KR101528444B1 - Laminate and method for manufacturing printed circuit board - Google Patents

Abstract

A laminate for use in an element mounting board obtained by forming a conductor circuit by etching a copper foil having an insulating layer and a copper foil located on at least one side of the insulating layer and comprising 55.9 g / L of sulfuric acid and 19.6 cc of 34.5% hydrogen peroxide / L and an etching rate of 0.68 탆 / min or more and 1.25 탆 / min or less under the condition of immersing the laminate in an etching solution of sulfuric acid / hydrogen peroxide system having a liquid temperature of 30 ° C ± 1 ° C.

Description

Technical Field [0001] The present invention relates to a laminated board and a printed circuit board,

The present invention relates to a laminate and a method of manufacturing a printed wiring board.

With the demand for higher functionality of electronic devices and the like, high density integration of electronic components and high density mounting have been progressing. Printed wiring boards and the like for high density mounting used in these devices have been increasing in the past, and miniaturization, miniaturization and multilayering have progressed .

A semi additive process has begun to be used as a method for efficiently forming a conductor circuit layer having high pattern accuracy on a substrate of a printed wiring board at a high density. A manufacturing method of a printed wiring board using the semi-additive method is described in, for example, Patent Document 1 and Patent Document 2. [

In the manufacturing methods described in Patent Documents 1 and 2, first, a laminated plate having a copper foil on one side of an insulating layer is prepared, and a resist pattern is formed on the laminated plate. Subsequently, the plating layer is filled in the opening portion of the resist pattern. Subsequently, the resist pattern is removed. Thereafter, the lower layer copper foil is etched using the pattern of the plating layer as a mask to form a conductor circuit composed of the plating layer and the copper foil.

Japanese Patent Application Laid-Open No. 2003-69218 Japanese Patent Application Laid-Open No. 2003-60341

In the manufacturing processes of Patent Documents 1 and 2, the copper foil residue may be generated on the fine irregularities formed on the surface of the insulating layer. The etching residues of the copper foil remaining between the conductor circuits become short-circuited due to insufficient insulation or the like in the conductor circuit as the miniaturization progresses. Therefore, the etching residue of the copper foil on the surface of the insulating layer is preferably removed.

In order to remove the etching residue of the copper foil, it is necessary to excessively etch the surface of the insulating layer. However, when the insulating layer is excessively etched, the conductor circuit is excessively etched, so that formation of a conductor circuit or cutting or omission of the conductor circuit may occur. Even if excessive etching is continued, it is difficult to maintain the wiring shape in a desired shape.

As described above, in the laminated boards of Patent Documents 1 and 2, there is room for improvement in the reduction of the etching residues of the copper foil and the balance of wiring shape retention.

According to the present invention,

A laminated board for use in an element mounting board obtained by forming a conductor circuit by etching an insulating layer and a copper foil located on at least one side of the insulating layer,

A sulfuric acid / hydrogen peroxide system etchant consisting of 55.9 g / L of sulfuric acid and 19.6 cc / L of 34.5% hydrogen peroxide and having a liquid temperature of 30 ° C ± 1 ° C was subjected to etching of the copper foil under the condition of immersing the laminate A speed of 0.68 탆 / min or more, and 1.25 탆 / min or less.

The inventors of the present invention thought that both the reduction of the etching residue of the copper foil and the maintenance of the wiring shape can be achieved by increasing the etching rate of the copper foil.

As a result of further investigation, it has been found that the results vary depending on the composition of the etchant, the component concentration, and the liquid temperature in the method of evaluating the etching rate.

Here, it was confirmed that the irregularity of the result was reduced by setting the conditions for the component concentration to be the etching solution to be sulfuric acid, pure water and hydrogen peroxide solution, and the liquid temperature to 30 DEG C +/- 1 DEG C as the premise of the evaluation method.

The inventors of the present invention conducted various experiments with respect to the etching rate of copper under the conditions of the conditions. As a result, it was confirmed that the etching residue of the copper foil was reduced and the wiring shape was improved by setting the lower limit of the etching rate of copper to 0.68 탆 / Thereby completing the present invention.

According to the present invention, there is also provided a method of manufacturing a semiconductor device, comprising the steps of: preparing a laminate including an insulating layer and a copper foil located on at least one side of the insulating layer; and forming a conductor circuit by selectively removing the copper foil, There is provided a method for producing a printed wiring board which is the above-mentioned laminated board.

According to the present invention, there is provided a laminated board in which the etching residue of the copper foil is reduced and the wiring shape becomes good.

1 is a cross-sectional view schematically showing an example of a method for manufacturing a printed wiring board according to the first embodiment.
2 is a cross-sectional view schematically showing an example of a method for producing a printed wiring board according to the first embodiment.
3 is a cross-sectional view schematically showing an example of a method for producing a printed wiring board according to the second embodiment.
4 is a cross-sectional view schematically showing an example of a method of manufacturing a printed wiring board according to the second embodiment.
5 is a cross-sectional view schematically showing an example of a method for manufacturing a printed wiring board according to the second embodiment.
6 is a cross-sectional view schematically showing an example of a method for manufacturing a printed wiring board according to the third embodiment.
7 is a cross-sectional view schematically showing a modified example of the method for manufacturing a printed wiring board according to the third embodiment.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the drawings, the same components are denoted by the same reference numerals, and a description thereof will be omitted.

(First Embodiment)

1 and 2 are cross-sectional views showing a process sequence of a method for manufacturing a printed wiring board according to the first embodiment.

First, the outline of the printed wiring board 101 of the present embodiment will be described.

The manufacturing method of the printed wiring board 101 of the present embodiment includes the following steps. First, a laminated plate (copper clad laminate 100) having a copper foil (copper foil layer 104) located on at least one side of the insulating layer 102 and the insulating layer 102 is prepared. Then, the conductor circuit (conductor circuit 119) is formed by selectively removing the copper foil. The printed wiring board 101 is used as an element mounting substrate.

The method for manufacturing the printed wiring board 101 of the present embodiment uses a laminate (copper clad laminate 100) obtained by forming a conductor circuit by etching a copper foil.

The etching rate of the copper foil (copper foil layer 104) in the laminate (copper-clad laminate 100) was 55.9 g / L of sulfuric acid and 19.6 cc / L of 34.5% hydrogen peroxide, / Hydrogen peroxide-based etchant under the conditions of immersing the laminated plate at 0.68 탆 / min or more and 1.25 탆 / min or less.

