KR20170045069A

KR20170045069A - Resin coated copper using halogen-free adhesive composition and method of manufacturing the same

Info

Publication number: KR20170045069A
Application number: KR1020150144999A
Authority: KR
Inventors: 신금식; 이정우; 류효곤; 엄태수
Original assignee: 도레이첨단소재 주식회사
Priority date: 2015-10-16
Filing date: 2015-10-16
Publication date: 2017-04-26

Abstract

The present invention relates to a copper foil-attached adhesive sheet using a nonhalogenated adhesive composition and a manufacturing method thereof. The copper foil-attached adhesive sheet using a nonhalogenated adhesive composition does not generate harmful gas to human bodies in combustion, has excellent flame retardancy and thermal resistance, has excellent migration resistance in a copper foil stacked plate of not only a single layer structure but a high intensity multilayer structure, and can be thin and highly intensified.

Description

TECHNICAL FIELD [0001] The present invention relates to a copper foil-bonded sheet and a method of manufacturing the same. More particularly, the present invention relates to a copper foil-

More particularly, the present invention relates to a copper foil adhesive sheet using a halogen-free adhesive composition, and more particularly, to a copper foil-bonded sheet having excellent flame retardancy and heat resistance without generating harmful gas for human body during combustion, Halogenated adhesive composition capable of achieving thinning and densification of a flexible circuit board due to excellent migration resistance even in the case of a copper-clad laminate having a multi-layered plate structure and a method for producing the same.

2. Description of the Related Art In recent years, with the trend toward integration, miniaturization, thinning, high density and high bending of electronic products, there is an increasing need for printed circuit boards (PCBs) that are easy to be embedded even in a narrower space. Accordingly, a flexible printed circuit board (FPCB) capable of miniaturization and high density and having repeated flexing has been developed. The demand for FPCB has been increasing due to the rapid increase in use due to technological development of mobile phones, DVDs, digital cameras or PDPs.

Generally, in order to manufacture a flexible printed circuit board, a dry film is applied to a flexible copper-clad laminate (FCCL) in which a copper foil layer is formed on both sides or an end face of an insulating base film such as polyimide having high heat resistance and high flexibility. A circuit pattern is formed by exposure, development and etching in sequence, and then a coverlay film is attached to the outer side of the circuit pattern, and the flexible circuit board (FPCB) is bonded by a hot press, .

The copper-clad laminate is composed of a three-layer type composed of three layers of a copper foil, a polyimide base film and an epoxy thermosetting adhesive layer, a two-layer type having a polyimide-based adhesive which is homogeneous with the polyimide base film, There is a two-story type that does not own a floor. The coverlay is laminated for the purpose of protecting the copper wiring of the copper clad laminate, and is generally composed of a polyimide base film and an epoxy thermosetting adhesive layer. At this time, adhesives used for electronic materials such as semiconductor sealing materials or epoxy-based flexible circuit boards generally exhibit excellent flame retardancy due to blending of epoxy resins containing bromine and phenoxy resins.

However, halogen-containing compounds such as bromine have recently been studied for the non-halogenation of materials used in adhesives because there is a possibility that toxic gases such as dioxin compounds may be generated during combustion.

In addition, a conventional flexible circuit board is required to have high heat resistance and high bending property due to the FPCB manufacturing process and product characteristics, and thus a polyimide film is used as an insulating base material film.

However, the polyimide film is expensive compared to other films, and the thickness of the film basically increases the thickness of the entire product. In recent printed circuit board products requiring thinning and high densification, there is a need for a resin-coated copper (RCC) adhesive sheet composed of an adhesive layer and a copper foil layer to remove such insulating base film layer.

Further, according to the present invention, it has been found that even when migration resistance is excellent in the conventional single-layered plate structure, migration resistance is insufficient when the multilayered substrate for a flexible printed wiring is made high in density, okay.

Japanese Unexamined Patent Application Publication No. 2008-302161 Korean Patent Publication No. 2005-0107999

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a flame retardant and heat resistant material which does not contain halogens, The present invention also provides a copper foil-bonded sheet using the non-halogen-based adhesive composition, which is excellent in migration resistance even in the case of a plate-structured copper-clad laminate or the like and capable of achieving thinning and high density of a flexible circuit board.

These and other objects and advantages of the present invention will become more apparent from the following description of a preferred embodiment thereof.

The above object is achieved by a semiconductor device comprising a copper foil layer; An adhesive layer formed of a non-halogen-based adhesive composition; And a peelable protective film on the surface of the copper foil.

Preferably, the non-halogen based adhesive composition may comprise a non-halogenated epoxy resin, a thermoplastic resin, a curing agent, an inorganic filler and an ion scavenger.

