WO2013089410A1

WO2013089410A1 - Cyanate ester resin composition for manufacturing circuit board and flexible metal-clad laminates including same

Info

Publication number: WO2013089410A1
Application number: PCT/KR2012/010743
Authority: WO
Inventors: 박영석; 박순용; 장세명
Original assignee: 주식회사 엘지화학
Priority date: 2011-12-12
Filing date: 2012-12-11
Publication date: 2013-06-20

Abstract

The present invention relates to an adhesive resin composition for manufacturing a circuit board and the use thereof. The adhesive resin composition according to the present invention comprises: a cyanate ester resin; fluorinated resin powder which is dispersed within said cyanate ester resin; and a rubber component, wherein the invention has low dielectric permittivity and a low dielectric loss coefficient, thereby capable of manufacturing a circuit board having a further improved electric characteristic.

Description

【Specification】

[Name of invention]

Cyanate ester resin composition for circuit board manufacture and flexible metal foil laminate comprising same

Technical Field

The present invention relates to a cyanate ester-based adhesive resin composition and its use which can be applied to the production of circuit boards.

Background Art

Recently, according to the trend of thinning and densification of various electronic components, flexible printed circuit boards (FPCBs) are being used in various fields, and market uniformity is gradually increasing.

A flexible printed circuit board is a substrate having a flexible and flexible structure, which forms a conductor pattern capable of transmitting an electrical signal on an electrically insulating substrate. Copper clad laminates (CCL) are used for such a flexible printed circuit board, and the copper foil laminate is an electrical insulating film and a copper foil laminated, and an adhesive for bonding a polyimide film and copper foil is interposed therebetween. Moreover, the copper foil of the copper foil laminated board was processed and the wiring pattern was formed. Coverlay covering the wiring pattern forming surface to protect the wiring afterwards, Bonding sheet for bonding the copper foil laminate and coverlay when manufacturing multilayer circuit board, Interlayer insulation and adhesion and flexible printed circuit board Adhesives are used in the production of prepreg and the like for imparting hardness to the resin.

Such a flexible printed circuit board basically requires adhesion between the electrically insulating film and the copper foil, heat resistance, solvent resistance, dimensional stability, flame retardancy, and the like. Furthermore, with the recent trend of higher performance of electronic devices, faster internal signal transfer speeds are required in printed circuit boards, and therefore, various materials used in flexible printed circuit boards require lower dielectric constants and dielectric loss coefficients. have.

As a result, various materials or methods are available that can improve the dielectric constant and dielectric loss factor while meeting the basic performance requirements of the substrate. It is being proposed, but the degree of improvement is still insufficient. In particular, epoxy resin adhesives generally used in the manufacture of flexible metal foil laminates have limitations in lowering the dielectric constant and dielectric loss coefficient of laminates due to the inherent dielectric properties of epoxy resins, and introducing fluorine groups. It is difficult to sufficiently overcome these limitations with the modified epoxy resin through, and there is an urgent need for improvement.

[Content of invention]

[Problem to solve]

The present invention is useful in the manufacture of high performance circuit boards with low dielectric constant and dielectric loss coefficient. To provide an adhesive resin composition that can be used.

In addition, the present invention is to provide a bonding sheet, cover, a prepreg and a flexible metal foil laminate comprising the adhesive resin composition.

[Measures of problem]

According to the invention,

An adhesive resin composition for producing a circuit board comprising a cyanate ester resin and a fluorine-based resin powder and a rubber component dispersed in the cyanate ether resin is provided.

The adhesive resin composition may include 10 to 90 parts by weight of the fluorine resin powder and 1 to 80 parts by weight of the rubber component based on 100 parts by weight of the cyanate ester resin.

In addition, the fluorine-based resin powder included in the composition may have a number average particle diameter of 10 or less.

In addition, the bloso resin powder is poly tetrafluoro ethylene (PTFE), perfluoroalkoxy polymer (PFA), fluorinated ethylene-propylene copolymer (FEP), chlorotrifluoro ethylene (CTFE) ), Tetrafluoro ethylene / chlorotrifluoroethylene copolymer (TFE / CTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), ethylene-tetrafluoroethylene copolymer (ETFE), and polychloro It may be a powder of at least one fluorine resin selected from the group consisting of trifluoro ethylene (PCTFE). And, the cyanate ester resin may be at least difunctional aliphatic cyanate ester, at least difunctional aromatic cyanate ester, or a combination thereof.

And, the rubber component is natural rubber, styrene butadiene rubber (SBR), isoprene rubber (IR), acrylonitrile butadiene rubber (NBR) ethylene propylene diene monomer (EFDM) rubber, polybutadiene rubber, and modified polybutadiene rubber It may be one or more selected from the group consisting of.

On the other hand, the composition may further comprise an organic solvent.