In the copper-clad laminate 100, the etching rate of the copper foil layer 104 is specified to be 0.68 탆 / min or more. This makes it possible not only to suppress the copper foil layer 104 from remaining on the insulating layer 102 between the conductor circuits 119 in the process of manufacturing the printed wiring board 101, The shape can be improved.

Hereinafter, the manufacturing process of the printed wiring board 101 of the present embodiment will be described in detail.

First, as shown in Fig. 1A, a carrier-foiled copper clad laminate 10 having the copper foil layer 104 and the carrier foil layer 106 bonded to both surfaces of the insulating layer 102 is prepared. The copper-clad copper-clad laminate 10 has an insulating layer 102, a copper foil layer 104, and a thin carrier layer 106. On both sides of the insulating layer 102, a thin copper foil layer 106 is adhered together with a copper foil layer 104. In this embodiment, the copper foil layer 104 is formed on both surfaces of the insulating layer 102, but the copper foil layer 104 may be formed only on one surface of the insulating layer 102.

The carrier foil-coated copper clad laminate 10 is, for example, laminated on at least one surface of a copper clad laminate 100 with a peelable carrier foil layer 106. The copper clad laminate 100 (hereinafter sometimes referred to as a laminate) is not particularly limited. For example, a copper clad layer 104 is formed on at least one surface of an insulating layer 102 having an insulating resin layer containing a base material (The fiber substrate is omitted in the drawing). The laminate may be a single layer or may have a multilayer structure. That is, the laminated board may be composed of only the core layer, but a buildup layer may be formed on the core layer. The laminate may be, for example, a laminate of several prepregs or the like. The prepreg is not particularly limited, but can be obtained by, for example, impregnating a base material such as glass cloth with a resin composition containing a curable resin, a curing agent and a filler. The laminates may be formed by superimposing an ultra thin metal foil having a carrier foil on at least one surface thereof, followed by hot pressing and the like. The same material as that of the core layer may be used for the interlayer insulating layer of the buildup layer, but the substrate or the resin composition may be different. In this embodiment, the insulating layer 102 corresponds to the insulating resin layer constituting the core layer or the buildup layer, and may be a single layer or a multilayer structure. An example using a laminated plate having a buildup layer will be described later in the second embodiment.

The resin composition constituting the laminate and the interlayer insulating layer used in the present embodiment can be a known resin used as an insulating material for a printed wiring board (hereinafter also referred to as an insulating resin composition), and usually has good heat resistance and chemical resistance A curable resin is mainly used. The resin composition is not particularly limited and is preferably a resin composition containing a curable resin which is cured at least by heat and / or light irradiation.

Examples of the curable resin include a urea resin, a melamine resin, a maleimide compound, a polyurethane resin, an unsaturated polyester resin, a resin having a benzoxazine ring, a bisallylnadiimide compound, a vinylbenzyl resin, Vinyl benzyl ether resin, benzocyclobutene resin, cyanate resin, and epoxy resin. Among them, a combination in which the curable resin has a glass transition temperature of 200 ° C or more is preferable. Examples thereof include epoxy resins having two or more functional groups such as spiro ring, heterocyclic, trimethylol, biphenyl, naphthalene, anthran and novolak, cyanate resins (including prepolymer of cyanate resin) A maleimide compound, a benzocyclobutene resin, and a resin having a benzoxazine ring are preferably used. When an epoxy resin and / or a cyanate resin is used, the linear expansion is small and the heat resistance is remarkably improved. Further, when epoxy resin and / or cyanate resin is combined with a high filler filler, it has an advantage of being excellent in flame retardancy, heat resistance, impact resistance, high rigidity and electrical characteristics (low dielectric constant, low dielectric loss tangent). Here, the improvement in heat resistance is considered to be attributable to the fact that the glass transition temperature after the curing reaction of the curable resin becomes 200 DEG C or higher, the thermal decomposition temperature of the resin composition after curing becomes high and the low molecular weight such as the reaction residue at 250 DEG C or higher is reduced And the like. Further, it is considered that the improvement of the flame retardancy is attributed to the fact that the benzene ring is easily carbonized (graphitized) and the carbonized portion is generated because of the high proportion of the benzene ring due to its structure due to the aromatic curing resin.

The resin composition may also contain a flame retardant within a range that does not impair the effects of the present invention, but a non-halogen flame retardant is preferable in terms of environment. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicon-based flame retardant, and a metal hydroxide. Examples of the organophosphorus flame retardant include phosphine compounds such as HCA, HCA-HQ and HCA-NQ from Sanko Co., Ltd., phosphorus-containing benzooxazine compounds such as HFB-2006M manufactured by Showa Kobunshi Co., Phosphorus-containing epoxy compounds such as PPQ of Kakugo Kogyo Co., OP930 of Clariant Co., and PX200 of Daihachi Chemical Co., Ltd., phosphorus-containing epoxy compounds such as FX289 and FX310 manufactured by TOTOKASEI Co., Resin, and phosphorus-containing phenoxy resins such as ERF001 manufactured by TOTOKASEI CO., LTD. Examples of organic nitrogen-containing phosphorus compounds include phosphate ester imide compounds such as SP670 and SP703 manufactured by Shikoku Seiko Co., Ltd., SPB100, SPE100 manufactured by Otsuka Chemical Co., Ltd., FP-series manufactured by Fushimi Corporation Of phosphazene compounds. Examples of the metal hydroxide include aluminum hydroxide such as magnesium hydroxide such as UD650 and UD653 manufactured by Ube Industries, Ltd., CL310 manufactured by Sumitomo Chemical Co., Ltd., HP-350 manufactured by Showa Denko K.K.

