 (purchased from DAIWA KASEI).

In particular, since the resin composition for coating a metal thin film according to an embodiment of the present invention contains the thermosetting resin in an amount of 400 parts by weight or less based on 100 parts by weight of the amine compound, the physical properties of the thermosetting resin can be prevented The properties are changed by fillers filled with a high content, and without being affected by the fillers, the thermosetting resin is induced to uniformly cure at a sufficient level, thereby improving the reliability of the final manufactured product, improving mechanical properties such as toughness, and sufficient Lower the glass transition temperature.

Conventionally, as in the case where the thermosetting resin is included in an amount of 400 parts by weight or less based on 100 parts by weight of the amine curing agent, the addition of a relatively excessive amount of the amine compound may result in excessive curing of the thermosetting resin. The problem of reduced flow properties and moldability. However, even when excessively adding a specific amine curing agent having reduced reactivity by including the above electron withdrawing group (EWG), the rapid increase in the curing rate of the thermosetting resin can be suppressed due to the reduced reactivity of the curing agent . Therefore, the metal film-coated resin composition and the metal foil thus obtained can exhibit high flow properties even during long-term storage, and have excellent flow properties.

Specifically, based on 100 parts by weight of the amine curing agent, the metal film-coated resin composition according to an embodiment of the present invention may include 400 parts by weight or less, from 150 parts by weight to 400 parts by weight, and 180 parts by weight The thermosetting resin in an amount of 1 part to 300 parts by weight, 180 parts by weight to 290 parts by weight, 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 thermosetting resin is a mixture of two or more types thereof, based on 100 parts by weight of the amine curing agent mixture, the content of the thermosetting resin mixture may also be 400 parts by weight or less than 400 parts by weight, 150 parts by weight Parts to 400 parts by weight, 180 parts to 300 parts by weight, 180 parts to 290 parts by weight, 190 parts to 290 parts by weight, or 240 parts to 260 parts by weight.

If 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 sufficient level due to the influence of the filler filled at a high content. Therefore, the reliability of the final manufactured product may be deteriorated, and mechanical properties such as toughness may also be deteriorated.

In addition, according to the present invention, based on the total weight of the amine compound and the resin component (specifically, the total amount of the thermosetting resin and the thermoplastic resin), the content of the epoxy resin may be 30% to 80% by weight, and the double-horse The content of lemethyleneimine may be 1% to 20% by weight. Preferably, based on the total weight of the amine compound and the resin component (specifically, the total amount of the thermosetting resin and the thermoplastic resin), the content of the epoxy resin may be 35% to 70% by weight. In addition, based on the total weight of the amine compound and the resin component (specifically, the total amount of the thermosetting resin and the thermoplastic resin), the content of bismaleimide may be 1% to 10% by weight.

If the amount of the epoxy resin is less than 30% by weight, there is a problem that it is difficult to implement high Tg, and if the amount of the epoxy resin is more than 80% by weight, there is a problem that the flow properties deteriorate.

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

Meanwhile, the resin composition coated with the metal thin film may have an equivalent weight of 1.4 or more, 1.4 to 2.5, 1.45 to 2.5, 1.45 to 2.1, 1.45 to 1.8, 1.49 to 1.75, or 1.6 to 1.7 calculated from the following mathematical equation 1 ratio. [Mathematical Equation 1] Equivalent ratio = total active hydrogen equivalent weight contained in amine compound (curing agent) / total curable functional group equivalent weight contained in thermosetting resin

More specifically, in the mathematical equation 1, the total active hydrogen equivalent weight contained in the amine curing agent means that the total weight (unit: grams) of the amine curing agent is divided by the active hydrogen equivalent weight of the amine curing agent ( G/equivalent).

When the amine curing agent is a mixture of two or more types thereof, the value is calculated by dividing the weight of each compound (unit: g) by the equivalent weight of active hydrogen unit (g/equivalent), and using The value obtained by summing the divided values can determine the unit equivalent weight of the total active hydrogen contained in the amine curing agent according to Mathematical Equation 1.