At this time, the organic solvent is Ν, Ν-dimethylformamide, Ν, Ν-dimethylacetamide, acetone, methyl ethyl ketone, cyclohexanone, Ν-methyl-2-pyridone, methyl salosolve, toluene, Methane, ethane, propanol, and dioxolane. The organic solvent may be included in an amount of 50 to 500 parts by weight based on 100 parts by weight of the total solids of the composition.

Meanwhile, according to another embodiment of the present invention, a bonding sheet including a cured product of the adhesive resin composition is provided.

In addition, according to another embodiment of the present invention, a coverlay including an electrically insulating film and the bonding sheet bonded to at least one side of the electrically insulating film is provided.

And according to another embodiment of the present invention, a prepreg comprising a reinforcing fiber and the adhesive resin composition impregnated in the reinforcing fiber is provided.

And, according to another embodiment of the present invention, comprising an electrically insulating film, a metal foil laminated on at least one side of the electrically insulating film, and an adhesive resin layer interposed between the electrically insulating film and the metal foil; The said flexible resin layer is provided with the flexible metal foil laminated board containing the hardened | cured material of the adhesive resin composition mentioned above.

【Effects of the Invention】

The adhesive resin composition according to the present invention has a low dielectric constant and a low dielectric loss coefficient, which enables the production of a circuit board having more improved electrical properties. [Brief Description of Drawings]

1 and 2 are cross-sectional views schematically showing the configuration of a flexible metal foil laminate according to an embodiment of the present invention, respectively.

[Specific contents to carry out invention]

Hereinafter, the adhesive resin composition and its uses according to embodiments of the present invention will be described.

Prior to that, unless otherwise stated throughout the specification, the terminology is merely for reference to specific embodiments and is not intended to limit the invention.

As used herein, the singular forms “a,” “an” and “the” include plural forms as well, unless the phrases clearly indicate the opposite.

In addition, the meaning of "include" as used herein specifies a particular characteristic, region, integer, step, operation, element or component, excluding the addition of other specific characteristics, region, integer, step, operation, element, or component. It is not meant to be. On the other hand, the inventors of the present invention in the process of studying the adhesive resin composition for circuit board manufacturing, in the case of a composition in which the fluorine-based resin powder is dispersed in the cyanate ester resin, compared to the previously known epoxy resin or cyanate ester resin adhesive, It was confirmed that lower permittivity and smaller dielectric loss factor can be obtained at the same time. And, it was confirmed that such a composition enables the manufacture of a circuit board capable of exhibiting more improved electrical properties, and completed the present invention.

Previously, epoxy resins were mainly used as adhesives for the production of circuit boards such as flexible printed circuit boards. In order to improve the dielectric constant characteristic of the epoxy resin adhesive, various methods of using a fluorine-modified epoxy resin having a fluorine group introduced into the epoxy resin have been attempted. However, the type of epoxy resin capable of fluorine modification is limited, and there is a restriction in that an epoxy resin suitable for the type of circuit board to be applied can not be freely selected. In addition, the introduction of a fluorine-modified epoxy resin not only leads to an increase in manufacturing cost, but also has a limit in securing a sufficient low dielectric constant characteristic. there was. Above all, epoxy resins have limitations in applications where low dielectric constant properties are required due to the inherent physical properties of dielectric constants of 3.5 or more and dielectric loss coefficient of 0.02 or more.

The adhesive resin composition according to the present invention is a composition in which fluorine-based resin powder is uniformly dispersed on a matrix containing cyanate ester resin, and is applicable to cyanate esters, unlike the aforementioned epoxy resins or fluorine-modified epoxy resins. The kind of resin is not specifically limited. In addition, the adhesive resin composition according to the present invention may include a fluorine-based resin powder in a sufficient amount such that there is no problem such as deterioration of physical properties even when applied to the production of ½ printed circuit board, the intrinsic physical properties of the adhesive resin composition The degradation of the electrical, physical or thermal properties of the flexible printed circuit engine can be minimized. According to one embodiment of the present invention as described above,

There is provided an adhesive resin composition for producing a circuit board comprising a cyanate ester resin and a bloso resin powder and a rubber component dispersed in the cyanate ester resin.

First, the cyanate ester resin is a base resin, as long as it is suitable for use as an adhesive resin in the art to which the present invention pertains, it can be applied without particular limitation of its configuration.

However, according to the present invention, the cyanate ester resin may be at least bifunctional aliphatic cyanate ester, at least bifunctional aromatic cyanate ester, or a combination thereof.

