KR20150076525A - Adhsive composition, coverlay film and copper clad laminate using the same - Google Patents

Abstract

(A) 30 to 150 parts by weight of a thermoplastic resin (B), 5 to 20 parts by weight of a curing agent (C) and 10 to 50 parts by weight of an inorganic filler (D) relative to 100 parts by weight of a nonhalogen epoxy resin A pressure-sensitive adhesive composition and a copper-clad laminate and a coverlay film using the same. The coverlay film or the copper-clad laminate produced by applying the adhesive composition of the present invention does not contain halogens and does not generate toxic gases upon human combustion. In addition, a polyether sulfone film can be applied as an insulating film to reduce manufacturing cost compared with FPCB using a conventional polyimide film, and can be applied to a process requiring UV curing or the like.

Description

TECHNICAL FIELD [0001] The present invention relates to a pressure-sensitive adhesive composition, a copper-clad laminate and a cover-

The present invention relates to a pressure-sensitive adhesive composition, a coverlay film using the same, and a copper-clad laminate, and more particularly, to an adhesive resin composition comprising a non-halogen epoxy resin and a polyether sulfone- To a copper-clad laminate and a coverlay film which are free from the generation of harmful gas of human body and can be applied to processes requiring reduction in manufacturing cost and UV curing compared with FPCB using a conventional polyimide film.

In recent years, with the tendency toward integration, miniaturization, thinning, densification and high bending of electronic products, there has been 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 is increasing due to the rapid increase in use due to technological development of mobile phones, DVDs, digital cameras and 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 includes a three-layer type comprising three layers of a copper foil, a polyimide base film and an epoxy thermosetting adhesive layer, a two-layer type including a polyimide-based adhesive which is homogeneous with the polyimide base film, There is a two-layer type that does not include a layer. 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 by blending an epoxy resin containing bromine and a phenoxy resin. 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, polyimide films are more expensive than other insulating films. Particularly, the polyimide film has a transparency of less than 80% and a yellow index (YI) of 50 or more because of its unique color, so that the adhesive layer can not be UV-cured after lamination of the copper foil.

An object of the present invention is to provide an adhesive composition free from the generation of harmful gas of human body during combustion.

Another object of the present invention is to provide a copper-clad laminate to which the composition is applied to a polyethersulfone film.

It is still another object of the present invention to provide a coverlay film in which the composition is applied to a polyethersulfone film.

(A) 30 to 150 parts by weight of a thermoplastic resin (B), 5 to 20 parts by weight of a curing agent (C) and 10 to 50 parts by weight of an inorganic filler (D) relative to 100 parts by weight of a nonhalogen epoxy resin A coverlay film or a pressure-sensitive adhesive composition for a copper foil laminate.

The non-halogen type epoxy resin is preferably a mixture of a bisphenol A type epoxy and a phosphorus-linked epoxy resin.

The thermoplastic resin is preferably an acrylonitrile-butadiene copolymer having at least one functional group selected from the group consisting of an amino group, a carboxyl group, an epoxy group, a hydroxyl group, a methoxy group, an isocyanate group, a vinyl group and a silanol group.

The inorganic filler is preferably aluminum hydroxide or silica having an average particle size of 0.2 to 5 mu m.

Further, in the present invention, an insulating film; An adhesive layer formed by applying the pressure-sensitive adhesive composition on the insulating film; And a copper foil laminated on the adhesive layer.

Further, in the present invention, an insulating film; An adhesive layer formed by applying the pressure-sensitive adhesive composition on the insulating film; And a peelable protective film laminated on the adhesive layer.

The insulating film is preferably a polyethersulfone film having a transparency of 80% or more as measured by the ASTM D1746-09 measurement method and a yellow index (YI) of 10 or less as measured by the ASTM E313 measurement method.

The coverlay film or the copper-clad laminate produced by applying the adhesive composition of the present invention does not contain halogens and does not generate toxic gases upon human combustion.

In addition, a polyether sulfone film can be applied as an insulating film to reduce manufacturing cost compared with FPCB using a conventional polyimide film, and can be applied to a process requiring UV curing or the like.

Hereinafter, the adhesive composition according to the present invention, the coverlay film using the adhesive composition, and the copper-clad laminate will be described in detail.