Preferably, the non-halogenated epoxy resin may include at least one selected from the group consisting of a bisphenol F type epoxy resin, a bisphenol A type epoxy resin and a phosphorus-bonded epoxy resin, and the thermoplastic resin may include acrylonitrile- Butadiene copolymer (NBR), acrylonitrile-butadiene rubber-styrene resin (ABS), polybutadiene, styrene-butadiene-ethylene resin (SEBS), an acrylic acid ester resin having a side chain of 1 to 8 carbon atoms (a side chain modified to a side chain), a meta possessing a side chain of 1 to 8 carbon atoms (a side chain modified to a side chain) At least one selected from the group consisting of methacrylic acid ester resin, polyvinyl butylal, polyamide, polyester, polyimide, polyamideimide and polyurethane And the inorganic filler may include at least any one selected from the group consisting of metal hydroxides, metal oxides, metal fine particles, and carbon black, and the ion trapping agent may include hydrotalcite ion capture A bismuth oxide ion trapping agent, an antimony oxide ion trapping agent, a titanium phosphate ion trapping agent, and a zirconium phosphate ion trapping agent.

Preferably, the non-halogen type epoxy resin may include a bisphenol A type epoxy resin and a phosphorus type epoxy resin, and the thermoplastic resin may include an acrylonitrile-butadiene copolymer (NBR) , The inorganic filler may include aluminum hydroxide or silica, and the ion scavenger may include a hydrotalcite ion scavenger and an antimony oxide scavenger.

Preferably, the phosphorus-linked epoxy resin may be contained in an amount of 40 to 100 parts by weight based on 100 parts by weight of the bisphenol A type epoxy resin.

Preferably, the number of functional groups of the curing agent relative to the number of functional groups of the epoxy resin may be 1: 1.5 to 4.0.

Preferably, the non-halogen adhesive composition comprises 50 to 60 parts by weight of a thermoplastic resin, 5 to 20 parts by weight of a curing agent, 10 to 50 parts by weight of an inorganic filler, and 1 to 5 parts by weight of an ion trapping agent per 100 parts by weight of a non- .

The present invention also provides a method for producing a halogen-free adhesive composition comprising a halogen-free epoxy resin, a thermoplastic resin, a curing agent, an inorganic filler and an ion scavenger; A second step of coating the non-halogen adhesive composition prepared in the first step on the non-glossy surface of the continuously running copper foil to form an adhesive layer; A third step of passing the copper foil having the adhesive layer formed thereon through an in-line dryer and drying the same; And a fourth step of preparing a copper foil-bonded sheet obtained by laminating a protective film on a dried adhesive layer using a roll laminator.

Preferably, the fifth step of adjusting the degree of curing of the adhesive layer after the fourth step is further included.

Preferably, the fifth step can be aged in a convection oven at 40 to 60 DEG C for 12 to 96 hours.

According to the present invention, it is possible to provide a flexible circuit board having excellent flame retardancy and heat resistance while not containing halogens and generating no harmful gas for human body during combustion, and also has excellent migration resistance in a multilayered copper plate laminate having a high density as well as a single- It is possible to achieve a thin film and a high density.

However, the effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned can be clearly understood by those skilled in the art from the following description.

1 is a cross-sectional view of a copper foil-bonded sheet according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to embodiments and drawings of the present invention. It will be apparent to those skilled in the art that these embodiments are provided by way of illustration only for the purpose of more particularly illustrating the present invention and that the scope of the present invention is not limited by these embodiments .

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.

In describing and / or claiming the present invention, the term "copolymer" is used to refer to a polymer formed by copolymerization of two or more monomers. Such copolymers include binary copolymers, terpolymers, or higher order copolymers.

1, a copper foil-bonded sheet 100 according to one aspect of the present invention comprises a copper foil layer 10, a non-halogen-based adhesive composition The adhesive layer 20 formed and the peelable protective film 30 in this order.

Conventionally, in the case of a three-layer flexible copper-clad laminate and a coverlay film used for a flexible printed circuit board, a halogen-containing material is used for excellent flame retardancy, which may cause harmful gas during combustion. However, as described above, the adhesive sheet with a copper foil according to an embodiment of the present invention can exhibit flame retardancy without containing halogen, and it is also possible to reduce the thickness and thickness of the adhesive sheet by using a heat- And high density can be achieved.

In one embodiment, the copper foil may be a rolled copper foil or an electrolytic copper foil. The copper foil-bonded sheet 100 may have a thickness of 35 mu m for the copper foil layer 10, 30 mu m for the adhesive layer 20, It is preferable that the protective film 30 has a thickness of 12.5 to 125 탆.

In one embodiment, the non-halogen based adhesive composition may include a non-halogenated epoxy resin (A), a thermoplastic resin (B), a curing agent (C), an inorganic filler (D) and an ion trapping agent (E).