Examples of such cyanate ester resins include 1,3,5-tricyanatobenzene (1,3,5-tricyanatobenzene),

1.3-dicyanatonaphthalene (1,3-dicyanatonaphthalene),

1.4-dianetononaphthalene (1,4-dicyanatonaphthalene),

1,6-dicyanatonaphthalene (1,6-dicyanatonaphthalene),

1,8-dicyanatonaphthalene (1,8-dicyanatonaphthalene),

2,6-dicyanatonaphthalene (2,6-dicyanatonaphthaIene), Polymers of at least one polyfunctional cyanate ester selected from the group consisting of 2,7-dicyanatonaphthalene; Bisphenol A cyanate ester resin or those in which hydrogen is added; Bisphenol F type cyanate ester resin or hydrogenated thereto; 6F bisphenol A dicyanate ester resin; Bisphenol E type diacid ester resin; Tetramethylbisphenol F di ^' cyanate resin; Bisphenol M disyanate ester resin; Dicyclopentadiene bisphenol dicyanate ester resin; Or cyanate novolac resins.

And as a commercial item of the said cyanate ester resin, for example, brand name AcroCy B (made by Ciba-Geigy, the average cyanate ester group in about 1 molecule), AcroCy F (made by Ciba-Geigy, in 1 molecule), for example. Average cyanate ester group about 2), AcroCy L (manufactured by Ciba-Geigy, 1 molecule increase average cyanate ester group about 2), AcroCy M (manufactured by Ciba-Geigy, about 2 average cyanate ester groups in 1 molecule) ), RTX 366 (manufactured by Ciba-Geigy, about 2 average cyanate ester groups in 1 molecule), XU-71787 (manufactured by Dow Chmical, average 2 cyanate ester groups in 1 molecule), Primaset PT-30 (Lonza Production, at least about 2 cyanate ester groups in one molecule), BTP-6020 (manufactured by Lonza, at least about 2 average cyanate ester groups in one molecule), BA-230 (manufactured by Lonza, cyanate esters in one molecule) About 2 or more), BA-3000 (manufactured by Lonza, cyanate ester group in 1 molecule) And about two or more). On the other hand, the adhesive resin composition according to the present invention contains a fluorine-based resin powder dispersed in the cyanate ester resin.

In particular, the smaller the particle size of the fluorine-based resin powder may have a greater effect of lowering the dielectric constant. And, considering that the thickness of the flexible copper foil laminate is generally about tens of micrometers, the fluorine-based resin powder is 10 or less, preferably 0.1 to 10, more preferably 0.1 to 7 βη, even more preferably 0.1 It may be to have a number average particle diameter of 5 to.

In addition, according to the present invention, as the fluorine-based resin powder It can be used that can express the effect of improving the dielectric properties, preferably polytetrafluoroethylene (PTFE), perfluoroalkoxy polymer (PFA), fluorinity J ethylene-propylene copolymer (FEP), Chlorotrifluoroethylene (CTFE), tetrafluoroethylene / chlorotrifluoroethylene copolymer (TFE / CTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), ethylene-tetrafluoroethylene copolymer (ETFE ), And polychlorotrifluoroethylene (PCTFE) may be a powder of at least one fluorine-based resin selected from the group consisting of.

In particular, among the fluorine resins exemplified above, the use of a powder of polytetrafluoroethylene (PTFE) resin having a high glass transition temperature (Tg) while having a low dielectric constant and a dielectric loss coefficient is excellent. It is advantageous to be able to minimize the deterioration of the physical properties of the composition with the addition of the powder.

However, polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), and the like, even in the case of fluorine resin, are not preferable because they can express low dielectric properties required in the present invention.

And, the amount of the fluorine resin powder contained in the adhesive resin composition of the present invention is 10 to 90 parts by weight, preferably 10 to 70 parts by weight, more preferably 20 to 60 parts by weight of 100 parts by weight of the cyanate ester resin. It may be part by weight. That is, in order to sufficiently express characteristics such as low dielectric constant, low dielectric loss, and low water absorption according to the addition of the fluorine resin powder, the fluorine resin powder is included in an amount of 10 parts by weight or more based on 100 parts by weight of cyanate ester resin. It is advantageous. In addition, when the fluorine-based resin powder is included in an excessive amount, the mechanical properties of the coating layer formed using the adhesive resin composition is relatively poor, the coating layer may be torn or broken. 1, In order to prevent this phenomenon, the fluorine-based resin powder is It is unique to include 90 parts by weight or less based on 100 parts by weight of cyanate ester resin. Meanwhile, the adhesive resin composition according to the present invention may further include a rubber component dispersed in the cyanate ester resin. In other words, in order to use the adhesive resin composition in the manufacture of a flexible printed circuit board, the composition itself should have a layered ductility, and the adhesive resin composition may further include a rubber component to compensate for the ductility.

At this time, the rubber component may be natural rubber or synthetic rubber, preferably styrene butadiene rubber (SBR), isoprene rubber (IR), acrylonitrile butadiene rubber (NBR), ethylene propylene diene monomer (EPDM) rubber, Synthetic rubber such as polybutadiene rubber, modified polybutadiene rubber, and the like.