Examples of the epoxy resin used in the resin composition include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, Novolak type epoxy resins, biphenyl type epoxy resins, alicyclic epoxy resins, alicyclic epoxy resins, norbornene type epoxy resins, norbornene type epoxy resins, anthracene type epoxy resins, dihydroanthracene type epoxy resins, trifunctional phenol type epoxy resins, A compound obtained by the reaction of a hydroxyl group-containing silicone resin with epichlorohydrin, and the like, a compound obtained by epoxidizing a double bond such as an epoxy resin, a polyol epoxy resin, glycidylamine, glycidyl ester or butadiene, . Among them, the epoxy resin is preferably a naphthalene type or aryl alkylene type epoxy resin. The arylalkylene type epoxy resin is an epoxy resin containing at least one combination of an aromatic group and an alkylene group such as methylene in the repeating unit, and is excellent in heat resistance, flame retardancy and mechanical strength. In the laminate obtained by using the naphthalene type or aryl alkylene type epoxy resin, the moisture absorption solder heat resistance (solder heat resistance after moisture absorption) and flame retardancy can be improved. HP-4700, HP-4032D, HP-5000, HP-6000 manufactured by DIC Corporation, NC-7300L manufactured by Nippon Kayaku Co., Ltd., Shinnetsu Tetsukagaku Co., NC-3000, NC-3000L, NC-3000-FH manufactured by Nippon Kayaku Co., Ltd. and NC-3000-FH manufactured by Nippon Kayaku Co., Ltd. are used as the arylalkylene type epoxy resin, 7300L manufactured by Shin-Etsu Chemical Co., Ltd., and ESN-375 manufactured by Shin-Ten Tetsu Kabushiki Kaisha.

The cyanate resin used in the resin composition can be obtained, for example, by reacting a halogenated cyanide compound with a phenol. Specific examples of the cyanate resin include, for example, novolac cyanate resins such as phenol novolak type cyanate resins and cresol novolak type cyanate resins, naphthol aralkyl type cyanate resins, dicyclopentadiene type cyanates Bisphenol-type cyanate resins such as biphenyl type cyanate resins, bisphenol A type cyanate resins, bisphenol AD type cyanate resins and tetramethyl bisphenol F type cyanate resins.

Among these, novolak type cyanate resins, naphthol aralkyl type cyanate resins, dicyclopentadiene type cyanate resins and biphenyl type cyanate resins are particularly preferable. Further, it is preferable that the resin composition contains 10% by weight or more of the cyanate resin in the total solid content of the resin composition. As a result, the heat resistance (glass transition temperature, thermal decomposition temperature) of the prepreg can be improved. Further, the coefficient of thermal expansion of the prepreg (in particular, the coefficient of thermal expansion in the thickness direction of the prepreg) can be reduced. When the thermal expansion coefficient in the thickness direction of the prepreg is lowered, stress deformation of the multilayer printed wiring can be reduced. In addition, in a multilayered printed circuit board having a fine interlayer connecting portion, its connection reliability can be greatly improved.

Among the novolak type cyanate resins used in the resin composition, novolak type cyanate resins represented by the following formula (1) are preferable. A novolak type cyanate resin represented by the formula (1) having a weight average molecular weight of 2000 or more, more preferably 2,000 to 10,000, and still more preferably 2,200 to 3,500, and a cyanate resin having a weight average molecular weight of 1,500 or less, more preferably 200 (1) to (1,300) (hereinafter, " ~ " means that the upper limit and the lower limit are included unless otherwise specified). In the present embodiment, the weight average molecular weight is a value measured by gel permeation chromatography in terms of polystyrene.

In the formula (1), n represents an integer of 0 or more.

As the cyanate resin, a cyanate resin represented by the following general formula (2) is also preferably used. The cyanate resin represented by the following general formula (2) is obtained by reacting naphthols such as? -Naphthol or? -Naphthol with p-xylene glycol,?,? '- dimethoxy-p- Hydroxy-2-propyl) benzene and the like and a cyanic acid. In the general formula (2), n is 1 or more, but is more preferably 10 or less. When n is 10 or less, the resin viscosity does not become high, impregnation into the substrate is good, and performance deterioration as a laminated board can be suppressed. Further, intramolecular polymerization hardly occurs at the time of synthesis, and the liquidity at the time of washing with water is improved, so that the decrease in yield can be prevented.

In the formula (2), R represents a hydrogen atom or a methyl group, Rs may be the same or different, and n represents an integer of 1 or more.

As the cyanate resin, a dicyclopentadiene-type cyanate resin represented by the following general formula (3) is also preferably used. In the dicyclopentadiene-type cyanate resin represented by the following general formula (3), n in the general formula (3) is more preferably 0 or more and 8 or less. When n is 8 or less, the resin viscosity is not increased, the impregnation property to the substrate is good, and the performance degradation as a laminated board can be prevented. Further, by using a dicyclopentadiene-type cyanate resin, low hygroscopicity and chemical resistance are improved.

In the formula (3), n represents an integer of 0 to 8.

The resin composition may further contain a curing accelerator. For example, if the curable resin is an epoxy resin or a cyanate resin, a phenol resin, an epoxy resin, or a curing accelerator of a cyanate resin can be used. Examples of the phenol resin include, but not limited to, novolac phenol resins such as phenol novolac resin, cresol novolak resin, bisphenol A novolak resin and aryl alkylene novolac resin, unmodified resol phenol resin, Tung oil), a resol-type phenol resin such as a starch-modified resol phenol resin modified with flaxseed oil and fomed oil, and the like. As the phenol resin, phenol novolak or cresol novolak resin is preferable. Among them, biphenyl aralkyl-modified phenol novolac resins are preferable from the standpoint of heat resistance and heat resistance.

One of them may be used alone, or two or more types having different weight average molecular weights may be used in combination, or one type or two or more types thereof may be used in combination with their prepolymers.

The curing accelerator is not particularly limited. Examples of the curing accelerator include organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, cobalt bis (II) acetate and trisacetylacetonate cobalt (III) Tertiary amines such as triethylamine, tributylamine and diazabicyclo [2,2,2] octane, 2-methylimidazole, 2-phenylimidazole, 2-phenyl- Benzyl-2-phenylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl Phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl-4,5-dihydroxyimidazole, Imidazoles such as 2,3-dihydro-1H-pyrrolo (1,2-a) benzimidazole, phenol compounds such as phenol, bisphenol A and nonylphenol, acetic acid, benzoic acid, salicylic acid, paratoluenesulfonic acid And organic acids such as an onium salt compound Or it may be a mixture. These derivatives may be used singly or two or more kinds of these derivatives may be used in combination.