1. Adhesive composition

The adhesive composition of the present invention comprises (A) a non-halogen epoxy resin, (B) a thermoplastic resin, (C) a multifunctional curing agent for epoxy resin, and (D) an inorganic filler.

1.1. Non-halogen epoxy resin

The adhesive composition produced by the production method of the present invention contains (A) a non-halogen type epoxy resin. By including an epoxy resin, balance of properties such as heat resistance, insulation at high temperatures, chemical resistance, and strength in the form of an adhesive layer can be realized. The epoxy resin is not particularly limited as long as it contains two or more epoxy groups in a molecule, and examples thereof include cresol novolack type epoxy resins, phenol novolac type epoxy resins, Epoxy resin containing skeleton, epoxy resin containing naphthalene skeleton, bisphenol epoxy resin, dicyclopentadiene epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, and heterocyclic epoxy resin. And a phosphorus-bonded epoxy resin to which phosphorus or the like is bonded and imparted with flame retardancy. These may be used singly or in combination of two or more.

Of these epoxy resins, bisphenol F type epoxy resins, bisphenol A type epoxy resins, phosphorus-linked epoxy resins and the like are preferably used in the present invention from the standpoint of adhesiveness and excellent film formability when sheeting an adhesive composition Among them, a bisphenol A type epoxy resin and a phosphorus-bonded type epoxy resin are particularly preferable.

1.2. Thermoplastic resin

The adhesive composition produced by the production method of the present invention contains (B) a thermoplastic resin. By containing a thermoplastic resin, effects such as improvement in adhesion, improvement in flexibility, and relaxation of thermal stress can be obtained.

Examples of the thermoplastic resin include acrylonitrile-butadiene copolymer (NBR), acrylonitrile-butadiene-styrene resin (ABS), polybutadiene, styrene Styrene-butadiene-ethylene resin (SEBS), acrylic acid and / or methacrylic acid ester resin (acrylic rubber) containing side chain of 1 to 8 carbon atoms, Polyvinyl butyral, polyamide, polyester, polyimide, polyamideimide, polyurethane and the like.

These thermoplastic resins preferably contain a functional group capable of reacting with the above-mentioned (A) epoxy resin. Specific examples thereof include an amino group, a carboxyl group, an epoxy group, a hydroxyl group, a methoxy group, and an isocyanate group. Such a functional group is preferable because bonding with the epoxy resin becomes strong and the heat resistance improves.

Among these thermoplastic resins, acrylonitrile-butadiene copolymer (NBR) is particularly preferably used in view of adhesion, flexibility, and thermal stress relieving effect. These copolymers may also contain functional groups capable of reacting with the epoxy resin. Specific examples thereof include an amino group, a carboxyl group, an epoxy group, a hydroxyl group, a methoxy group, an isocyanate group, a vinyl group and a silanol group. Among them, it is more preferable to include a carboxyl group.

Specific examples of the carboxyl group-containing NBR include PNR-1H (manufactured by JSR Corporation), Nipol 1072J and Nipol DN631 (manufactured by Nippon Zeon Co., Ltd.).

In the present invention, the content of the thermoplastic resin (B) is preferably 30 to 150 parts by weight, more preferably 50 to 100 parts by weight, based on 100 parts by weight of the epoxy resin. When the amount is less than 30 parts by weight, adhesion can not be obtained, and when it is more than 150 parts by weight, heat resistance is decreased.

1.3. Hardener

The adhesive composition prepared by the production method of the present invention contains (C) a curing agent. Examples of the curing agent include 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetraethyl-4,4'-dia 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'-triaminodiphenylsulfone And the like; Novolac resins such as phenol novolac resin, cresol novolak resin, and naphthol novolak resin; Tris (hydroxyphenyl) methane, 1,1,2-tris (hydroxyphenyl) ethane, 1,1,3-tris (hydroxyphenyl) propane, condensates of terpene and phenol, di Compounds containing a phenolic hydroxyl group such as phenol resin containing cyclopentadienes skeleton, phenol aralkyl resin, and nattoaralkyl resin; Anhydrous carbonic acid such as maleic anhydride, phthalic anhydride, and pyromellitic anhydride; Dicyandiamide; And the like. These may be used alone or in combination.