In one embodiment, the non-halogen epoxy resin (A) can realize balance of physical properties such as heat resistance, insulation at high temperatures, chemical resistance and strength at the time of production with an adhesive layer. Is not particularly limited as far as it possesses two or more epoxy groups in one molecule and includes, for example, cresol Novorack type epoxy resin, phenol novolack type epoxy resin, phenylbenzene type skeleton A phosphorus-bonded epoxy resin, a naphthalene skeleton-containing epoxy resin, a bisphenol epoxy resin, a dicyclopentadiene-type epoxy resin, a linear aliphatic epoxy resin, an alicyclic epoxy resin, a heterocyclic epoxy resin, Type epoxy resin. A bisphenol F type epoxy resin, a bisphenol A type epoxy resin, and a phosphorus-bonded type epoxy resin, from the viewpoints of adhesion and film formability when the adhesive composition is formed into a sheet. Among them, bisphenol A type epoxy resin and phosphorus It is particularly preferable to include a bonded epoxy resin.

In one embodiment, when bisphenol A type epoxy and phosphorus-containing epoxy resin are used together as the non-halogen type epoxy resin, it is preferable that 40 to 100 parts by weight of phosphorus-bonded epoxy resin is added to 100 parts by weight of bisphenol A type epoxy resin . Is less than 40 parts by weight, there is a disadvantage in that the flame retardancy is lowered. When the amount exceeds 100 parts by weight, the unit cost of the adhesive increases, which is uneconomical and deteriorates in adhesive strength and heat resistance.

In one embodiment, the thermoplastic resin (B) is an acrylonitrile-butadiene copolymer (NBR), an acrylonitrile-butadiene rubber-styrene resin (ABS) Polybutadiene, styrene-butadiene-ethylene resin (SEBS), acrylic acid having a side chain of 1 to 8 carbon atoms and / or methacrylic acid ester ) Resin (acrylic rubber), polyvinylbutylal, polyamide, polyester, polyimide, polyamideimide, polyurethane and the like.

In one embodiment, the thermoplastic resin (B) is capable of improving the adhesiveness, improving the flexibility, and alleviating the thermal stress. It is preferable that the thermoplastic resin (B) has a functional group capable of reacting with the non- desirable. Specifically, it is preferable to possess an amino group, a carboxyl group, an epoxy group, a hydroxyl group, a methoxy group, an isocyanate group and the like. Such a functional group strengthens the bond with the epoxy resin, and the heat resistance can be improved.

Further, acrylonitrile-butadiene copolymer (NBR) can be used particularly preferably for the thermoplastic resin (B) in view of adhesiveness, flexibility and alleviation of thermal stress. It is preferable that the NBR also possesses a functional group capable of reacting with the epoxy resin. Specifically, it may possess an amino group, a carboxyl group, an epoxy group, a hydroxyl group, a methoxy group, an isocyanate group, a vinyl group, a silanol group and the like, and more preferably a carboxyl group . Specific examples of the NBR, which is an acrylic rubber containing a carboxyl group, include PNR-1H (manufactured by JSR Corporation), Nipol 1072J and Nipol DN631 (carboxylated nitrile elastomers) (manufactured by Nippon Zeon Co., Ltd.).

In one embodiment, the thermoplastic resin (B) content is 50 to 60 parts by weight based on 100 parts by weight of the non-halogen epoxy resin (A). When the amount is less than 50 parts by weight, sufficient adhesion can not be obtained. There is a disadvantage in that heat resistance is deteriorated.

In one embodiment, the curing agent (C) comprises a multi-functional curing agent for an epoxy resin. Examples of such a curing agent include 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetraethyl- Diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2 ', 3,3'-tetrachloro-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfido, 3,3'-diaminobenzophenone, 3,3' -Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone, 3,4,4'-triaminodiphenyl (Hydroxyphenyl) methane, 1,1,2-tris (hydroxyphenyl) ethane, and the like; aromatic amines such as phenol novolak resin, cresol novolac resin and naphthol novolak resin; , 1,1,3-tris (hydroxyphenyl) propane, a condensate of terpene and phenol, a phenolic resin containing a dicyclopentadienene skeleton, a phenol-formaldehyde resin, And a compound possessing a phenolic hydroxyl group of the resin, and the like, maleic anhydride, phthalic anhydride, acid anhydride, dicyandiamide, such as anhydrous pyromellitic acid, etc., can be used to merge them alone or in combination.

In one embodiment, the content of the curing agent (C) is adjusted by the blending ratio with the epoxy resin (A). The preferred mixing ratio of the non-halogen type epoxy resin (A) to the curing agent (C) is 1.5 to 0.4 in terms of the number of functional groups. Here, the compounding ratio means the ratio of the number of functional groups of the curing agent to the number of functional groups of the epoxy resin. The content of the curing agent (C) is 5 to 20 parts by weight based on 100 parts by weight of the non-halogen epoxy resin. If the amount of the curing agent (C) is less than 5 parts by weight, the adhesive hardens sufficiently during the thermocompression bonding process, If the amount is more than 20 parts by weight, the adhesive strength may be reduced due to over-curing after thermocompression, and the heat resistance is lowered due to the remaining unreacted curing agent.