The curable resin may contain a maleimide compound in view of heat resistance. The maleimide compound is not particularly limited as long as it is a compound having at least one maleimide group in one molecule. Specific examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) Maleimide phenyl) methane, bis (3,5-dimethyl-4-maleimide phenyl) methane, bis (3-ethyl- , Polyphenylmethane maleimide, prepolymer of these maleimide compounds, and prepolymer of maleimide compound and amine compound.

The curable resin may include a phenoxy resin, a polyvinyl alcohol resin, a polyimide, a polyamide, a polyamideimide, a polyether sulfone resin, and a polyphenylene ether resin from the viewpoint of adhesiveness with a metal foil.

Examples of the phenoxy resin include a phenoxy resin having a bisphenol skeleton, a phenoxy resin having a naphthalene skeleton, and a phenoxy resin having a biphenyl skeleton. Further, a phenoxy resin having a plurality of these skeletons may be used.

Among them, it is preferable to use a phenoxy resin having a biphenyl skeleton and a bisphenol S skeleton as the phenoxy resin. Accordingly, not only the glass transition temperature of the phenoxy resin can be increased by the rigidity of the biphenyl skeleton, but also the adhesion of the phenoxy resin and the metal can be improved by the presence of the bisphenol S skeleton. As a result, the heat resistance of the insulating layer 102 can be improved, and the adhesion of the wiring portion (the conductor circuit 118) to the insulating layer 102 can be improved when the multi-layer substrate is manufactured. As the phenoxy resin, it is also preferable to use a phenoxy resin having a bisphenol A skeleton and a bisphenol F skeleton. This makes it possible to further improve the adhesion of the wiring portion to the insulating layer 102 at the time of manufacturing the multilayer substrate.

Examples of commercially available phenoxy resins include FX280 and FX293 manufactured by Tohto Kasei Co., Ltd. and YX8100, YX6954, YL6974, YL7482, YL7553, YL6794, YL7213 and YL7290 manufactured by Japan Epoxy Resins Co., The molecular weight of the phenoxy resin is not particularly limited, but the weight average molecular weight is preferably 5,000 to 70,000, more preferably 10,000 to 60,000.

When a phenoxy resin is used, its content is not particularly limited, but it is preferably 1 to 40% by weight, more preferably 5 to 30% by weight based on the whole resin composition.

Examples of commercially available products of polyvinyl alcohol resin include DENKA BUTYRAL 4000-2, 5000-A, 6000-C and 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd. Esserb BH series manufactured by Sekisui Chemical Co., Ltd., BX Series, KS series, BL series and BM series. Particularly, it is particularly preferable that the glass transition temperature is 80 DEG C or higher.

Examples of commercially available products of polyimide, polyamide and polyamideimide include "Bioromax HR11NN (registered trademark)" and "HR-16NN" "HR15ET" available from Toyobo Co., Amide imide " KS-9300 " and the like. , "Neoprim C-1210" manufactured by Mitsubishi Chemical Corporation, soluble polyimide "Rika coat SN20 (registered trademark)" and "Rika coat PN20 (registered trademark)" available from Shin-Nippon Rika Co., VU815 "manufactured by Nippon Kayaku Co., Ltd., and the like, polyetherimide" Urutem (registered trademark) "manufactured by GE Plastics Corporation," V8000 "and" V8002 " .

Commercially available products of the polyethersulfone resin include known ones such as PES4100P, PES4800P, PES5003P and PES5200P available from Sumitomo Chemical Co., Ltd.

Examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) oxide, poly (2,6- Methyl-6-ethyl-1,4-phenylene) oxide, poly (2-methyl- Oxide, poly (2-ethyl-6-propyl-1, 4-phenylene) oxide and the like. (Number average molecular weight Mn = 14,000), " Noryl 640-111 (registered trademark) " (number average molecular weight Mn = 25,000), and Asahi Kasei Quot ;, and " SA202 " (number average molecular weight Mn = 20,000), and they can be used by lowering the molecular weight by a known method.

Of these, reactive oligophenylene oxides whose terminals are modified with functional groups are preferred. As a result, the compatibility with the curable resin is improved and the three-dimensional cross-linking structure between the polymers can be formed, so that the mechanical strength is excellent. For example, the polycondensation product of 2,2 ', 3,3', 5,5'-hexamethylbiphenyl-4,4'-diol-2,6-dimethylphenol and the condensation product of 2,2 ', 3,3' And reaction products of chloromethylstyrene.

These reactive oligophenylene oxides can be prepared by a known method. Commercially available products may also be used. For example, OPE-2st 2200 (manufactured by Mitsubishi Gas Chemical Company) can be preferably used.

The weight average molecular weight of the reactive oligophenylene oxide is preferably 2,000 to 20,000, more preferably 4,000 to 15,000. When the weight average molecular weight of the reactive oligophenylene oxide exceeds 20,000, it is difficult to dissolve the reactive oligophenylene oxide in the volatile solvent. On the other hand, if the weight average molecular weight is less than 2,000, the crosslinking density becomes too high, and the elastic modulus and plasticity of the cured product are adversely affected.

The amount of the curable resin in the resin composition used in the present embodiment may be suitably adjusted according to the purpose and is not particularly limited. However, the total solid content of the resin composition is preferably 10 to 90% by weight, more preferably 20 to 70% More preferably 25 to 50% by weight.

When an epoxy resin and / or a cyanate resin is used as the curable resin, the epoxy resin is preferably contained in the total solid content of the resin composition in an amount of 5 to 50 wt%, more preferably 5 to 25 wt% . The cyanate resin is preferably contained in the total solid content of the resin composition in an amount of 5 to 50% by weight, and more preferably 10 to 25% by weight in terms of the cyanate resin.

The resin composition preferably contains an inorganic filler in view of low thermal expansion and mechanical strength. The inorganic filler is not particularly limited, and examples thereof include silicates such as talc, calcined clay, unbaked clay, mica and glass, oxides such as titanium oxide, alumina, silica and fused silica, calcium carbonate, magnesium carbonate, hydrotalcite, (I.e., Al ₂ O ₃ .xH ₂ O, where x = 1 to 2), magnesium hydroxide (magnesium hydroxide), aluminum hydroxide, , Metal hydroxides such as calcium hydroxide, sulfates or sulfates such as barium sulfate, calcium sulfate and calcium sulfite, borates such as zinc borate, barium metaborate, aluminum borate, calcium borate and sodium borate, aluminum nitride, boron nitride, silicon nitride And titanate such as strontium titanate, barium titanate, etc. One of these may be used alone, or two or more of them may be used in combination.