The content of the curing agent (C) is adjusted by the blending ratio with the epoxy resin (A). The mixing ratio of the epoxy resin (A) and the curing agent (C) is preferably 1.5 to 0.4 as the number of functional groups. It is preferable to use the curing agent at a ratio of 5 to 20 parts by weight based on 100 parts by weight of the epoxy resin within the above-mentioned functional group magnification. When the content of the curing agent is less than 5 parts by weight, curing is insufficient. When the content of the curing agent is more than 20 parts by weight, there is a problem that the curing and stability with time are deteriorated.

1.4. Inorganic filler

The adhesive composition produced by the production method of the present invention contains (D) an inorganic filler. By containing an inorganic filler, it is possible to improve the heat resistance and control the resin flow of the adhesive. Examples of the inorganic filler include metal hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium aluminate hydrate; metal hydroxides such as zinc oxide, magnesium oxide, silica, alumina, zirconium oxide, antimony trioxide, antimony pentoxide, titanium oxide, Metal oxides such as chromium oxide and talc; metal fine particles such as aluminum, gold, silver, nickel and iron; carbon black; and the like. Of these, aluminum hydroxide and silica are particularly preferable. These may be used alone or in combination of two or more.

The average particle diameter of the primary particles of the inorganic filler material is preferably 0.2 to 5 占 퐉 in consideration of transparency and dispersion stability. Here, the average particle diameter refers to the 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 material is preferably in the above range, in general, even when the average particle diameter of the primary particles is in the above range, the primary particles are aggregated and the average particle diameter of the apparent particle is large . When the flame-retardant adhesive composition is prepared by mixing the inorganic filler material agglomerated with such primary particles intact or in an insufficient dispersion state, the aggregation material of the inorganic filler material may cause the flame- Resulting in appearance unevenness, deterioration of heat resistance, and the like. For this reason, it is preferable that the inorganic filler should follow the steps of dispersing the aggregated primary particles in the organic solvent, and mixing the inorganic filler dispersed by the electric step with the other components in this order.

In the step of dispersing the agglomerated primary particles in the organic solvent, it is preferable to sufficiently disperse the inorganic filler until the particle diameter distribution after dispersion reaches the following range.

The preferred particle size distribution (silica) in the step of dispersing the inorganic filler in the organic solvent

d10 = 1 탆 or less

d50 = 1-3 mu m

d90 = 4-8 탆

(Aluminum hydroxide) in the step of dispersing the inorganic filler in the organic solvent,

d10 = 2-4 m

d50 = 3-6 탆

d90 = 4-8 탆

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, homogenizer, sand blast, bead mill, cone, ultrasonic dispersion, etc. can be applied.

The content of the inorganic filler is preferably 10 to 50 parts by weight based on 100 parts by weight of the epoxy resin. If the amount is less than 10 parts by weight, it is difficult to control the flowability of the adhesive and the heat resistance is reduced. When the amount is more than 50 parts by weight, the adhesive strength is decreased.

The inorganic filler may be subjected to a surface treatment for the purpose of preventing deterioration such as oxidation or hydrolysis of the filler, the purpose of improving the wettability between the filler and other organic components in the adhesive composition, and improving 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 given. Among them, surface treatment with a silane coupling agent is particularly preferable in terms of ease of surface treatment. 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- Acrylamidopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane , N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3- 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like, but are not limited thereto. Two or more of these silane coupling agents may be used in combination. The amount of the silane coupling agent used for 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 other than the inorganic filler is contained in the adhesive composition and the filler is surface-treated, it is preferably about 0.3 to 3 parts by weight based on 100 parts by weight of the inorganic filler.

1-5. Additional Composition

The adhesive composition according to the present invention may contain a curing accelerator in addition to the above components (A) to (D) for controlling the curability. As the curing accelerator, an amine complex of boron trifluoride such as a boron trifluoride triethylamine complex, an amide complex of 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, Phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl 2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl- Imidazole derivatives such as nonyl-2-phenylimidazole, organic acids such as phthalic anhydride and trimellitic anhydride, and the like. These may be used alone or in combination of two or more. The content of the curing accelerator is usually used in a proportion of less than 10 parts by weight based on 100 parts by weight of the epoxy resin content.