In one embodiment, the inorganic filler (D) is a metal hydroxide such as aluminum hydroxide, magnesium hydroxide, calcium aluminate hydrate or the like, or a metal hydroxide such as zinc oxide, magnesium oxide, silica, alumina, zirconium oxide, antimony trioxide, antimony pentoxide, Metal oxides such as iron oxide, cobalt oxide, chromium oxide and talc; metal fine particles such as aluminum, gold, silver, nickel and iron; carbon black; In particular, aluminum hydroxide and silica are preferred.

The average particle diameter of primary particles of the inorganic filler is preferably 0.2 to 5 占 퐉 in consideration of transparency and dispersion stability. Here, the average particle diameter means a particle diameter at which the cumulative weight becomes 50% in the particle size distribution analyzed by the laser diffraction scattering method after the particles are completely dispersed in the primary particles using a dispersing machine such as a ball mill. Although the average particle diameter of the primary particles of the inorganic filler is preferably in the above range, generally, the average particle diameter of the primary particles in the inorganic filler aggregates with each other even if the average particle diameter of the primary particles is within the above range, . When the flame-retardant adhesive composition is prepared by mixing the inorganic fillers agglomerated with each other or insufficiently dispersed in the flame-retardant adhesive composition, the aggregation of the inorganic filler is caused when the flame-retardant adhesive composition is coated on the polyimide film, Unevenness may occur, and defects such as deterioration of heat resistance may occur. For this reason, it is preferable that the inorganic filler should follow the step of dispersing the aggregated primary particles in the organic solvent, and the step of mixing the inorganic filler dispersed by the electric step with the other components in this order.

In the step of dispersing the aggregated primary particles in the organic solvent, it is preferable to sufficiently disperse the inorganic filler until the particle diameter distribution after dispersion becomes the following range. The preferable particle diameter distribution in the step of dispersing the inorganic filler in the organic solvent is as follows: silica d10 = 1 탆 or less, d50 = 1 to 3 탆 and d90 = 4 to 8 탆 in the case of silica, d10 = 2 D50 = 3 to 6 占 퐉, and d90 = 4 to 8 占 퐉. d10, d50, and d90 mean particle diameters corresponding to 10%, 50%, and 90% of the size percentage in the particle size distribution curve, respectively.

The dispersion method that can be used in the step of dispersing the inorganic filler in the organic solvent is not particularly limited, and for example, a homogenizer, sandblast, bead mill, cone, ultrasonic dispersion or the like can be applied.

Such an inorganic filler can be subjected to surface treatment to prevent deterioration such as oxidation and hydrolysis of the filler or to improve the wettability of the filler with other organic components in the adhesive composition or to improve the physical properties of the flame retardant adhesive composition. Specifically, coating with silica, phosphoric acid or the like, treatment with an oxide film, surface treatment with a silane coupling agent, a titanate-based coupling agent, a silane compound or the like can be carried out. From the standpoint of ease of surface treatment, surface treatment with a silane coupling agent is particularly preferable. Specific examples of the silane coupling agent used for the surface treatment include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-glycidoxypropyl Trimethylsilane, trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- Aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-tri 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, but are not limited thereto. The silane coupling agent may be used alone or in combination of two or more. The content of the silane coupling agent used in the surface treatment is preferably 0.3 to 3 parts by weight based on 100 parts by weight of the inorganic filler. When the filler is contained in the adhesive composition and contains a filler other than the inorganic filler, Is preferably 0.3 to 3 parts by weight.

In one embodiment, the content of the inorganic filler (D) is 10 to 50 parts by weight based on 100 parts by weight of the non-halogen epoxy resin (A). When the amount is less than 10 parts by weight, sufficient flame retardancy can not be secured. There is a disadvantage in that the adhesive force is lowered after thermocompression and the adhesive becomes hard.

In one embodiment, the ion trapping agent (E) makes it possible to improve the migration resistance even when applied to a single-layer plate and a multilayer plate flexible circuit board. The ion trapping agent (E) is a compound having an ion trapping function and reduces ionic impurities by capturing a phosphate anion, an organic acid anion, a halogen anion, an alkali metal cation, and an alkaline earth metal cation. When ionic impurities are contained in a large amount, the corrosion resistance of the wiring and the migration resistance of the insulating layer are remarkably lowered. The ion trapping agent (E) may be at least one selected from the group consisting of a hydrotalcite ion trapping agent, a bismuth oxide ion trapping agent, an antimony oxide ion trapping agent, a titanium phosphate ion trapping agent and a zirconium phosphate ion trapping agent . (Hydrotalcite ion capturing agent, manufactured by Kyoe Kagaku Kogyo Co., Ltd.), IXE-100 (manufactured by Toagosei Co., Ltd., zirconium phosphate ion capturing agent), IXE-300 (IXE-500, manufactured by Toagosei Co., Ltd., bismuth oxide ion trapping agent), IXE-600 (manufactured by Toa Kosei Co., Ltd., antimony oxide ion trapping agent) Antimony oxide-bismuth oxide ion trapping agent manufactured by Kosei Co., Ltd.).