Among these, magnesium hydroxide, aluminum hydroxide, boehmite, silica, fused silica, talc, fired talc, and alumina are preferable. Silica is particularly preferred in view of low thermal expansion and insulation reliability, and more preferably spherical fused silica. In addition, from the viewpoint of flame resistance, aluminum hydroxide is preferable. Further, in the present embodiment, since an inorganic filler uses a substrate which is easy to impregnate, the amount of the inorganic filler in the resin composition can be increased. When the inorganic filler is present in a high concentration in the resin composition, the drill abrasion is deteriorated, but when the inorganic filler is boehmite, the drill abrasion is preferable.

The particle size of the inorganic filler is not particularly limited, but an inorganic filler having an average particle size of monodisperse may be used, and an inorganic filler having an average particle size of a polydispersity may be used. It is also possible to use one type or two or more kinds of mono-dispersed and / or polydispersed inorganic fillers having an average particle size. The average particle diameter of the inorganic filler is not particularly limited, but is preferably from 0.1 mu m to 5.0 mu m, particularly preferably from 0.1 mu m to 3.0 mu m. If the particle diameter of the inorganic filler is less than the above lower limit value, the viscosity of the resin composition becomes high, which may affect the workability at the time of preparing the prepreg. In addition, when the upper limit is exceeded, the phenomenon such as settling of the inorganic filler may occur in the resin composition. The average particle diameter can be measured using a laser diffraction / scattering particle size distribution measuring apparatus (a general apparatus such as SALD-7000 manufactured by Shimadzu Corporation).

The content of the inorganic filler is not particularly limited, but is preferably from 10 to 90% by weight, more preferably from 30 to 80% by weight, and even more preferably from 50 to 75% by weight of the total solid content of the resin composition. When the cyanate resin and / or the prepolymer is contained in the resin composition, the content of the inorganic filler is preferably 50 to 75% by weight based on the total solid content of the resin composition. If the content of the inorganic filler exceeds the upper limit value, the fluidity of the resin composition may deteriorate remarkably. Therefore, if the content is below the lower limit value, the strength of the insulating layer made of the resin composition may not be sufficient.

In addition, the resin composition used in the present embodiment can be compounded with a rubber component. For example, preferred examples of the rubber particles that can be used in the present embodiment include core-shell rubber particles, crosslinked acrylonitrile-butadiene rubber particles, Particles, acrylic rubber particles, silicon particles, and the like.

The core-shell-type rubber particles are rubber particles having a core layer and a shell layer, for example, a two-layer structure in which the shell layer of the outer layer is composed of a glassy polymer and the core layer of the inner layer is a rubbery polymer, Layer structure in which the intermediate layer is composed of a rubber-like polymer and the core layer is composed of a glass-like polymer, and the like. The glassy polymer layer is composed of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is composed of, for example, a butyl acrylate polymer (butyl rubber). Specific examples of the core-shell-type rubber particles include STAPHILLOID AC3832, AC3816N (trade name, manufactured by Kanto Kasei Corporation) and Metablen KW-4426 (trade name, manufactured by Mitsubishi Rayon K.K.). Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle diameter 0.5 mu m, manufactured by JSR Corporation).

Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 (average particle diameter 0.5 mu m, manufactured by JSR Corporation). Specific examples of the acrylic rubber particles include Metablen W300A (average particle diameter 0.1 mu m) and W450A (average particle diameter 0.2 mu m) (manufactured by Mitsubishi Rayon Co., Ltd.).

The silicone particles are not particularly limited as long as they are rubber elastic fine particles formed of an organopolysiloxane. For example, fine particles made of a silicone rubber (organopolysiloxane crosslinked elastomer) itself and a core portion made of silicon of a two- And core shell structure particles coated with silicon as a main component. As silicone rubber fine particles, KMP-605, KMP-600, KMP-597, KMP-594 (manufactured by Shin-Etsu Chemical Co., Ltd.), TREFILL E-500, TREFILL E-600 (manufactured by Toray Dow Corning Co., ) Can be used.

The resin composition may further contain a coupling agent. The coupling agent improves the wettability of the interface between the curable resin and the inorganic filler so that the resin and the inorganic filler are uniformly fixed to the substrate so as to improve heat resistance, particularly solder heat resistance after moisture absorption.

The coupling agent is not particularly limited, and examples thereof include an epoxy silane coupling agent, a cationic silane coupling agent, an aminosilane coupling agent, a titanate-based coupling agent, and a silicone oil-type coupling agent. As a result, the wettability with the interface of the inorganic filler can be increased, thereby further improving the heat resistance.

The amount of the coupling agent to be added is not particularly limited, but is preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the inorganic filler. If the content is less than the above lower limit value, the inorganic filler can not be sufficiently coated, so the effect of improving the heat resistance may be deteriorated. If the content exceeds the upper limit value, the reaction may be affected and the bending strength or the like may be lowered.

If necessary, additives other than the above-described components such as a defoaming agent, a leveling agent, an ultraviolet absorber, a foaming agent, an antioxidant, a flame retardant, a flame retardant such as silicone powder, and an ion scavenger may be added to the resin composition used in the present embodiment.

The resin composition preferably contains at least an epoxy resin, a cyanate resin and an inorganic filler since it is easy to realize low linear expansion, high rigidity and high internal resistance of the prepreg. Among them, the solid content of the resin composition preferably contains 5 to 50% by weight of an epoxy resin, 5 to 50% by weight of a cyanate resin and 10 to 90% by weight of an inorganic filler, more preferably 5 to 25% 10 to 25% by weight of a cyanate resin and 30 to 80% by weight of an inorganic filler.