In the present invention, a phosphorus compound such as an antioxidant, an ionic additive, a melamine and a derivative thereof, a phosphoric compound such as various phosphoric acid esters, a phosphazene compound or the like may be added in the range of not damaging the properties of the above- The addition of the organic and inorganic components of the nitrogen-containing compound and the silicon compound is not limited. Specific examples of phosphorus compounds such as the various phosphoric acid esters include adducts PFR, FP-600, FP-700 (manufactured by ADEKA Corporation), SP-703 and SP-670 (manufactured by Shikoku Kasei Kogyo Co., PX-200, CR-733S and CR 20-741 (all of which are manufactured by Daihachi Chemical Industry Co., Ltd.).

2. Coverlay film, copper clad laminate

2-1. Insulating film

The coverlay film or the copper clad laminate according to the present invention is characterized by using a film formed of polyethersulfone (PES) as an insulating film to which the above-described composition is applied as an adhesive layer. A conventional insulating film used for producing a coverlay film or a copper-clad laminate is polyimide. The polyethersulfone film is economical and transparent compared to a polyimide film and has no design limit, and has advantages of being usable in a process using UV.

The polyethersulfone used in the present invention refers to those having an ether functional group and a sulfone functional group at the same time in the repeating unit. Solvent casting method or melt extrusion method may be used.

The polyethersulfone film preferably has a transparency of 80% or more, more preferably 85% or more as measured by the ASTM D1746-09 measurement method. The higher the transparency is, the better, but the transparency of commercially purchased is found to be about 95% upper limit.

On the other hand, the polyethersulfone film has a yellow index (YI) of 10 or less, more preferably 5 or less as measured by ASTM E313 measurement method. In the present invention, by limiting the insulating film to a polyetherimide film having transparency and YI value as described above, it is possible to include a step requiring UV curing in the subsequent step. Specifically, after the copper foil is laminated on the adhesive layer, only the plastic base film is the surface on which the light transmission is possible. Therefore, in the case of a copper-clad laminate produced by using a conventional polyimide film as a base film, when the copper-clad laminate is exposed to a process such as a paste bonding process at the time of post-processing, for example, energy ray- There is a problem that curing of the adhesive is impossible. The present invention can solve such a problem that occurs when a polyimide film is used.

As the polyetherimide films satisfying the above-mentioned transmittance and yellow index values, those commercially available are, for example, Glastic® products of i-Component, Sumilite® FS products of Sumitomo Bakelite, And Solvay's Ajedium ™ products.

The thickness of the insulating film is preferably 5 to 200 占 퐉, more preferably 10 to 125 占 퐉. In this range of thickness, a single film or sheet may be used, or a plurality of films or sheets may be laminated. If the thickness of the insulating film is less than 5 탆, the mechanical strength is deteriorated. If the thickness is more than 200 탆, flexible characteristics are lost. On the other hand, the insulating film may be subjected to surface treatment such as hydrolysis, corona discharge, low-temperature plasma, physical surface irregularity treatment, or adhesion coating treatment, if necessary.

2-2. Adhesive layer

The adhesive layer is formed by applying the above-mentioned adhesive composition on the insulating film made of the polyethersulfone. More specifically, it is preferable to uniformly stir (A) a halogen-free epoxy resin, (B) a thermoplastic resin, (C) a multifunctional curing agent for epoxy resin, and (D) an inorganic filler with a solvent, To form an adhesive layer. Examples of the solvent include methyl ethyl ketone, methyl isobutyl ketone, chlorobenzene, and benzyl alcohol. On the other hand, 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 or the like may be used.

The adhesive layer is formed by applying the adhesive composition onto an insulating substrate that continuously runs the adhesive composition, passing the substrate coated with the adhesive composition through an inline dryer, drying the adhesive by removing the organic solvent at 100 to 170 DEG C for 2 to 10 minutes, State.

The thickness of the adhesive layer is preferably 1 to 30 占 퐉, more preferably 5 to 25 占 퐉. If the thickness of the adhesive layer is less than 1 占 퐉, the adhesive strength is deteriorated. If the thickness exceeds 30 占 퐉, the heat resistance and flame retardancy are reduced.

2-3. Coverlay film

The coverlay film according to the present invention comprises an insulating film, a semi-cured adhesive layer formed of the adhesive composition of the present invention, and a peelable protective film laminated in this order.