The active hydrogen contained in the amine curing agent means a hydrogen atom contained in the amine group (—NH ₂ ) present in the amine curing agent, and the active hydrogen can form a cured structure by reacting with the curable functional group of the thermosetting resin.

In addition, in Mathematical Equation 1, the total equivalent weight of the curable functional group contained in the thermosetting resin means that the total weight (unit: g) of the thermosetting resin is divided by the equivalent weight of the curable functional group of the thermosetting resin (g/equivalent) ) The value obtained.

When the thermosetting resin is a mixture of two or more types thereof, the value is calculated by dividing the weight of each compound (unit: gram) by the equivalent weight of the curable functional unit (gram/equivalent), and Using the value obtained by summing the divided values, the equivalent weight of the total curable functional group contained in the thermosetting resin can be determined according to Mathematical Equation 1.

The curable functional group included in the thermosetting resin means a functional group that forms a cured structure by reacting with active hydrogen of an amine curing agent, and the type of the curable functional group may vary according to 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. When the bismaleimide resin is used as the thermosetting resin, the curable functional group contained in the bismaleimide resin may be a maleimide group.

That is, the fact that the metal film-coated resin composition satisfies the equivalent ratio of 1.4 or greater calculated from Mathematical Equation 1 means that the amine curing agent is included at such a level that all thermosetting resins contained The curing functional group causes sufficient curing reaction. Therefore, in the resin composition coated with the metal thin film, when the equivalent ratio calculated by Mathematical Equation 1 is reduced to less than 1.4, it is difficult for the thermosetting resin to uniformly cure to a sufficient level due to the influence of the filler filled at a high content. Therefore, there is a disadvantage that the reliability of the final manufactured product may be deteriorated, and mechanical properties such as toughness may also be deteriorated.

Meanwhile, the metal film-coated resin composition according to an embodiment of the present invention may include a thermoplastic resin.

Thermoplastic resins have the effect of increasing toughness after curing and reducing the coefficient of thermal expansion and elastic modulus, thereby being used to reduce warpage of metal thin films. Specific examples of the thermoplastic resin include (meth)acrylate-based polymers.

Examples of the (meth)acrylate-based polymer are not particularly limited, and examples thereof may be acrylic acid containing a repeating unit derived from a (meth)acrylate-based monomer and a repeating unit derived from (meth)acrylonitrile An ester copolymer, or an acrylate copolymer containing repeating units derived from butadiene. For example, the (meth)acrylate-based polymer may be a copolymer copolymerized using monomers, for example, in the range of 1% to 40% by weight (based on the total weight of the entire monomer) Butyl acrylate, ethyl acrylate, acrylonitrile, methyl methacrylate and glycidyl methacrylate.

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 of increasing toughness and reducing the coefficient of thermal expansion and elastic modulus after curing will be reduced, which may be technically disadvantageous.

The weight average molecular weight as used herein refers to the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) method. In the process of measuring the weight-average molecular weight in terms of polystyrene measured by the GPC method, a detector and an analytical column can be used, such as a well-known analytical device and a differential refractive index detector, and Use common temperature conditions, solvents and flow rates. Specific examples of the measurement conditions are as follows: Waters PL-GPC220 instrument equipped with Polymer Laboratories PL Gel (PLgel) MIX-B, that is, a 300 mm column is used, and the evaluation temperature is 160 ℃, using 1,2,4-trichlorobenzene as the solvent, a flow rate of 1 ml/min, and prepare a sample with a concentration of 10 mg/10 ml, and then enter the amount of 200 μl, and the value of Mw can be used by The calibration curve formed by the polystyrene standard is determined. The polystyrene standard molecular weight is 9 kinds, 2000 / 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 PARACRON KG-3015P available from Negami Chemical Industrial Co., Ltd.

Meanwhile, based on the total amount of 100 parts by weight of the amine compound and the thermosetting resin, the thermoplastic resin may be included in an amount of 40 parts by weight to 90 parts by weight. Preferably, the thermoplastic resin may be included in an amount of 41 to 80 parts by weight, 42 to 70 parts by weight, or 42.7 to 67 parts by weight based on 100 parts by weight of the total amount of the amine compound and the thermosetting resin. If the content of the thermoplastic resin is less than 40 parts by weight, there is a problem that the fluidity of the resin is too high, and therefore the thickness deviation increases. If the content of the thermoplastic resin exceeds 90 parts by weight, there is a problem that the flow property is too small, and thus the filling property of the pattern deteriorates.