In one embodiment, the content of the ion trapping agent (E) is usually 1 to 5 parts by weight, particularly preferably 1 to 3 parts by weight based on 100 parts by weight of the nonhalogen epoxy resin (A). When the amount is less than 1 part by weight, the ion capturing performance is deteriorated. When the amount is more than 5 parts by weight, the production cost is increased, which is uneconomical, and the adhesive strength and heat resistance are deteriorated.

In one embodiment, the non-halogen based adhesive composition comprises, in addition to the non-halogen epoxy resin (A), the thermoplastic resin (B), the curing agent (C), the inorganic filler (D) A curing accelerator may be added. The curing accelerator may be an amine complex of boron trifluoride such as a boron trifluoride triethylamine complex, an amine complex of 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, Phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- Imidazole derivatives such as ethyl-2-phenylimidazole, phthalic anhydride, and organic acids such as trimellitic anhydride. These may be used singly or in combination of two or more.

The halogen-free adhesive composition may contain phosphorus compounds such as an antioxidant, an ionic supplement, a melamine and a derivative thereof, various phosphoric acid compounds such as various phosphoric acid esters, and a phosphazene compound, without departing from the object of the present invention. A nitrogen-containing compound, and an organic or inorganic component of a silicon-based compound. FP-600, FP-700 (manufactured by ADEKA Corporation), SP-703, SP-670 (manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a commercially available phosphorus compound such as various phosphoric acid esters, Ltd.), PX-200, CR-733S and CR 20-741 (manufactured by Daishi Chemical Industry Co., Ltd.).

The adhesive sheet with a copper foil according to an embodiment of the present invention can produce a build-up printed circuit board by subjecting the copper foil to a printed wiring process, forming a circuit, or processing a laser hole and a through hole. In addition, miniaturization, thinning, and weight reduction of electronic equipment can be achieved by using a buildup printed circuit board manufactured using a copper-clad adhesive sheet.

Hereinafter, a method for manufacturing an adhesive sheet with a copper foil according to another aspect of the present invention will be described.

According to another aspect of the present invention, there is provided a method for manufacturing a copper-clad adhesive sheet comprising the steps of: preparing a halogen-free adhesive composition comprising a halogen-free epoxy resin, a thermoplastic resin, a hardener, an inorganic filler and an ion scavenger; A second step of coating the non-halogen adhesive composition prepared in the first step on the non-glossy surface of the continuously running copper foil to form an adhesive layer; A third step of passing the copper foil having the adhesive layer formed thereon through an in-line dryer and drying the same; And a fourth step of preparing a copper foil-bonded sheet obtained by laminating a protective film on a dried adhesive layer using a roll laminator. The above-described non-halogen-based adhesive composition is coated on a low-illuminated copper foil by a method for producing a copper-clad adhesive sheet, and then laminated with a peelable protective film to provide an adhesive sheet with a copper foil. Hereinafter, the overlapping description with respect to the non-halogen-based adhesive composition will be omitted.

In one embodiment, the method for manufacturing a copper-clad adhesive sheet may further comprise a fifth step of adjusting the degree of curing of the adhesive layer of the copper-clad adhesive sheet after the fourth step.

In one embodiment, the first step is a step of mixing 50 to 60 parts by weight of the thermoplastic resin (B), 5 to 20 parts by weight of the curing agent (C), 10 to 20 parts by weight of the inorganic filler (D) 10 And 1 to 5 parts by weight of the ion trapping agent (E) are uniformly stirred together with a solvent to prepare a thermosetting epoxy adhesive composition. At this time, as the solvent, methyl ethyl ketone, methyl isobutyl ketone, chlorobenzene, benzyl alcohol and the like can be used. In the second step, the adhesive composition may be applied to the non-glossy surface of the continuously running copper foil to form an adhesive layer. In the third step, the substrate having the adhesive layer formed thereon is passed through an in-line dryer and dried at 100 to 170 ° C for 2 to 10 minutes by removing the organic solvent to make it semi-cured. In the fourth step, the semi-cured adhesive layer is pressed and laminated with a peelable protective film using a roll laminator to produce a copper foil adhesive sheet. The fifth step may be aged in a 40 to 60 ° C convection oven for 12 to 96 hours to adjust the degree of curing of the adhesive layer. In this case, the method of applying the adhesive may be a comma coating, a lip coating, a roll coating, a gravure coating, a blade coating, a wire bar coating, a reverse coating ) Coating or the like may be used.

The adhesive sheet with a copper foil manufactured by the process for producing a copper-clad adhesive sheet according to an embodiment of the present invention can be used to lower the overall thickness when manufacturing a multi-product structure of a flexible printed circuit board.