Here, it is preferable that the molecular weight of the said synthetic rubber is 20,000-200,000. That is, in order to ensure the minimum thermal stability required for the rubber component, the molecular weight of the synthetic rubber is preferably 20,000 or more. In addition, when the molecular weight of the rubber component is larger than necessary, the solubility in the solvent is lowered, thereby increasing the viscosity of the composition, and thus, the workability may be poor and the adhesion may also be lowered. In order to prevent this, the molecular weight of the synthetic rubber is 200,000. It is preferable that it is the following.

In particular, EPDM rubber having a ethylene content of about 10 to 40% by weight of the synthetic rubber (dielectric constant about 24, dielectric loss factor about 0.001) is the SBR (dielectric constant about 2.4, dielectric loss factor about 0.003) or NBR (dielectric constant about 2.5 The dielectric loss factor and the dielectric loss factor of the resin composition may be lowered as compared to the dielectric loss factor of about 0.005). In addition, the EPDM rubber is low in water absorption, excellent in weatherability and electrical insulation, it can be preferably included in the composition of the present invention. However, the EPDM rubber has a relatively poor solubility in solvents, making it difficult to secure compatibility with cyanate ester resins, and thus has a relatively high solubility in solvents and dielectric constant and dielectric loss coefficient similar to those of the EPDM rubber. It is also contemplated to use the SBR having

And, the rubber component is 1 to 80 parts by weight, preferably 10 to 70 parts by weight, more than 100 parts by weight of the cyanate ester resin Preferably it may be included in 20 to 60 parts by weight. That is, in order to express the minimum effect according to the content of the rubber component, the rubber component is preferably included 1 part by weight or more based on 100 parts by weight of the cyanate ester resin. In addition, when the rubber component is included in an excessive amount, the flowability of the composition may be excessively excessive, or the adhesion and heat resistance may be drastically reduced. In order to prevent the rubber component, the rubber component is included in an amount of 80 parts by weight or less based on 100 parts by weight of cyanate ester resin. It is desirable to be. On the other hand, the adhesive resin composition according to the present invention can be prepared by a conventional method of mixing a cyanate ester resin, a fluorine resin powder and a rubber component; Preferably, the fluorine resin powder may be prepared by dispersing it in an organic solvent and then mixing it with the rubber component and the cyanate ester resin.

Therefore, the adhesive resin composition according to the present invention may further include an organic solvent. In this case, the type of the organic solvent may be selected in consideration of the type of the fluorine-based resin powder within the range that does not adversely affect the physical properties of the composition, preferably Ν, Ν-dimethylformamide,

Ν, Ν-dimethylacetamide, acetone, methyl ethyl ketone, cyclonucleanone,

N-methyl-2-pyrrolidone, methyl salosolve, toluene, methanol, ethane may be one or more selected from the group consisting of propanol, and dioxolane.

The organic solvent may be included in an amount of 50 to 500 parts by weight, preferably 100 to 400 parts by weight, and more preferably 100 to 300 parts by weight, based on 100 parts by weight of the total solid of the adhesive resin composition. That is, the content of the organic solvent is within the above-described range in view of the dispersibility of the fluorine-based resin powder, the efficiency of the adhesive layer forming process, and the like while ensuring the minimum flowability, coating property, and the like required for the adhesive resin composition. It is advantageous to adjust at. In addition, the adhesive resin composition according to the present invention may further include a cyanate ester curing accelerator as necessary.

At this time, the cyanate ester curing accelerator may be an organometallic salt or Organometallic complexes may be used, for example organometallic salts or organometallic complexes including iron, copper, zinc, cobalt, nickel, manganese, tin and the like. Specifically, the cyanate escuring hardening accelerator may include naphthenic acid manganese, iron naphthenate, copper naphthenate, zinc naphthenate, cobalt naphthenate, iron octylate, copper octylate, zinc octylate, and cobalt octylate. Organometallic salts; Organic metal complexes such as acetylacetonate lead and acetylacetonate cobalt.

The cyanate ester resin curing accelerator may be included in an amount of 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the cyanate ester resin. That is, with respect to 100 parts by weight of the cyanate ester resin, if the content of the curing accelerator is less than 0.05 parts by weight, semi-ungseong and curability can be divided into layers. If it exceeds 5 parts by weight, it is difficult to control reaction. It may accelerate or decrease sex formation. In addition, the composition for forming an adhesive resin layer may further include inorganic particles such as a phosphorus-based flame retardant to compensate for flame retardancy. At this time, the phosphorus-based flame retardant may be included in 5 to 30 parts by weight, preferably 10 to 20 parts by weight based on 100 parts by weight of the cyanate ester resin. That is, in order to fully express the effect of containing the phosphorus-based flame retardant, the phosphorus-based flame retardant is preferably included 5 parts by weight or more based on 100 parts by weight of the cyanate ester resin. In addition, when the phosphorus-based flame retardant is included in excess, the flowability and adhesion of the composition may be reduced. In order to prevent this, the phosphorus-based flame retardant may be included in an amount of 30 parts by weight or less based on 100 parts by weight of the cyanate ester resin. desirable. On the other hand, the above-mentioned adhesive resin composition can be used in the manufacture of bonding sheets, coverlays, prepregs and the like. The bonding sheet, coverlay or prepreg may be applied to a flexible printed circuit board (FPCB) such as a flexible metal foil laminate, for example, the adhesive resin described above in the preparation thereof. Improved electrical properties can be expressed when using the composition.