In addition, the metal film-coated thermosetting resin composition according to an embodiment of the present invention may include an inorganic filler.

As the inorganic filler, those inorganic fillers commonly used in thermosetting resin compositions coated with metal films can be used without limitation, and specific examples thereof include materials selected from the group consisting of silicon dioxide, aluminum trihydroxide, magnesium hydroxide, molybdenum oxide, and molybdenum. One or more of the group consisting of zinc acid, zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined kaolin, calcined talc, mica, short glass fiber, fine glass powder, and insulating glass.

Based on the total amount of 100 parts by weight of the amine compound and the thermosetting resin, the metal film-coated thermosetting resin composition may include 200 to 500 parts by weight, 205 to 450 parts by weight, 210 to 400 parts by weight, An inorganic filler in an amount of 210 to 300 parts by weight, 210 to 250 parts by weight, or 210 to 220 parts by weight. When the content of the inorganic filler is too small, the coefficient of thermal expansion increases, and thus the warpage phenomenon intensifies during the reflow process, and the rigidity of the printed circuit board decreases.

In addition, when using surface-treated fillers, the packing density can be increased by using the small-sized nanoparticle size and the large-sized particle size together, thereby increasing the filling rate.

The inorganic filler may include two or more types of inorganic fillers having different average particle diameters. Specifically, at least one of the two or more types of inorganic fillers may be an inorganic filler having an average particle diameter of 0.1 to 100 microns, and the other may be an average particle diameter of 1 nanometer to 90 nanometers Inorganic filler for rice.

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

From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler may be silicon dioxide surface-treated with a silane coupling agent.

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

Specific examples of the silane coupling agent include aminosilane coupling agents, such as 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-2-(aminoethyl Group)-3-aminopropyltrimethoxysilane; epoxy silane coupling agent, such as 3-glycidoxypropyl trimethoxysilane; vinyl silane coupling agent, such as 3-methacryloxypropyl Trimethoxysilane; cationic silane coupling agent, such as N-2-(N-vinylbenzylaminoethyl)-3-aminopropyltrimethoxysilane hydrochloride; and phenylsilane coupling agent. The silane coupling agent may be used alone, or if necessary, at least two silane coupling agents may be used in combination.

More specifically, the silane compound may include aromatic amine silane or (meth)acrylic silane. As the inorganic filler having an average particle diameter of 0.1 to 100 microns, silica dioxide treated with aromatic amine silane can be used, and as the inorganic filler having an average particle diameter of 1 nm to 90 nm, ( Base) propylene silane-treated silica. Specific examples of silicon dioxide surface-treated with aromatic amine silane include SC2050MTO (available from Admatechs), and specific examples of (meth)acrylic silane-treated silica may include AC4130Y (available from Nissan Chemical Company). (Meth)acrylic acid is meant to include acrylic acid or methacrylic acid.

The thermosetting resin composition coated with a metal thin film according to an embodiment of the present invention can be used as a solution by adding a solvent when necessary. If the solvent exhibits good solubility in the resin component, its type is not particularly limited, and alcohols, ethers, ketones, amides, aromatic hydrocarbons, esters, nitriles, etc. can be used. These solvents may be used alone, or a mixed solvent of two or more thereof may be used.

In addition, the thermosetting resin composition coated with a metal film may further contain various polymer compounds, such as other thermosetting resins, thermoplastic resins, oligomers and elastomers thereof, and other flame retardant compounds or additives, as long as the inherent characteristics of the resin composition are not Just be damaged. These compounds are not particularly limited as long as they are selected from compounds commonly used in the art. Examples of additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, pigments, dyes, thickeners, lubricants, defoamers, dispersants, leveling agents and Brightener. The composition can be used by mixing these additives to match the purpose.