The peelable protective film may be a release film known in the art or a release film made of a plastic material, and is preferably coated with polyethylene or silicone resin to impart peelability.

After laminating the releasing paper, aging is generally carried out in a convection oven at 40 to 60 ° C for 12 to 96 hours so as to make the flowability of the adhesive appropriate, and the degree of curing of the adhesive layer is generally adjusted.

2-4. Copper clad laminate

The copper-clad laminate according to the present invention is obtained by laminating a copper foil on the aforementioned pressure-sensitive adhesive layer. The copper-clad laminate is produced by laminating the semi-cured composition layer with a non-glossy surface of the copper foil using a roll laminator. Specifically, an insulating film on which an adhesive layer is formed is laminated on a copper foil, followed by heating in a convection oven at 50 to 90 캜 for 12 to 72 hours to obtain a cured copper-clad laminate.

As the copper foil, those known in the art such as rolled copper foil and electrolytic copper foil can be used. Normally, those having a thickness of 5 to 50 mu m are used.

The copper clad laminate may be of a single-sided or double-sided type. When the double-sided copper-clad laminate is manufactured, an adhesive is applied to the surface of the insulating substrate such as electricity, the copper foil is laminated, the adhesive layer is formed on the opposite side of the substrate, and the copper foil is laminated again on the adhesive.

On the other hand, the coverlay film according to the present invention is a laminate of a peelable protective film on the semi-cured adhesive.

2-5. Coverage film, use of copper clad laminate

As the use of the copper-clad laminate and the coverlay film employing the adhesive composition obtainable by the production method of the present invention, for example, a flexible printed circuit board made of a copper-clad laminate, a plurality of flexible printed circuit boards A multilayered copper-claded laminate circuit board obtained by laminating a rigid laminate and a flexible printed circuit board using an adhesive sheet, a flex-rigid circuit board laminated using an adhesive sheet, a TAB substrate, various package applications ( CSP, BGA), and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is intended to more specifically illustrate the present invention, and the scope of the present invention is not limited to these embodiments.

1. Copper clad laminate

[Example 1]

(Epoxy equivalent: 230, manufactured by Japan Epoxy Resin Co., Ltd.) and phosphorus-bonded epoxy resin (FX-289BEK75, manufactured by Tohto Kasei Co., Ltd.) as a non-halogen epoxy resin at a ratio of 2: 1 Respectively. 80 parts by weight of a carboxyl group-containing acrylonitrile-butadiene rubber (PNR-1H, manufactured by JSR Corporation) as a thermoplastic resin, 100 parts by weight of an aluminum hydroxide powder (Heidellite H-42I, primary particle average particle diameter 1.0 15 parts by weight of 4,4'-diaminodiphenylsulfone as a curing agent and 2 parts by weight of 2-ethyl-4-methylimidazole as a curing catalyst were mixed and dissolved in methyl isobutyl (manufactured by Showa Denko KK) And dissolved in a ketone (MIBK) to prepare an adhesive composition.

The composition was dried as an insulating film on a polyethersulfone film (Glastic SCL +, 25 占 퐉, i-component) and dried so as to have an adhesive thickness of 10 占 퐉 and dried at 170 占 폚 for 2 minutes. An electrolytic copper foil (WCF, 1 oz, LS Mtron) to produce a copper clad laminate. 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 added at 3Pass and mixed with an aluminum hydroxide dispersion.

[Example 2]

A copper clad laminate was produced in the same manner as in Example 1 except that the content of bisphenol A-type epoxy resin and phosphorus-linked epoxy resin was 5: 3 as an epoxy resin under the conditions of Example 1.

[Example 3]

A copper-clad laminate was prepared in the same manner as in Example 1, except that the content of the thermoplastic resin was changed to 100 parts by weight in the condition of Example 1.

[Example 4]

The same procedure as in Example 1 was carried out except that 40 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 laminate. 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 mixing with a silica particle dispersion.

[Comparative Example 1]

The composition ratio of the adhesive solution was the same as in Example 1, except that the dispersion of aluminum hydroxide powder was not carried out in the same manner as in Example 1 to prepare a copper clad laminate. At this time, the same amount of methyl isobutyl ketone as used in the dispersion in Example 1 was used.