As one example, according to another embodiment of the present invention, a bonding sheet including a cured product of the above-described adhesive resin composition is provided.

The bonding sheet may include an adhesive layer including the above-described composition and a protective layer (releasing film or the like) covering the adhesive layer. The protective layer is not particularly limited as long as the protective layer can be peeled off without damaging the form of the adhesive layer. However, according to the present invention, the protective layer is a plastic film such as polyethylene (PE) film, polypropylene (PP) film, polymethylpentene (TPX) film, polyester film; The release paper which coated the polyolefin film, TPX film, etc. of said PE film, PP film, etc. to one side or both sides of a paper material, etc. are mentioned.

The bonding sheet is formed by applying the above-mentioned composition on the protective layer using a comma coater, reverse roll coater, etc. to form an adhesive layer, drying it to a semi-cured state, and laminating a separate protective layer thereon. It can be prepared by the method.

In this case, the thickness of the bonding sheet (that is, the adhesive layer) including the cured product of the adhesive resin composition described above may be determined in consideration of the adhesive force required for the bonding sheet, the thickness of the circuit board to be applied, and the like, and is not particularly limited. . However, according to the present invention, the thickness of the bonding sheet may be 5 to 100 / 皿. On the other hand, according to another embodiment of the present invention, a coverlay including an electrically insulating film and the bonding sheet bonded to at least one side of the electrically insulating film is provided.

The coverlay is a bonding sheet comprising a cured product of the above-described resin composition is bonded to at least one side of the electrically insulating film, a protective layer (release film, etc.) may be further bonded on the bonding sheet, if necessary. .

Here, the type of the electrically insulating film is not particularly limited as long as it is commonly applied to a flexible copper foil laminate, and preferably may be a low-temperature plasma treatment.

And, according to the present invention, the electrically insulating film is a polyimide film, liquid crystal polymer film, polyethylene terephthalate film, polyester film, Polyparavanic acid film, polyetheretherketone film, polyphenylene sulfide film, aramid film and the like; Or a film or sheet formed by impregnating a substrate including ^ L fiber, aramid fiber, polyester fiber, and the like into a matrix of cyanate ester resin, polyester resin, diallyl phthalate resin, and the like. .

In particular, a polyimide film may be preferable in view of heat resistance, dimensional stability, mechanical properties, etc. of the coverlay, and it may be more preferable to use a low temperature plasma treated polyimide film for the coverlay.

In addition, the thickness of the electrically insulating film may be selected in an appropriate range in consideration of a sufficient degree of electrical insulation and the thickness and ductility of the application target, preferably 5 to 200 im, more preferably 7 to 100 days have.

Such a coverlay is applied to the electrically insulating film by using a comma coater, a reverse coater, etc. to form an adhesive layer and dried to form a semi-cured reaction (curing reaction proceeds in a dried state or a part thereof). Present), and then laminated with the above-described protective layer.

On the other hand, according to another embodiment of the present invention, there is provided a prepreg comprising a reinforcing fiber and the above-mentioned adhesive resin composition impregnated in the reinforcing fiber.

Here, the prepreg is a No Flow Prepreg (ie, Dust Free Prepreg) that can be used for interlayer insulation and adhesion, and impregnated with the above-mentioned adhesive resin composition on a reinforcing fiber and then dried to provide a sheet in a semi-cured state. Can be.

At this time, the reinforcing fiber may be applied without particular limitation that is common in the art to which the present invention belongs, preferably _E glass fiber, D glass fiber, NE glass fiber, H glass fiber, T glass fiber and aramid fiber It may be one or more fibers selected from the group. In particular, in order to minimize the dielectric constant and dielectric loss coefficient of prepreg as much as possible, NE glass fibers having a lower dielectric constant and dielectric loss coefficient than other glass fibers (a dielectric constant of about 4.8, dielectric loss coefficient About 0.0015) may be advantageous. Meanwhile, according to another embodiment of the present invention, there is provided a flexible copper clad laminate comprising the adhesive resin composition described above.

Specifically, the flexible metal foil laminate includes an electrically insulating film, a metal foil laminated on at least one side of the electrically insulating film, and an adhesive resin layer interposed between the electrically insulating film and the metal foil, wherein the adhesive number The ground layer may include the cured product of the above-mentioned adhesive resin composition.

1 and 2 are diagrams schematically showing a cross section of a flexible metal foil laminate according to a preferred embodiment of the present invention, respectively.