Examples of other thermosetting resins include epoxy resins. As the epoxy resin, its type is not limited, but bisphenol A type epoxy resin, novolak type epoxy resin, phenyl aralkyl type epoxy resin, tetraphenylethane type epoxy resin, naphthalene can be used Type epoxy resin, its mixture, etc.

Specifically, the epoxy resin may include one or more selected from the group consisting of: a bisphenol A type epoxy resin represented by the following chemical formula 5, a novolac type epoxy resin represented by the following chemical formula 6, A phenylaralkyl type epoxy resin represented by the following chemical formula 7, a tetraphenylethane type epoxy resin represented by the following chemical formula 8, and a naphthalene type epoxy resin represented by the following chemical formula 9 and chemical formula 10. [Chemical Formula 5]

或

，且 n為0或1至50的整數。In Chemical Formula 5, R is

or

, And n is 0 or an integer from 1 to 50.

More specifically, depending on the type of R, the epoxy resin of Chemical Formula 5 may be bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-M type epoxy resin or bisphenol Phenol-S type epoxy resin. [Chemical Formula 6]

In Chemical Formula 6, R is H or CH ₃ , and n is 0 or an integer of 1 to 50.

[化學式8]

[化學式9]

[化學式10]

More specifically, depending on the type of R, the novolak-type epoxy resin of Chemical Formula 6 may be a phenol novolak-type epoxy resin or a cresol novolak-type epoxy resin, respectively. [Chemical Formula 7]

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical Formula 10]

Meanwhile, the metal film-coated thermosetting resin composition according to an embodiment of the present invention may include the above-mentioned amine compound, and may further include an additional curing agent other than the amine compound.

The thermosetting resin composition coated with a metal film according to an embodiment of the present invention having such a configuration can satisfy 2000 Pa·sec or less than 2000 Pa·sec in the minimum viscosity window of the rheometer in the range of 120℃ to 180℃ The complex viscosity conditions.

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 proposed in the present invention, the temperature window satisfying the viscosity conditions is as wide as 120°C to 180°C. That is, the flow property in the lamination process portion is high, and therefore no empty space is generated after resin lamination, and the filling property of the pattern is excellent.

Since the metal film-coated thermosetting resin composition according to the present invention has excellent resin flow properties as described above, the flow properties can be ensured during the process of preparing or constructing a metal film or metal laminate using the metal film, thereby easily Fill fine patterns and improve the crack resistance of the film. II. Resin-coated metal film

According to another embodiment of the present invention, a resin-coated metal film including a cured product of a metal film-coated thermosetting resin composition can be provided. The details of the metal film-coated thermosetting resin composition include the details explained above with reference to the examples.

Specifically, a resin-coated metal thin film including a cured product and an inorganic filler dispersed between the cured products can be provided: an amine compound containing one or more functional groups, the one or more functional groups The group is selected from i) a sulfonyl group, a carbonyl group, a halogen group, an unsubstituted or substituted nitro group, a cyano group or a halogen group, an alkyl group having 1 to 20 carbon atoms, ii) an unsubstituted or substituted nitro group, a cyano group Aryl group having 6 to 20 carbon atoms substituted by a group or a halogen group, iii) heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted by a nitro, cyano or halogen group, and iv) without A group consisting of alkylene groups having 1 to 20 carbon atoms substituted or substituted by nitro, cyano or halogen groups; thermosetting resins; and thermoplastic resins.

As described above, the present invention can provide a resin-coated metal thin film exhibiting excellent thermal and mechanical properties by a simple method of directly coating a resin composition having excellent resin flow properties and pattern filling properties onto metal foil. According to the above process, a thermosetting resin including a filler can be formed in the metal thin film, and specifically, the filler can be in a form in which the filler is uniformly dispersed in the cured product formed on the resin coating the metal thin film.

Therefore, the filler dispersed between the cured product and the cured product can be formed by a process including the steps of: applying the thermosetting resin composition to the metal thin film; and applying the thermosetting resin composition to the metal thin film Steps of curing.

According to an embodiment of the present invention, the resin-coated metal thin film can be manufactured by a simple method in which the above components are mixed to produce a coated varnish, which is then coated on the metal foil On, followed by curing and drying.