Further, the copper foil of the copper-clad adhesive sheet produced by the method for producing an adhesive sheet with a copper foil according to an embodiment of the present invention may be printed and interconnected to form a circuit, or laser holes and through holes may be formed, Can be produced. In addition, miniaturization, thinning, and weight reduction of electronic equipment can be achieved by using a buildup printed circuit board manufactured using a copper-clad adhesive sheet.

Hereinafter, the structure and effect of the present invention will be described in more detail with reference to examples and comparative examples. However, this embodiment is intended to explain the present invention more specifically, and the scope of the present invention is not limited to these embodiments.

[Example 1]

50 parts by weight of a phosphorus-linked epoxy resin (FX-289BEK75, manufactured by Tohto Kasei Co., Ltd.) was added to 100 parts by weight of a bisphenol A type epoxy resin (EP834CB60, Japan Epoxy Resin Co., 80 parts by weight of a carboxyl group-containing acrylonitrile-butadiene rubber (PNR-1H, manufactured by JSR Corporation) as a resin, 30 parts by weight of an aluminum hydroxide powder (Heiditeite H-42I, primary particle average particle diameter 1.0 탆, manufactured by Showa Denko KK) , 1 part by weight of DHT4A (hydrotalcite ion trapping agent, manufactured by Kyoe Kagaku Kogyo Co., Ltd.) as an ion trapping agent, 1 part by weight of IXE-300 (antimony oxide ion trapping agent manufactured by Toagosei Co., Ltd.) 15 parts by weight of 3'-diaminodiphenylsulfone (amine equivalent 62) and 2 parts by weight of 2-ethyl-4-methylimidazole as a curing catalyst were mixed to prepare an adhesive composition, which was dissolved in methyl isobutyl ketone After drying on an electrolytic copper foil (12 탆, LS Mtron Co., Ltd.) (Polyethylene terephthalate film having a thickness of 38 占 퐉 treated with a silicone release agent ("Film Barna" or "GT" manufactured by Fujimori Kogyo K.K.) was applied to each other to a thickness of 20 μm, .

The thus obtained copper-clad adhesive sheet was subjected to aging under the conditions of 40 占 폚 until the flowability of the adhesive was in the range of 150 to 170 占 퐉 and the flowability was controlled, . At this time, the aluminum hydroxide powder (H-42I) was mixed with methyl isobutyl ketone (MIBK) at a weight ratio of 20/80, and the beads mill was subjected to 3 passes and mixed with an aluminum hydroxide dispersion.

[Example 2]

A copper-clad adhesive sheet was prepared in the same manner as in Example 1, except that the content of the phosphorus-containing epoxy resin was changed to 60 parts by weight under the conditions of Example 1.

[Example 3]

The same procedure as in Example 1 was carried out except that 30 parts by weight of silica particles (Adomafine SO25R, spherical silica, primary average particle diameter 0.5 占 퐉, manufactured by Edmertex Co., Ltd.) was used instead of aluminum hydroxide as an inorganic filler in Example 1 To prepare a copper-clad adhesive sheet. At this time, the silica particles were mixed with methyl isobutyl ketone at a weight ratio of 20/80, and the mixture was subjected to a bead mill 3Pass and mixed with a silica particle dispersion.

[Comparative Example 1]

Under the conditions of Example 1, the contents of the remaining components were the same without using the ion trapping agent to prepare the copper-clad adhesive sheet.

[Comparative Example 2]

A copper-clad adhesive sheet was prepared in the same manner as in Example 1, except that 0.5 parts by weight of DHT4A and 0.5 parts by weight of IXE-300 were added as ion scavengers under the conditions of Example 1.

[Comparative Example 3]

Except that the content of the thermoplastic resin was changed to 100 parts by weight in the condition of Example 1 and the content of DHT4A was changed to 1 part by weight except for IXE-300 as the ion trapping agent, .

[Comparative Example 4]

Except that the content of the thermoplastic resin was changed to 100 parts by weight and the content of IXE-300 was changed to 1 part by weight except for DHT4A as an ion trapping agent under the conditions of Example 1 to prepare a copper-clad adhesive sheet .

[Comparative Example 5]

The procedure of Example 1 was repeated except that the content of the phosphorus-containing epoxy resin was changed to 60 parts by weight and the content of DHT4A was changed to 1 part by weight except for IXE-300 as an ion scavenger, To prepare an adhesive sheet.

[Comparative Example 6]

Except that 30 parts by weight of silica particles (adomapine SO25R, spherical silica, primary average particle diameter 0.5 占 퐉, manufactured by Edmertex Co., Ltd.) was used instead of aluminum hydroxide as an inorganic filler in Example 1, and 0.5 parts by weight of DHT4A , And 0.5 parts by weight of IXE-300 were added to prepare a copper-clad adhesive sheet.

The properties of the non-halogenated copper-clad adhesive sheets (RCC) according to Examples 1 to 3 and Comparative Examples 1 to 6 were measured through the following experimental examples. The results are shown in Table 1 below.