[Comparative Example 2]

The composition ratio of the adhesive solution was the same as in Example 1, except that a polyimide film (Kapton 100V manufactured by Toray DuPont) was used instead of the polyethersulfone film as the electrically insulating substrate to prepare a copper clad laminate Respectively.

2. Coverlay film

[Example 5]

(Epoxy equivalent: 230, manufactured by Japan Epoxy Resin Co., Ltd.) and phosphorus-bonded epoxy resin (FX-289BEK75, manufactured by Tohto Kasei Co., Ltd.) as a non-halogen epoxy resin at a ratio of 2: 1 Respectively. 80 parts by weight of a carboxyl group-containing acrylonitrile-butadiene rubber (PNR-1H, manufactured by JSR) as a thermoplastic resin and 100 parts by weight of an aluminum hydroxide powder (Heidellite H-42I, , 30 parts by weight of Showa Denko KK), 15 parts by weight of 3,3'-diaminodiphenylsulfone (amine equivalent 62) as a curing agent, and 2 parts by weight of 2-ethyl-4-methylimidazole as a curing catalyst The adhesive composition was prepared and dissolved in methyl isobutyl ketone (MIBK), dried on an electrically insulating substrate (polyethersulfone film, 25 탆, i-component), applied with an adhesive thickness of 25 탆, After drying, the release treated surfaces of a 38 탆 -thick polyethylene terephthalate film (Filmbina " GT " manufactured by Fujimori Kogyo Co., Ltd.) treated with a silicone release agent were laminated together. With respect to the coverlay film thus prepared, the flowability of the adhesive was measured, and aging was carried out under the condition of 40 degrees until the adhesive flowability was in the range of 150 mu m to 170 mu m, and the flowability was adjusted to prepare a coverlay film. 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 added at 3Pass and mixed with an aluminum hydroxide dispersion.

[Example 6]

A coverlay film was prepared in the same manner as in Example 5 except that the content of bisphenol A-type epoxy resin and phosphorus-bondable epoxy resin was 5: 3 as an epoxy resin under the conditions of Example 5.

[Example 7]

A coverlay film was prepared in the same manner as in Example 5, except that 100 parts by weight of the thermoplastic resin was added under the conditions of Example 5.

[Example 8]

Same as Example 5 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 under the conditions of Example 5 To prepare a coverlay film. 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 mixing with a silica particle dispersion.

[Comparative Example 3]

The composition ratio of the adhesive solution was the same as in Example 5, but a coverlay film was produced in the same manner as in Example 5 except that the aluminum hydroxide powder was not dispersed. At this time, the same amount of methyl isobutyl ketone as used in the dispersion in Example 5 was used.

[Comparative Example 4]

The composition ratio of the adhesive solution was the same as in Example 5, except that a 25 μm thick polyimide film (Kapton 100V manufactured by Toray DuPont) was used in place of the polyester film as the electrically insulating substrate, .

[Experimental Example]

1. Adhesion strength (peeling adhesion strength)

Perform it according to JIS-C6481. The adhesive strength of the copper-clad laminate was determined by preparing a copper foil pattern having a width of 2 mm by etching on the copper foil side of the copper clad laminate, and then peeling the copper foil with a width of 2 mm using a tensilon (UT-11-5HR type, manufactured by Orientech Co., And the strength at the time of peeling in the direction of 90 degrees at a speed of 50 mm / min was measured.

The adhesive strength of the coverlay film was measured as follows. After removing the release film of the coverlay film, the adhesive surface of the coverlay film was coated with 160 (in terms of thickness) of the rolled copper foil (BHY foil, made by Nikko Metal Co., Ltd.) Under the conditions of x 4 MPa x 30 minutes to produce coverlay adhesive copper foil. A cut mark of 2 mm in width is put on the coverlay film side by using a cutter for the coverlay adhesive copper sheet thus manufactured. The peel strength at the time of delamination of this cut mark from the copper foil in the direction of 90 degrees at a tensile speed of 50 mm / min was measured.

2. Soldering heat resistance

This was carried out in accordance with the method of JIS-C6481. The solder heat resistance of the copper-clad laminate was evaluated by cutting the copper-clad laminate so that the cross-section thereof was 20 mm, treating the copper-clad laminate under conditions of 23 ° C. and 55% RH for 24 hours, rapidly spreading the copper foil over the brazing tank at a predetermined temperature for 30 seconds, The highest temperature without parts and peeling was measured.