In addition, in the present invention, the curing reaction of the resin is adjusted to lengthen the window where the lowest viscosity remains within the temperature window of the lamination process.

Preferably, curing may be performed at a temperature of 180°C to 250°C for 1 hour to 4 hours.

In addition, the method of applying the metal film-coated thermosetting resin composition to the metal foil is not particularly limited, and a coating method known in the art may be used.

As an example, a method in which a thermosetting resin composition coated with a metal thin film is placed on a metal foil in a coating device and is coated with a certain thickness can be used. As the coating device, a comma coater, a blade coater, a lip coater, a bar coater, an extrusion coater, a reverse coater, a transfer roll coater, a gravure coater can be used , Spray coating machine, etc.

In addition, a carrier film can be used to evaluate the flow properties, and as a carrier film, a plastic film such as polyethylene terephthalate (PET) film, polyester film, polyimide film, poly Amidimide film, polypropylene film, polystyrene film, etc.

Meanwhile, the varnish used for coating may be in a state in which a solvent is added to the thermosetting resin composition. The solvent used 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 thereof include ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons, such as benzene, toluene, and xylene; and amides, such as dimethylformamide and dimethylacetamide. Amine; fatty alcohols, such as methyl cellosolve and butyl cellosolve, etc.

The cured product may have a thickness of 5 to 90 microns, preferably 5 to 30 microns. Even if such a cured product is formed thinly on a metal foil, the cured product can be made to exhibit excellent thermal and mechanical properties relative to the metal foil. When the thickness of the cured product increases or decreases by a specific value, the physical properties measured in the resin-coated metal film can also change the specific value.

The coating cured coating layer of the metal film-coated thermosetting resin composition according to an embodiment of the present invention has a glass transition temperature (Tg) of 220°C to 240°C.

According to one embodiment of the present invention, the coating cured product of the metal film-coated thermosetting resin composition has 1% or more in the machine direction (MD) direction, 1% to 10%, 2% to 5% , 3% to 4% or 3.6% to 3.8% tensile elongation, the tensile elongation is based on IPC-TM-650 (2.4.18.3) using a universal testing machine (Instron (Instron) 3365) Measured.

That is, as a result of performing a tensile test with a resin composition composed of a single molecule type, it can be observed that the elongation at break is much better when compared at the same thickness, thereby confirming that the crack resistance is excellent of.

Therefore, the present invention can help to improve the efficiency of semiconductor devices, because at the same thickness, the crack resistance is superior to the conventional resin-coated copper foil composed of a single molecule type.

The metal foil includes a composite foil having a three-layer structure including copper foil; aluminum foil; nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, or lead-tin alloy as an intermediate layer, and A copper layer having different thicknesses is included on both sides; or a composite foil having a two-layer structure in which aluminum and copper foil are combined may be used.

According to a preferred embodiment, the metal foil used in the present invention is a copper foil or an aluminum foil, and a metal foil with a thickness of about 2 microns to 200 microns can be used, but a metal foil with a thickness of about 2 microns to 35 microns is preferred . Preferably, copper foil is used as the metal foil. In addition, according to the present invention, the following composite foil can be used as the metal foil: a composite foil having a three-layer structure including nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, and lead- A tin alloy or the like is used as an intermediate layer, and includes a copper layer of 0.5 μm to 15 μm and a copper layer of 10 μm to 300 μm provided on both sides thereof, or a composite foil having a two-layer structure in which the two-layer type Aluminum and copper foil are combined in the structure. III. Metal cladding laminate

According to still another embodiment of the present invention, there is provided a metal clad laminate including the resin-coated metal thin film of other embodiments. The details of the resin-coated metal thin film include those explained above with reference to other embodiments.

Specifically, the metal cladding laminate may be a metal cladding laminate obtained by laminating one or more resin-coated metal thin films obtained in other embodiments.

Therefore, the present invention can be used to manufacture double-sided or multi-layer printed circuit boards after laminating one or more resin-coated metal films. In the present invention, the metal clad laminate can be subjected to circuit processing to produce a double-sided or multilayer printed circuit board, and the circuit can be implemented by a method commonly used in the manufacturing process of double-sided or multilayer printed circuit boards deal with. [ Advantageous Effects ]

According to the present invention, it is possible to provide a metal film-coated thermosetting resin composition having excellent flow properties and improved mechanical properties such as crack resistance and tensile properties, and a resin-coated metal film and a metal cladding layer using the same Compound.