[Experimental Example]

1. Adhesion strength (peeling adhesion strength)

Resin coated copper sheets (RCC: Resin coated copper) of the above examples and comparative examples were laminated so as to be in contact with the polyimide surface and the copper foil surface of the three-layer single-sided copper-clad laminate (1D1L-ES10, Pressure of 40 kgf / cm < ² > at a temperature for 1 hour. The adhesive strength of the sample was measured using a tensile tester (UTM-11-5HR type, manufactured by Orientech Co., Ltd.) at a tensile speed of 50 mm / min while peeling the copper foil with a width of 1 cm . The polyimide surface and the copper foil surface were respectively measured.

2. Soldering heat resistance

A specimen was prepared in the same manner as in the preparation of the specimen for the adhesive strength measurement of Experimental Example 1, and the specimen was cut to a width of 50 mm in length and length and processed for 24 hours under the conditions of 23 degrees and 55% RH. The solder bath was placed on the brazing tank for 30 seconds, and the maximum temperature without peeling was measured inside the adhesive layer.

3. Heat Resistance Adhesive Strength

Each specimen was heat treated at 150 ° C for 5 hours, and peel strength was measured as in Experimental Example 1.

4. Flammability

The specimens for flame retardance measurement were prepared as follows. The copper-clad adhesive sheets of Examples and Comparative Examples were heat-pressed for ¹ hour by applying a pressure of 40 kgf / cm ² at a temperature of 160 ° C to a 25 μm-thick polyimide film, and then the surface of the copper foil was removed by etching, . The thus prepared specimens were subjected to flame retardancy test according to the flame retardancy test standard (UL94-V0). It is expressed as "O" if it satisfies UL94-V0 through flame retardancy test, or "X" if it does not.

5. Migration tolerance (single layer and multilayer plate evaluation)

Test piece for evaluating single layer board: The copper-clad adhesive sheets of Examples and Comparative Examples were heated and pressed on a 25 占 퐉 thick polyimide film at a temperature of 160 占 폚 under a pressure of 40 kgf / cm2 for ¹ hour and then subjected to width / space width = 100 占 퐉 / 100 Mu m of a circuit is manufactured to prepare a test piece for evaluation for a single layer.

- Test pieces for evaluation for multilayer: The copper-clad adhesive sheets of the examples and comparative examples were heat-pressed for ¹ hour under a pressure of 40 kgf / cm ² at a temperature of 160 ° C on a copper surface of a double-sided copper-clad laminate having patterns formed thereon, = 100 탆 / 100 탆 is manufactured to prepare test pieces for evaluation for multilayer.

The test piece prepared as described above was subjected to a DC voltage of 50 V to the anode of the circuit under the conditions of a temperature of 85 캜 and a relative humidity of 85% RH (migration tester, AMI-025-P ). The case where a short circuit (lowering of the resistance value) occurred within 1,000 hours after the voltage was applied or a case where the growth of the dendrite was confirmed after 1,000 hours of curing was evaluated as " Quot; good ", and the case where no dendrite is generated is evaluated as " good ".

[Table 1]

As clearly shown in Table 1, it can be seen that the adhesive sheet with a copper foil according to one embodiment of the present invention is excellent in flame retardancy, adhesiveness and heat resistance.

In addition, since the copper foil-bonded sheet using the halogen-free adhesive composition according to an embodiment of the present invention does not contain a halogen material, a halogen-free adhesive composition for a copper foil- It is possible to provide a copper-clad adhesive sheet used as an insulating material for a build-up printed circuit board using the same. In addition, it has excellent migration resistance even in the case of a single-layered plate structure as well as a high-density multilayered plate-like copper-clad laminate. By using a build-up printed circuit board manufactured using such a halogen- Thinning and weight reduction can be achieved.

It is to be understood that the present invention is not limited to the above embodiments and various changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention.

100: Adhesive sheet with copper foil
10: Copper foil layer
20: adhesive layer
30: Protective film

Claims

A copper foil layer;
An adhesive layer formed of a non-halogen-based adhesive composition; And
And a releasable protective film on the surface of the adhesive sheet.

The method according to claim 1,
Wherein the non-halogen-based adhesive composition comprises a non-halogen epoxy resin, a thermoplastic resin, a curing agent, an inorganic filler, and an ion capturing agent.