Referring to FIG. 1, in a flexible metal foil laminate according to an embodiment of the present invention, a metal foil 30 is laminated on an electrically insulating film 10, and interposed between the electrically insulating film 10 and the metal foil 30. The adhesive resin layer 20 is included. That is, in the above example, the electrically insulating film 10 and the metal foil 30 are bonded by the adhesive resin layer 20. On the other hand, Figure 1 is an embodiment of the flexible metal foil laminate in cross section, the flexible metal foil laminate according to another embodiment of the present invention may have a double-sided structure as shown in FIG. That is, referring to FIG. 2, in the flexible metal foil laminate according to another embodiment of the present invention, metal foils 30 and 30 ′ are laminated on both surfaces of the electrically insulating film 10, and the electrically insulating film 10 and the metal foil ( 30, 30 ') may have a structure in which adhesive resin layers 20 and 20' are interposed therebetween.

In the flexible metal foil laminate of the present invention, the electrically insulating film 10 may be applied without particular limitation to a film conventional in the art to which the present invention pertains. However, the electrically insulating film may be advantageously used to have heat resistance, flexibility, excellent mechanical strength and a coefficient of thermal expansion similar to that of metal. In addition, in consideration of the interfacial adhesion with the adhesive resin layer and the like, the surface of the electrically insulating film may be advantageously used to be treated with a low temperature plasma.

According to the invention, the electrically insulating film is a polyimide film, liquid crystal polymer film, polyethylene terephthalate film, polyester film, polyparabanic acid film, polyether ether ketone film, polyphenylene sulfide film, Aramid film or the like; Or what made into the film or sheet form by impregnating the base material containing glass fiber, aramid fiber, polyester fiber, etc. into cyanate ester resin, polyester resin, diallyl phthalate resin, etc. which become a matrix. In particular, in view of heat resistance, dimensional stability, mechanical properties and the like of the flexible metal foil laminate, a polyimide film may be preferably used as the electrically insulating film.

In this case, the thickness of the electrically insulating film may be selected in an appropriate range in consideration of the electrical insulation of the divided information and the thickness and ductility of the flexible metal foil laminate, preferably 5 to 50 m, more preferably 7 to 45 Can be.

Meanwhile, in the flexible metal foil laminate of the present invention, the metal foil 30 may be copper (Cu) or a copper alloy.

In this case, when the metal foil is copper (ie, copper foil), the copper foil may be used in the art, but according to the present invention, the roughness (Rz) of the Matte surface is 0.1 to 2.5! M. , Preferably it is 0.2-2.0! M, More preferably, it may be 0.2-1.0.

In addition, the thickness of the metal foil may be determined in consideration of electrical conductivity, interfacial adhesion with the electrically insulating film, ductility of the laminated plate, and the like, and preferably 5 urn or more, more preferably 7 to 35;

On the other hand, such a flexible metal foil laminate is coated with an adhesive resin layer-forming composition on the electrically insulating film 10 to form an adhesive resin layer 20, and then dried to a semi-cured state, and then the adhesive resin layer ( 20) can be produced by laminating the metal foil 30 on a thermal pressing method (thermal lamination). At this time, the final flexible metal foil laminate can be obtained by completely curing the adhesive resin layer 20 in a semi-cured state by post-curing the flexible metal foil laminate. Hereinafter, preferred embodiments will be presented to aid in understanding the present invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto.

Example 1 (Production of Adhesive Resin Composition)

Polytetrafluoroethylene (PTFE) powder (number average particle diameter: about 0.5 卿, product name: LUBRON, manufacturer: DAIKIN) and a polyester-based dispersant were added to toluene, and then homogenized using a homogenizer (15,000 rpm). Dispersed.

Here, cyanate ester resin was added in the content ratio shown in Table 1 below (reference: 100 parts by weight of cyanate ester resin), and then the resin was completely dissolved using a stirrer. Then, a 20% by weight solution of styrene butadiene rubber dissolved in toluene was added and stirred. Then, the cyanate ester resin composition which the fluororesin powder disperse | distributed was obtained by the method of fully mixing by adding cobalt naphthenic acid which is a cyanate ester hardening accelerator.

Example 2-3 and Comparative Example 1

(Production of Adhesive Resin Composition)

As shown in Table 1, except that the type or content of the cyanate ester resin or the content of the polytetrafluoroethylene powder was changed, the cyan in which the fluorine resin powder was dispersed in the same manner as in Preparation Example 1 Nate ester resin crude was obtained.

Comparative Example 2

(Production of Adhesive Resin Composition)

Polytetrafluoroethylene (ΡΊΤΕ) powder (number average particle diameter: about 0.5, product name: LUBRON, manufacturer: DAIKIN) and a polyester dispersant were added to toluene, and then dispersed evenly using a homogenizer (15,000 rpm). I was.

After adding a bisphenol-A epoxy resin and an epoxy-modified polybutadiene rubber here, the bisphenol-A epoxy resin composition in which the fluorine-type resin was disperse | distributed by adding pyrometallic anhydride (PMDA) with an epoxy hardening | curing agent, and fully mixing. Got it.