In the following, the invention is explained in further detail with reference to examples. However, these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. > Examples and comparative examples: Preparation of metal film-coated thermosetting resin composition and resin-coated copper film > (1) Preparation of metal film-coated thermosetting resin composition

According to the composition shown in Table 1 and Table 2 below, each component was added to methyl ethyl ketone with a solid content of 40% and mixed, and then stirred at a speed of 400 revolutions per minute (rpm) at room temperature for one day. Then, viscosity adjustment and defoaming were performed using a rotary evaporator to prepare metal film-coated resin compositions (resin varnishes) of Examples and Comparative Examples. In particular, the specific composition of the resin composition prepared in Examples is shown in Table 1 below, and the specific composition of the resin composition prepared in Comparative Examples is shown in Table 2 below. (2) Preparation of resin-coated copper foil

Using a comma coater (coating thickness: 16 microns), the metal film-coated resin compositions of Examples and Comparative Examples were applied to copper foil (thickness of 2 microns, manufactured by Mitsui), and then Cure for 100 minutes at 220°C and 35 kg/cm2. Then, it was cut into a size of 17 cm×15 cm to prepare a resin-coated copper foil sample. > Experimental example: measuring the physical properties of the resin composition coated with metal film and the copper foil coated with resin >

The physical properties of the metal film-coated resin composition and the resin-coated copper foil obtained in Examples and Comparative Examples were measured by the following methods, and the results are shown in Tables 1 and 2 below. 1. Measure viscosity and flow properties (1) Rheometer viscosity

The metal film-coated thermosetting resin compositions of Example 1 and Comparative Example 3 were applied to PET substrates, and then laminated using a laminator to prepare samples with appropriate thickness, and the viscosity of the rheometer (according to the temperature Viscosity measurement conditions, heating rate 5°/min, frequency: 10 Hz). (2) Filling properties of circuit patterns

A copper clad laminate (CCL) having a pattern in which about 60% of the total area of the copper foil (thickness 10 μm, manufactured by Mitsui Corporation) was etched was used. The resin copper foil coating samples obtained in Examples or Comparative Examples were laminated thereon, and the filling properties of circuit patterns were evaluated according to the following criteria. ○: No voids or delamination X: No voids or delamination 2. Physical properties of cured resin

In order to analyze the physical properties of the cured resin, the two resin-coated copper foils of the examples were used to laminate the resin layers so that they faced each other, and the vacuum hot press was used at 220°C and 35 kg/cm 2 Under conditions, curing will be performed for 100 minutes.

During the experiment, the copper foil was removed by etching, and the physical properties of the resin layer were measured by the following method. (1) Glass transition temperature (Tg)

By using a dynamic mechanical analyzer (DMA) (TA instrument, Q800) in the stretching mode, the measurement is performed from 25°C to 300°C under a temperature increase condition of 5°C/min, and the peak temperature of tanδ is Recorded as the glass transition temperature. (2) Coefficient of thermal expansion (CTE)

By using TMA (TA instrument, Q400), the measurement is performed from 30°C to 260°C at a temperature increase rate of 10°C/min, and then the measurement value in the range of 50°C to 150°C is recorded as the thermal expansion coefficient. (3) Storage modulus

The storage modulus was measured from 25°C to 300°C using DMA (TA instrument, Q800) in the stretching mode at a temperature increase of 5°C/min. (4) Tensile elongation