The prepreg used in the present embodiment is formed by impregnating or coating a varnish of a resin composition with a substrate. As the substrate, well-known materials used in various laminated plates for electrical insulating materials can be used. Examples of the material of the base material include inorganic fibers such as E glass, D glass, NE glass, T glass, S glass or Q glass, organic fibers such as polyimide, polyester or tetrafluoroethylene, and mixtures thereof. These substrates have shapes such as, for example, woven fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat and the like, but the material and shape are not limited to the intended use or performance And can be used alone or in combination with two or more kinds of materials and shapes. Thickness of the base material is not particularly limited, but it is usually 0.01 to 0.5 mm or so, preferably surface treated with a silane coupling agent or the like, and subjected to carding treatment and flattening mechanically in terms of heat resistance, moisture resistance and workability . The prepreg is usually impregnated or coated with a resin so that the content of the resin is 20 to 90% by weight after drying, and is heated and dried at a temperature of 120 to 220 캜 for 1 to 20 minutes to form a semi-hardened state (B- . In addition, a laminated board can be obtained by laminating 1 to 20 sheets of the prepregs, and heating and pressing in a configuration in which a polar thin foil with a carrier foil is disposed on both sides thereof (ultra-thin copper foil). The thickness of the plurality of prepreg layers differs depending on the use, but is usually preferably 0.03 to 2 mm. For example, a multi-stage press, a multi-stage vacuum press, a continuous molding, an autoclave molding machine, or the like is used, and usually a temperature of 100 to 250 DEG C, a pressure of 0.2 to 10 MPa, At a time of 0.1 to 5 hours or by using a vacuum laminator or the like under lamination conditions of 50 to 150 DEG C, 0.1 to 5 MPa, and vacuum pressure of 1.0 to 760 mmHg.

The copper foil with a carrier foil (the copper foil layer 104) is also called a burning plating layer (also referred to as burn plating) on the roughened surface of the polar foil, for example, -195096), oxidation treatment, reduction treatment, etching, or the like. Thereby, a hooking portion (also referred to as a roughening foot portion) is formed on one surface of the bulk portion of the copper foil layer 104.

Further, in the present embodiment, the copper foil layer 104 may be a copper foil comprising copper (excluding the mixture which is inevitably mixed in the manufacturing process), and a copper foil containing an additive metal component such as nickel or aluminum , The content of copper is not particularly limited, but is preferably 90% by weight or more, more preferably 95% by weight or more, and more preferably 99% by weight or more based on the total weight of the total metal components constituting the copper foil layer 104 The additive metal component may be used alone or in combination of two or more thereof). Instead of the copper foil layer 104, a metal foil such as a nickel foil or an aluminum foil may be used.

Here, a detailed method of forming a peelable copper foil used for the copper foil layer 104 will be described.

The method for producing the copper foil used in this embodiment is not particularly limited. For example, in the case of producing a peelable copper foil having a carrier, an inorganic compound such as a metal to be a release layer on a carrier foil having a thickness of 10 to 50 m Or an organic compound layer is formed, and a copper foil is plated on the release layer. As the plating solution, for example, copper sulfate or copper pyrophosphate can be used. In addition, various additives may be added to the bath in consideration of the physical properties and smoothness of the copper foil. The filler metal foil is a metal foil having a carrier, and the carrier can be peeled off.

In the present embodiment, the formation of the copper foil on the release layer can be achieved, for example, by cathodic electrolytic treatment using a copper sulfate plating bath containing gelatin and chloride ions as an additive. The copper sulfate plating bath contains, for example, 15 to 35 ppm of gelatin having an average molecular weight of 5,000 or less. The copper sulfate plating bath contains, for example, a chloride ion concentration of 0.1 to 100 ppm, preferably 0.5 to 50 ppm, particularly preferably 1 to 25 ppm.

In this case, the copper foil is formed by electrolytically treating the copper foil with the copper foil plating bath using a carrier foil having a release layer formed thereon as the negative electrode, and plating the copper foil on the release layer. According to this method for forming a copper foil, it is possible to form a copper foil having an appropriate mechanical strength even after high-temperature heating, excellent in etching property and excellent in operability. This effect is attributed to the fact that the crystal constituting the copper foil can be made finer by adding gelatin.

When the average molecular weight of the gelatin is 5000 or less, recrystallization of the beating layer by heating can be suppressed. This makes it possible to miniaturize crystals after heating. Although the reason for this is not clarified sufficiently, it is considered that gelatine is easily introduced into grain boundaries at the time of plating by reducing the molecular weight of gelatin to a certain value or less, and as a result, progress of recrystallization can be inhibited. The average molecular weight of the gelatin is preferably 500 to 5000, more preferably 1000 to 5000. When the average molecular weight of the gelatin is 500 or more, the gelatin participating in the copper sulfate plating bath can be inhibited from being decomposed in the acidic solution and decomposed into low molecular weight organic compounds such as amino acids. As a result, it is possible to suppress the deterioration of the effect of preventing gelatine from being introduced into the crystal grain boundaries during plating and thereby preventing recrystallization.

The gelatin concentration in the copper sulfate plating bath is preferably 15 to 35 ppm. When the concentration of gelatin is 15 ppm or more, an effect of suppressing recrystallization by heating can be sufficiently obtained. Therefore, it becomes possible to maintain a fine crystal state after heating. When the concentration of gelatin is 35 ppm or less, the internal stress of the copper foil formed by plating can be prevented from becoming high. This makes it possible to curl the carrier foil-attached ultrasonic vibrator while suppressing deformation during transportation.

As the copper sulfate plating bath, for example, a sulfuric acid-acid copper sulfate plating bath containing copper sulfate pentahydrate, sulfuric acid, gelatin and chlorine is preferably used. The concentration of copper sulfate pentahydrate in the copper sulfate plating bath is preferably 50 g / L to 300 g / L, more preferably 100 g / L to 200 g / L. The concentration of sulfuric acid is preferably 40 g / L to 160 g / L, more preferably 80 g / L to 120 g / L. The concentration of gelatin is the same as above. The chloride ion concentration is preferably 1 to 20 ppm, more preferably 3 to 10 ppm. The solvent of the plating bath is usually water. The temperature of the plating bath is preferably 20 to 60 캜, more preferably 30 to 50 캜. The current density at the electrolytic treatment is preferably 1 to 15 A / dm ² , and more preferably ² to 10 A / dm ² .

Strike plating using a plating bath having good adhesion can be used to prevent occurrence of pinholes before electrolytic treatment using the copper sulfate plating bath when forming the copper foil. Examples of the plating bath used for strike plating include a copper pyrophosphate plating bath, a copper citrate plating bath, and a copper-nickel-nickel plating bath.