[Table 1]

Production Examples 1 to 5 (Manufacture of Bonding Sheet)

Each composition according to Examples 1-3 or Comparative Examples 1 and 2 was applied onto a polyethylene terephthalate film having a thickness of about 38 ^ to be about 25 based on the thickness after drying and for about 10 minutes at about 150 ^° C. After drying, the thermosetting double-sided bonding sheet was prepared by laminating a release coating thickness of 100 / m and a release paper (product name: EX3, manufacturer: Lintec).

Preparation Examples 6 to 10 (Preparation of Coverlay)

On one side of the polyimide film (thickness: 12.5 / m, manufacturer: KANEKA), the respective compositions according to Examples 1 to 3 or Comparative Examples 1 and 2 were applied so as to be about 25 based on the thickness after drying, and After drying at 150 ° C. for about 10 minutes, a release paper (product name: EX3, manufacturer: Lintec) having a thickness of 100 ai with a release coating was laminated to prepare a thermosetting coverlay.

Preparation Examples 11 to 15 (Prepreg)

Example 1 to 3 or Comparative Example 1 in NE glass fiber having a thickness of about 25

After incorporating each composition according to 2, dried at about 150 ^° C. for about 12 minutes to prepare a thermosetting prepreg having a total thickness of about 50 kPa.

Production Examples 16 to 20 (production of flexible double-sided copper foil laminate)

On one side of the polyimide film (thickness: 12.5 / ^ 1, manufacturer: KANEKA), the respective compositions according to Examples 1 to 3 or Comparative Examples 1 and 2 were about 10; / m based on the thickness after drying After coating to form an adhesive resin layer, It was dried to form a semi-cured state. Then, the adhesive resin layer as described above was formed on the remaining surface of the polyimide film in the same manner to prepare an adhesive sheet.

Subsequently, copper foil (thickness: about lm, Matte surface roughness (Rz): Ι.βΐΜ, manufacturer: FUKUDA) was loaded on both sides of the adhesive sheet, and then, at about 180 ^' C, 30k _g f / cuf It was pressed under pressure and post-cured at about 1701: for about 5 hours to obtain a flexible double-sided copper foil laminate. Test example

The following physical property evaluation was performed about each bonding sheet, coverlay, prepreg, and flexible double-sided copper foil laminated board which concerns on manufacture examples 1-20. The specimens used at this time were prepared by the method described below according to the test object, the test results are shown in Tables 2 to 5, respectively.

1. Property evaluation method

1-1) Heat resistance: Pressure Cooker for sample cut to 50mmX50mm

After 12 hours of hygroscopic treatment using a tester (120 ^° C, 0.22 MPa.), The state of the test piece was visually observed by floating in a 260 ^° C. According to the observation result, if there was an abnormality, it represented with X and O if there was no abnormality.

1-2) Absorption rate: The copper foils on both sides of the sample cut into 50mm × 50mm were etched and soaked in distilled water for 24 hours, and then the absorption rate was calculated by comparing the weight before and after the immersion treatment.

1-3) Dielectric Properties: Dielectric constant and dielectric loss coefficient were measured at 1 MHz using an impedance analyzer in accordance with the test standard of JIS C6481.

1-4) Adhesive Strength: Prepare samples cut to 100mmXIOmm,

The adhesive strength of the adhesive layer formed by each composition was measured using a universal testing machine (UTM).

1-5) Flexural characteristics: Flexural characteristics were measured according to the test standard of JIS C5016. 2. Results of specimen preparation and physical property evaluation

2-1) Bonding sheet: Attach each bonding sheet according to Production Examples 1 to 5 in the form of [polyimide side / bonding sheet (25 / rni) / polyimide film (12.5 / ΛΠ) of cross-section flexible metal laminate plate]. After this, the specimen was pressed and cured at a pressure of 30 kgf / orf for 60 minutes while the upper and lower plates were placed in a hot press machine heated to 180 ^° C. to prepare a specimen.

And, the results of evaluation of physical properties thereof are shown in Table 2 below.

[Table 2]

2-2) Coverlay: Each coverlay according to Production Examples 6 to 10

After attaching in the form of [polyimide film of coverlay / adhesive surface of coverlay / shiny surface of copper foil (： ^)], it is placed on a hot press machine heated to 180 ^° C with the upper plate and the lower plate 30 kgf. The specimen was prepared by press hardening at a pressure of / orf for 60 minutes.

In addition, the results of evaluation of physical properties thereof are shown in Table 3 below.

[Table 3]

2-3) Prepreg: After attaching each prepreg according to Production Examples 11 to 15 in the form of [polyimide side / prapreg (50) / polyimide film (12.5) of cross-section soft metal laminate)], This is the hot top and bottom plate heated to 180 ^° C, The specimen was prepared by compression hardening at a pressure of 30 kgf / orf for 60 minutes while placed in a press.