[表2] 比較例的塗覆金屬薄膜之熱固性樹脂組成物的組成（單位：克）

*環氧樹脂（日本化藥公司；環氧當量253克/當量）*NC-3000H：環氧樹脂（日本化藥公司；環氧當量290克/當量） *BMI-2300：雙馬來醯亞胺系樹脂（大和化成公司；馬來醯亞胺當量179克/當量） *DDS：4,4'-二胺基二苯基碸（活性氫當量62克/當量） *丙烯酸橡膠（Mw 800,000）：帕拉克倫KG-3015P（內加米化工有限公司） *當量比：藉由以下數學方程式1計算。 [數學方程式1] 胺化合物對熱固性樹脂的當量比=(DDS的總環氧樹脂當量) / (XD-1000的總環氧樹脂當量 + NC-3000H的總環氧當量重量) + (BMI-2300的總馬來醯亞胺當量重量)According to IPC-TM-650 (2.4.18.3), a universal testing machine (Instron 3365) was used to measure the tensile elongation in the longitudinal direction. [Table 1] Composition of the thermosetting resin composition of the coated metal film of the example (unit: g)

[Table 2] Composition of the thermosetting resin composition of the metal film-coated comparative example (unit: g)

*Epoxy resin (Nippon Chemical Co., Ltd.; epoxy equivalent 253 g/equivalent) *NC-3000H: Epoxy resin (Japan Chemical Co., Ltd.; epoxy equivalent 290 g/equivalent) *BMI-2300: Shuangmalaya Amine-based resin (Daiwa Chemical Co., Ltd.; maleimide equivalent 179 g/equivalent) *DDS: 4,4'-diaminodiphenyl sulfone (active hydrogen equivalent 62 g/equivalent) *Acrylic rubber (Mw 800,000) : Paraclen KG-3015P (Negami Chemical Co., Ltd.) *Equivalent ratio: calculated by the following mathematical equation 1. [Mathematical Equation 1] Equivalent ratio of amine compound to thermosetting resin = (total epoxy resin equivalent of DDS) / (total epoxy resin equivalent of XD-1000 + total epoxy equivalent weight of NC-3000H) + (BMI-2300 (Equivalent weight of total maleimide)

In Mathematical Equation 1, the total active hydrogen equivalent weight of DDS is the value obtained by dividing the total weight of DDS (g) by the equivalent weight of active hydrogen unit of DDS (62 g/equivalent), The total epoxy equivalent weight of X-1000 is the value obtained by dividing the total weight (g) of X-1000 by the equivalent epoxy unit weight (253 g/equivalent) of X-1000, The total epoxy equivalent weight of NH-3000H is a value obtained by dividing the total weight (g) of NH-3000H by the equivalent epoxy unit weight of NH-3000H (290 g/equivalent), and The total equivalent weight of maleimide of BMI-2300 is a value obtained by dividing the total weight (grams) of BMI-2300 by the equivalent weight of maleimide of BMI-2300 (179 g/equivalent).

Referring to Tables 1 and 2 above, it is confirmed that in the case of the examples of the present invention, the resin-coated copper foil containing an amine compound having an electron-withdrawing group (EWG) has a glass transition temperature of 230°C to 235°C, and It exhibits a complex viscosity of 2000 Pa·s or less in the temperature range of 120°C to 180°C, and has a thermal expansion coefficient of 21 ppm/°C or less than 21 ppm/°C, and therefore has excellent filling properties of circuit patterns .

In contrast, in the case of Comparative Example 3, since an excessive amount of thermoplastic resin was added, there was no temperature window in which the complex viscosity appeared to be 2000 Pa·s or less, and the filling property of the circuit pattern was also very difference.

On the other hand, in the case of the example, the tensile elongation was measured as high as 3.6% to 3.8%, and it was excellent in crack resistance, while in Comparative Example 1 where no thermoplastic resin was added and comparison with a small amount of thermoplastic resin added In the case of Example 2, the tensile elongation is 0.4% and 0.9%, respectively, which is very low compared to the example.

no.

FIG. 1 shows temperature-dependent rheometer viscosity charts of Example 1 and Comparative Example 3. FIG.

no.