3. The method of claim 2,
Wherein the non-halogen epoxy resin comprises at least one selected from the group consisting of a bisphenol F type epoxy resin, a bisphenol A type epoxy resin and a phosphorus-bonded epoxy resin,
The thermoplastic resin may be at least one selected from the group consisting of acrylonitrile-butadiene copolymer (NBR), acrylonitrile-butadiene rubber-styrene resin (ABS), polybutadiene, Butadiene-ethylene resin (SEBS), an acrylic acid ester resin having a side chain of 1 to 8 carbon atoms, methacrylic acid having a side chain of 1 to 8 carbon atoms (methacrylic acid ) At least one selected from the group consisting of an ester resin, polyvinylbutylal, polyamide, polyester, polyimide, polyamideimide and polyurethane,
Wherein the inorganic filler comprises at least one selected from the group consisting of metal hydroxides, metal oxides, metal fine particles, and carbon black,
The ion trapping agent includes any one selected from the group consisting of a hydrotalcite ion trapping agent, a bismuth oxide ion trapping agent, an antimony oxide ion trapping agent, a titanium phosphate ion trapping agent and a zirconium phosphate ion trapping agent Wherein the adhesive sheet is a copper foil.

The method of claim 3,
Wherein the non-halogen epoxy resin comprises a bisphenol A epoxy resin and a phosphorus-bonded epoxy resin,
The thermoplastic resin includes an acrylonitrile-butadiene copolymer (NBR)
Wherein the inorganic filler comprises aluminum hydroxide or silica,
Wherein the ion trapping agent comprises a hydrotalcite ion capturing agent and an antimony oxide ion capturing agent.

5. The method of claim 4,
Wherein the phosphorus-containing epoxy resin is contained in an amount of 40 to 100 parts by weight based on 100 parts by weight of the bisphenol A type epoxy resin.

3. The method of claim 2,
Wherein the number of functional groups of the curing agent relative to the number of functional groups of the epoxy resin is 1: 1.5 to 4.0.

7. The method according to any one of claims 2 to 6,
The non-halogen-based adhesive composition comprises 50 to 60 parts by weight of the thermoplastic resin, 5 to 20 parts by weight of the curing agent, 10 to 50 parts by weight of the inorganic filler, and 1 to 50 parts by weight of the ion- 5 parts by weight of a copper-clad adhesive sheet.

A first step of preparing a non-halogen-based adhesive composition comprising a non-halogen epoxy resin, a thermoplastic resin, a curing agent, an inorganic filler, and an ion scavenger;
A second step of applying the halogen-free adhesive composition prepared in the first step onto a non-glossy surface of a copper foil continuously running to form an adhesive layer;
A third step of passing the copper foil having the adhesive layer formed thereon through an in-line dryer and drying the same; And
And a fourth step of preparing a copper foil-bonded sheet obtained by laminating a protective film on the dried adhesive layer using a roll laminator.

9. The method of claim 8,
And a fifth step of adjusting the degree of curing of the adhesive layer after the fourth step.

9. The method of claim 8,
Wherein the fifth step is aged in a convection oven at 40 to 60 DEG C for 12 to 96 hours.

9. The method of claim 8,
Wherein the non-halogen epoxy resin comprises at least one selected from the group consisting of a bisphenol F type epoxy resin, a bisphenol A type epoxy resin and a phosphorus-bonded epoxy resin,
The thermoplastic resin may be at least one selected from the group consisting of acrylonitrile-butadiene copolymer (NBR), acrylonitrile-butadiene rubber-styrene resin (ABS), polybutadiene, Butadiene-ethylene resin (SEBS), an acrylic acid ester resin having a side chain of 1 to 8 carbon atoms, methacrylic acid having a side chain of 1 to 8 carbon atoms (methacrylic acid ) At least one selected from the group consisting of an ester resin, polyvinylbutylal, polyamide, polyester, polyimide, polyamideimide and polyurethane,
Wherein the inorganic filler comprises at least one selected from the group consisting of metal hydroxides, metal oxides, metal fine particles, and carbon black,
The ion trapping agent includes any one selected from the group consisting of a hydrotalcite ion trapping agent, a bismuth oxide ion trapping agent, an antimony oxide ion trapping agent, a titanium phosphate ion trapping agent, and a zirconium phosphate ion trapping agent Wherein the copper foil is adhered to the copper foil.

9. The method of claim 8,
Wherein the non-halogen epoxy resin comprises a bisphenol A epoxy resin and a phosphorus-bonded epoxy resin,
The thermoplastic resin includes an acrylonitrile-butadiene copolymer (NBR)
Wherein the inorganic filler comprises aluminum hydroxide or silica,
Wherein the ion trapping agent comprises a hydrotalcite ion capturing agent and an antimony oxide ion capturing agent.

9. The method of claim 8,
Wherein the phosphorus-containing epoxy resin is contained in an amount of 40 to 100 parts by weight based on 100 parts by weight of the bisphenol-A epoxy resin.

9. The method of claim 8,
Wherein the number of functional groups of the curing agent relative to the number of functional groups of the epoxy resin is 1: 1.5 to 4.0.

15. The method according to any one of claims 8 to 14,
The non-halogen-based adhesive composition comprises 50 to 60 parts by weight of the thermoplastic resin, 5 to 20 parts by weight of the curing agent, 10 to 50 parts by weight of the inorganic filler, and 1 to 50 parts by weight of the ion- And 5 parts by weight of a copper foil.