The copper pyrophosphate plating bath is preferably a plating bath containing, for example, copper pyrophosphate and potassium pyrophosphate. The concentration of copper pyrophosphate in the copper pyrophosphate plating bath is preferably 60 g / L to 110 g / L, more preferably 70 g / L to 90 g / L. The concentration of potassium pyrophosphate is preferably 240 g / L to 470 g / L, more preferably 300 g / L to 400 g / L. The solvent of the plating bath is usually water. The pH of the plating bath is preferably 8.0 to 9.0, more preferably 8.2 to 8.8. Ammonia water or the like may be added for adjusting the pH value (the same applies hereinafter). The temperature of the plating bath is preferably 20 to 60 캜, more preferably 30 to 50 캜. The current density at the electrolytic treatment is preferably 0.5 to 10 A / dm ² , and more preferably 1 to 7 A / dm ² . The electrolytic treatment time is preferably 5 to 40 seconds, more preferably 10 to 30 seconds.

The copper citrate plating bath is preferably a plating bath containing, for example, copper sulfate pentahydrate and trisodium citrate dihydrate. The concentration of copper sulfate pentahydrate in the copper citrate copper plating bath is preferably 10 g / L to 50 g / L, more preferably 20 g / L to 40 g / L. The concentration of the tri-sodium citrate dihydrate is preferably 20 g / L to 60 g / L, more preferably 30 g / L to 50 g / L. The solvent of the plating bath is usually water. The pH of the plating bath is preferably 5.5 to 7.5, more preferably 6.0 to 7.0. The temperature of the plating bath is preferably 20 to 60 캜, more preferably 30 to 50 캜. The current density at the electrolytic treatment is preferably 0.5 to 8 A / dm ² , more preferably 1 to 4 A / dm ² . The electrolytic treatment time is preferably 5 to 40 seconds, more preferably 10 to 30 seconds.

As the copper-nickel-citrate plating bath, for example, a plating bath containing copper sulfate pentahydrate, nickel sulfate hexahydrate and trisodium citrate dihydrate is preferable. The concentration of copper sulfate pentahydrate in the copper-nickel-citrate plating bath is preferably 10 g / L to 50 g / L, more preferably 20 g / L to 40 g / L. The concentration of nickel sulfate hexahydrate is preferably 1 g / L to 10 g / L, more preferably 3 g / L to 8 g / L. The concentration of the tri-sodium citrate dihydrate is preferably 20 g / L to 60 g / L, more preferably 30 g / L to 50 g / L. The solvent of the plating bath is usually water. The pH of the plating bath is preferably 5.5 to 7.5, more preferably 6.0 to 7.0. The temperature of the plating bath is preferably 20 to 60 캜, more preferably 30 to 50 캜. The current density at the electrolytic treatment is preferably 0.5 to 8 A / dm ² , more preferably 1 to 4 A / dm ^{2. The} electrolytic treatment time is preferably 5 to 40 seconds, more preferably 10 to 30 seconds .

The peeling layer is an inorganic compound or an organic compound layer such as a metal oxide, and any known one can be used as long as it can be peeled off even if it is subjected to a heat treatment at 100 to 300 캜 during lamination. As the metal oxide, for example, a mixture of zinc, chromium, nickel, copper, molybdenum, alloys, metals and metal compounds is used. As the organic compound, it is preferable to use one or two or more selected from a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid.

The nitrogen-containing organic compound is preferably a nitrogen-containing organic compound having a substituent. Specific examples of the triazole compound having a substituent include 1,2,3-benzotriazole (hereinafter abbreviated as "BTA"), carboxybenzotriazole (hereinafter abbreviated as "CBTA"), N ', N'-bis (Abbreviated as "BTD-U" hereinafter), 1H-1,2,4-triazole (hereinafter abbreviated as "TA") and 3-amino-1H- -Triazole (hereinafter abbreviated as " ATA ") or the like is preferably used.

Examples of the sulfur-containing organic compound include mercaptobenzothiazole (hereinafter abbreviated as "MBT"), thiocyanuric acid (hereinafter abbreviated as "TCA") and 2-benzimidazole thiol Is preferably used.

As the carboxylic acid, monocarboxylic acid is particularly preferably used, and oleic acid, linolic acid and linoleic acid are preferably used among them.

As described above, desired orientation can be realized on the upper surface of the copper foil layer 104 of the present embodiment by suitably controlling the production method, such as increasing the electrolytic density or reducing the film thickness.

The adhesion between the copper foil layer 104 and the insulating layer 102 is set at a practical level or at least a part of the surface of the copper foil layer 104, The surface treatment may be carried out. Examples of the surface treatment for the metal foil used for the copper foil layer 104 include rust proofing, chromate treatment, silane coupling treatment, or a combination thereof. Any one of the surface treatment means can be selected appropriately in accordance with the resin material constituting the insulating layer 102. [

The rust preventive treatment can be carried out by forming a thin film of a metal such as nickel, tin, zinc, chromium, molybdenum, cobalt or the like on the metal foil by sputtering, electroplating or electroless plating. In terms of cost, electroplating is preferable. It is also possible to add a necessary amount of a complexing agent such as citrate, tartrate, sulfamic acid and the like in order to facilitate precipitation of metal ions. The plating solution is usually used in an acidic range and is carried out at room temperature (for example, 25 캜) to 80 캜. The plating conditions are appropriately selected from the range of current density of 0.1 to 10 A / dm ² and energization time of 1 to 60 seconds, preferably 1 to 30 seconds. Anti-corrosive treatment of metal amount varies depending upon the kind of metal, but is preferably 10~2000㎍ / dm ² in total. If the anticorrosive treatment is too thick, etching inhibition and deterioration of electrical characteristics are caused. If the anticorrosive treatment is too thin, it may cause a decrease in the peel strength with the resin.

When the cyanate resin is contained in the resin composition constituting the insulating layer 102, it is preferable that the rust-preventive treatment is performed by a metal containing nickel. This combination is useful because there is little decrease in the peel strength in the heat resistance deterioration test or the moisture resistance deterioration test.