Claims (15)

A thermosetting resin composition coated with a metal film, comprising: An amine compound containing one or more functional groups selected from the group consisting of i) a sulfonyl group, a carbonyl group, a halogen group, unsubstituted or substituted by a nitro group, a cyano group or a halogen group, having 1 to 20 Alkyl group with 2 carbon atoms, ii) aryl group having 6 to 20 carbon atoms unsubstituted or substituted with halogen group, iii) unsubstituted or substituted with nitro, cyano or halogen group having 2 to 30 A heteroaryl group of 1 carbon atom and iv) a group consisting of an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a nitro, cyano or halogen group; Thermosetting resin; Thermoplastic resin; and Inorganic fillers, Wherein the thermoplastic resin is included in an amount of 40 parts by weight to 90 parts by weight based on 100 parts by weight of the total amount of the amine compound and the thermosetting resin, and Wherein the thermosetting resin composition has a complex viscosity of 2000 Pa·s or less in the range of 120°C to 180°C. The thermosetting resin composition coated with a metal thin film as described in item 1 of the patent scope, wherein The thermosetting resin includes dicyclopentadiene type epoxy resin and biphenyl type epoxy resin. The thermosetting resin composition coated with a metal thin film as described in item 1 of the patent scope, wherein Based on 100 parts by weight of the dicyclopentadiene-type epoxy resin, the content of the biphenyl-type epoxy resin is less than 100 parts by weight. The thermosetting resin composition coated with a metal film as described in item 2 of the scope of patent application, in which The thermosetting resin further includes one or more resins selected from the group consisting of bismaleimide resin, cyanate resin, and bismaleimide-triazine resin. The thermosetting resin composition coated with a metal thin film as described in item 1 of the patent scope, wherein The thermosetting resin is included in an amount of 400 parts by weight or less based on 100 parts by weight of the amine compound. The thermosetting resin composition coated with a metal thin film as described in item 1 of the patent scope, wherein The equivalent ratio calculated by the following mathematical equation 1 is 1.4 or greater: [Mathematical Equation 1] Equivalent ratio = total active hydrogen equivalent weight contained in the amine compound / total curable functional group equivalent weight contained in the thermosetting resin. The thermosetting resin composition coated with a metal thin film as described in item 1 of the patent scope, wherein The amine compound includes an aromatic amine compound having 2 to 5 amine groups. The thermosetting resin composition coated with a metal thin film as described in item 1 of the patent scope, wherein The thermosetting resin includes a (meth)acrylate polymer. The thermosetting resin composition coated with a metal thin film as described in item 8 of the patent scope, wherein The (meth)acrylate-based polymer is an acrylate copolymer containing repeating units derived from (meth)acrylate-based monomers and repeating units derived from (meth)acrylonitrile; Acrylate copolymer of repeating units of diene. The thermosetting resin composition coated with a metal thin film as described in item 8 of the patent scope, wherein The (meth)acrylate-based polymer has a weight average molecular weight of 500,000 to 1,000,000. The thermosetting resin composition coated with a metal thin film as described in item 1 of the patent scope, wherein The inorganic filler is included in an amount of 200 parts by weight to 500 parts by weight based on 100 parts by weight of the total amount of the amine compound and the thermosetting resin. The thermosetting resin composition coated with a metal thin film as described in item 1 of the patent scope, wherein The inorganic filler includes two or more types of inorganic fillers having different average particle diameters, and At least one of the two or more types of inorganic fillers is an inorganic filler with an average particle diameter of 0.1 to 100 microns, and the other is an inorganic filler with an average particle diameter of 1 to 90 nanometers. A resin-coated metal film, including the cured product of the metal film-coated thermosetting resin composition as described in item 1 of the patent application. A resin-coated metal film, including An amine compound containing one or more functional groups selected from the group consisting of i) a sulfonyl group, a carbonyl group, a halogen group, an unsubstituted or substituted by a nitro group, a cyano group or a halogen group having 1 to 20 Alkyl group with 2 carbon atoms, ii) unsubstituted or substituted with nitro, cyano or halogen groups having 6 to 20 carbon atoms, iii) unsubstituted or substituted with nitro, cyano or halogen groups Substituted heteroaryl groups having 2 to 30 carbon atoms and iv) unsubstituted or substituted by nitro, cyano or halogen groups having 1 to 20 carbon atom alkylene groups; thermosetting resins; And the cured product between the thermoplastic resin, and Inorganic filler dispersed between the cured products. A metal-clad laminate comprising a resin-coated metal film as described in item 13 or item 14 of the patent application.

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