The solder heat resistance of the coverlay film was evaluated by evaluating the soldering heat resistance of the coverlay adhesive copper foil by the same method as the evaluation method of the copper-clad laminate, by pressing the coverlay film on the copper foil under the same conditions as in the measurement of the adhesive strength, did.

3. Heat Resistance Adhesive Strength

 Each specimen is heat treated at 150 ° C for 5 hours, and then the peel strength is measured as in the above 1.

4. Surface observation (defect observation)

The surface of the produced copper-clad laminate was visually observed on the side of the polyester film surface, and the defects having a size of 2 mm ² or more and 10 or less were 10 cm or more and 5 or less in size, respectively.

5. UV process applicability

The applicability of the UV process was evaluated by judging whether the product was cured by passing it through a UV curing machine.

Evaluation items Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Adhesive strength 9 N / cm 8 N / cm 10 N / cm 10 N / cm 5 N / cm 10 N / cm Soldering heat resistance 280 ℃ 280 ℃ 280 ℃ 270 ℃ 200 ℃ 300 ° C Heat-resistant adhesive strength 8 N / cm 8 N / cm 9 N / cm 8 N / cm 4 N / cm 9 N / cm Exterior quality Good Good Good Good Many shortcomings Good UV process application possible possible possible possible possible impossible

Evaluation items Example 5 Example 6 Example 7 Example 8 Comparative Example 3 Comparative Example 4 Adhesive strength 10 N / cm 10 N / cm 10 N / cm 8 N / cm 5 N / cm 10 N / cm Soldering heat resistance 270 ℃ 270 ℃ 270 ℃ 270 ℃ 200 ℃ 290 ° C Heat-resistant adhesive strength 9 N / cm 9 N / cm 9 N / cm 7 N / cm 4 N / cm 9 N / cm Exterior quality Good Good Good Good Many shortcomings Good UV process application possible possible possible possible possible impossible

As clearly shown in Tables 1 and 2, the flame-retardant adhesive composition produced by using the production method of the present invention has excellent adhesiveness and heat resistance. In addition, by using this invention, the surface quality is increased in addition to the above- A copper-clad laminate, and a coverlay film without a film. In addition, since the adhesive composition of the present invention does not contain a halogen material, no harmful gas for human body is generated during combustion, and manufacturing cost is reduced as compared with FPCB using a conventional polyimide film by applying a polyethersulfone film as an insulating substrate film. It is possible to provide a copper-clad laminate and a coverlay film that can be applied to a process requiring curing and the like.

Claims (8)

(A) a coverlay film comprising (A) 30 to 150 parts by weight of (B) a thermoplastic resin, (C) a curing agent, 5 to 20 parts by weight, and (D) 10 to 50 parts by weight of an inorganic filler per 100 parts by weight of the non- Or a copper-clad laminate. The pressure-sensitive adhesive composition according to claim 1, wherein the non-halogen epoxy resin is a mixture of a bisphenol A epoxy resin and a phosphorus-bonded epoxy resin. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is acrylonitrile-butadiene having at least one functional group selected from the group consisting of an amino group, a carboxyl group, an epoxy group, a hydroxyl group, a methoxy group, an isocyanate group, Wherein the pressure-sensitive adhesive composition is a copolymer. The pressure-sensitive adhesive composition according to claim 1, wherein the inorganic filler is aluminum hydroxide or silica having an average particle size of 0.2 to 5 占 퐉. Insulating film; An adhesive layer formed by applying the pressure-sensitive adhesive composition of claim 1 on the insulating film; And a copper foil laminated on the adhesive layer. [6] The insulating film according to claim 5, wherein the insulating film is a polyethersulfone film having a transparency of 80% or more as measured by ASTM D1746-09, and a yellow index (YI) of 10 or less as measured by ASTM E313 measurement method Copper clad laminates. Insulating film; An adhesive layer formed by applying the pressure-sensitive adhesive composition of claim 1 on the insulating film; And a peelable protective film laminated on the adhesive layer. The method according to claim 7, wherein the insulating film is a polyethersulfone film having a transparency of 80% or more as measured by the ASTM D1746-09 measurement method and a yellow index (YI) of 10 or less as measured by ASTM E313 measurement method Coverlay film.