In addition, the results of evaluation of physical properties thereof are shown in Table 4 below.

Table 4

2-4) Flexible double-sided copper foil laminate: The ductility ⁽ copper foil laminate was used as a specimen according to Preparation Examples 16 to 20, and the results of evaluation of physical properties thereof are shown in the following 5.

Table 5

As shown in Tables 2 to 5, the adhesive resin composition according to Examples 1 to 3 has a low dielectric constant and a small dielectric loss coefficient, and thus, a bonding sheet, a coverlay, a prepreg, and a flexible double-sided sheet prepared by applying the same. It was confirmed that the copper foil laminated sheet exhibited more improved low dielectric properties while having equivalent heat resistance and adhesive strength as compared with those produced by applying the adhesive resin composition according to Comparative Example 1. In addition, those prepared by applying the adhesive resin compositions according to Examples 1 to 3 were found to exhibit significantly improved low dielectric properties compared to those prepared by applying the composition of Comparative Example 2. .

[Explanation of code] : Electrically insulating film, 20 ': adhesive resin layer, 30': metal foil

Claims

[Patent Claims]

[Claim 1]

Adhesive resin composition for circuit board manufacture containing a cyanate ester resin, the fluorine-type resin powder disperse | distributed in the said cyanate ester resin, and a rubber component.

[Claim 2]

The method of claim 1,

Adhesive resin composition containing 10-90 weight part of fluororesin powders and 1-80 weight part of said rubber components with respect to 100 weight part of cyanate ester resins.

[Claim 3]

The method of claim 1,

The fluororesin powder is an adhesive resin composition having a number average particle diameter of 10 m or less.

[Claim 4]

The method of claim 1,

The fluororesin powder is polytetrafluoroethylene (PTFE), perfluoroalkoxy polymer (PFA), fluorinated ethylene-propylene copolymer (FEP), chlorotrifluoroethylene (CTFE), tetrafluoro Styrene / chlorotrifluoro ethylene copolymer (TFE / CTFE), ethylene-chlorotrifluoro ethylene copolymer (ECTFE), ethylene-tetrafluoro ethylene copolymer (ETFE), and polychlorotrifluoro Adhesive resin composition that is a powder of at least one fluorine resin selected from the group consisting of ethylene (PCTFE).

[Claim 5]

The method of claim 1 Wherein said cyanate ester resin is at least difunctional aliphatic cyanate ester, at least difunctional aromatic cyanate ester, or a mixture thereof.

[Claim 6]

The method of claim 1,

The rubber components are natural rubber, styrene butadiene rubber (SBR), isoprene rubber (IR), acrylonitrile butadiene rubber (NBR), ethylene propylene diene monomer (EPDM) rubber, polybutadiene rubber And at least one rubber selected from the group consisting of modified polybutadiene rubbers.

[Claim 7]

The method of claim 1,

Adhesive resin composition further containing an organic solvent.

[Claim 8]

According to claim,

The organic solvent is Ν, Ν- dimethylformamide, Ν, Ν-dimethylacetamide, acetone, methyl ethyl ketone, cyclonucananone, Ν-methyl-2-pyridone, methyl cellosolve, toluene, Adhesive resin composition in which methane is at least one selected from the group consisting of ethanol, propanol, and dioxolane.

[Claim 9]

The method of claim 7, wherein

The organic solvent is 50 to 500 parts by weight based on 100 parts by weight of the total solids of the composition.

[Claim 10]

An electrically insulating film, a metal foil laminated on at least one surface of the electrically insulating film, and an adhesive resin layer interposed between the electrically insulating film and the metal foil. Includes;

The said adhesive resin layer is a flexible metal foil laminated board containing the hardened | cured material of the adhesive resin composition of Claim 1.

[Claim 11]

The method of claim 10,

The electrically insulating film is composed of a polyimide film, a liquid crystal polymer film, a polyethylene terephthalate ^' film, a polyester film, a poly parabanic acid film, a polyether ether ketone film, a polyphenylene sulfide film, and an aramid film A flexible metal foil hopper is at least one film selected from the group.

[Claim 12]

The method of claim 10,

The metal foil is a flexible metal foil laminated plate made of copper or a copper alloy.

[Claim 13]

Bonding sheet containing the hardened | cured material of the adhesive resin composition of Claim 1, and having a thickness of 5-100.

[Claim 14]

Electrically insulating films; And

The bonding sheet of claim 12 bonded to at least one side of the electrically insulating film.

Cover cover (coverlay).

[Claim 15]

Reinforcing fibers; And

The adhesive resin composition of claim 1 impregnated in the reinforcing fiber

Prepreg comprising a. [Claim 16]

The method of claim 15,

The reinforcing fiber is a prepreg of at least one fiber selected from the group consisting of E glass fiber, D glass fiber, NE glass fiber, H glass fiber, T glass fiber and aramid fiber.