As the chromate treatment, an aqueous solution containing hexavalent chromium ions is preferably used. The chromate treatment can be carried out by a simple immersion treatment, but is preferably carried out by a cathode treatment. It is preferable that the treatment is carried out under the conditions of 0.1 to 50 g / L sodium bicarbonate, pH 1 to 13, bath temperature 0 to 60 캜, current density 0.1 to 5 A / dm ² and electrolysis time 0.1 to 100 sec. It is also possible to use chromic acid or potassium dichromate instead of sodium dichromate. Further, it is preferable that the chromate treatment is carried out over the rust-preventive treatment. As a result, the adhesion between the insulating resin composition layer (insulating layer 102) and the metal foil (copper foil layer 104) can be further improved.

Examples of the silane coupling agent used for the silane coupling treatment include epoxy functional silanes such as 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Amino functional silanes such as 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropyltrimethoxysilane and N-2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, vinyl Olefin functional silanes such as trimethoxysilane, vinylphenyltrimethoxysilane and vinyltris (2-methoxyethoxy) silane, acrylic functional silanes such as 3-acryloxypropyltrimethoxysilane, 3-methacryloyl Methacryl-functional silanes such as oxypropyltrimethoxysilane, and mercapto-functional silanes such as 3-mercaptopropyltrimethoxysilane. These may be used alone, or a plurality of them may be mixed. These coupling agents are dissolved in a solvent such as water at a concentration of 0.1 to 15 g / L, and the resulting solution is applied or electrodeposited on the metal foil at a temperature of from room temperature to 50 캜 to adsorb the silane coupling agent to the metal foil. These silane coupling agents are condensed with the hydroxyl groups of the rust-inhibited metal on the surface of the metal foil to form a film on the metal foil. After the silane coupling treatment, this bond is stabilized by heating, ultraviolet irradiation, or the like. In the heat treatment, for example, it is preferable to carry out drying at a temperature of 100 to 200 캜 for 2 to 60 seconds. The ultraviolet ray irradiation is preferably carried out in a wavelength range of ^{200 to} 400 nm and 200 to 2500 mJ / cm ² , for example. The silane coupling treatment is preferably carried out in the outermost layer of the metal foil. When the cyanate resin is contained in the insulating resin composition constituting the insulating layer 102, it is preferably treated with an amino silane-based coupling agent. This combination is useful because there is little decrease in the peel strength in the heat resistance deterioration test or the moisture resistance deterioration test.

The silane coupling agent used for the silane coupling treatment is preferably chemically reacted with the insulating resin composition constituting the insulating layer 102 by heating at 60 to 200 캜, more preferably 80 to 150 캜 Do. As a result, the functional group in the insulating resin composition and the functional group of the silane coupling agent can be chemically reacted to obtain better adhesion. For example, for an insulating resin composition containing an epoxy group, it is preferable to use a silane coupling agent containing an amino functional silane. This is because the epoxy group and the amino group easily form a strong chemical bond by heat and the bond is remarkably stable with respect to heat or moisture. As such a combination for forming a chemical bond, a combination of an epoxy group, an epoxy group, an epoxy group, an epoxy group, a mercapto group, an epoxy group, a hydroxyl group, an epoxy group, a carboxyl group, an epoxy group, a cyanato group, Earthenware, and the like.

It is preferable to use an epoxy resin liquid at room temperature as the insulating resin composition of the insulating resin composition used in the present embodiment. In this case, since the viscosity at the time of melting decreases greatly, the wettability at the bonding interface improves, A chemical reaction between the resin and the silane coupling agent tends to occur, and as a result, a strong peel strength can be obtained. Specifically, a bisphenol A type epoxy resin having an epoxy equivalent of about 200, a bisphenol F type epoxy resin, and a phenol novolak type epoxy resin are preferable.

When the insulating resin composition contains a curing agent, it is particularly preferable to use a heat curing type latent curing agent as the curing agent. That is, when the functional group in the insulating resin composition and the functional group of the silane coupling agent are chemically reacted, the curing agent is selected so that the reaction temperature of the functional group of the insulating resin composition with the functional group of the silane coupling agent becomes lower than the temperature at which the curing reaction of the insulating resin composition starts . Thereby, the reaction between the functional group in the insulating resin composition and the functional group of the silane coupling agent is preferentially and selectively performed, and the adhesion between the metal foil (the copper foil layer 104) and the insulating resin composition layer (insulating layer 102) becomes higher. Examples of the thermosetting latent curing agent for an insulating resin composition containing an epoxy resin include solid dispersion-heat-dissolving type curing agents such as dicyandiamide, dihydrazide compounds, imidazole compounds and amine-epoxy adducts, Compound, onium salt, boron trichloride · amine salt, block carboxylic acid compound and the like.

The above-described copper foil laminate (10) having a carrier foil as shown in Fig. 1 (a) can be obtained by laminating and integrating a prepreg containing an insulating resin composition and a polar foil with a carrier foil according to the above- Can be obtained. Then, as shown in Fig. 1 (b), the copper foil layer 106 is peeled off to obtain the copper clad laminate 100 having the copper foil layer 104 on both surfaces of the insulating layer 102. [ The copper foil layer 104 may be formed on at least one surface of the insulating layer 102 or may be formed on the entire surface or a part of the insulating layer 102. [ It is also preferable that the copper foil layer 104 of the present embodiment has a bulk portion and a coarsened portion.

Here, the details of the laminate (the copper clad laminate 100) will be described.

The etching rate of the copper foil layer 104 (thin-layer copper foil) under the aforementioned conditions is 0.68 탆 / min to 1.25 탆 / min, more preferably 0.68 탆 / min to 1.24 탆 / min, / Minute and not more than 1.23 m / min. The etching rate of the copper foil layer 104 described here refers only to the etching rate of the bulk portion in particular.

In the present embodiment, by setting the etching rate of the copper foil layer 104 to a lower limit value or more, etching residues of the copper foil layer 104 can be reduced, and the wiring shape can be improved. In addition, by setting the etching rate of the copper foil to be not more than the upper limit value, it is possible to suppress the deterioration of the adhesion between the wiring and the insulating layer by forming a cut in the side wall of the copper foil layer 104. That is, it is possible to suppress occurrence of an abnormal concave portion in the bulk portion of the copper foil layer 104 when etching to the coarsened portion of the copper foil layer 104.

In the present embodiment, the etching rate of the bulk portion of the copper foil can be measured by the following method.

1. A substrate (copper clad laminate 100) obtained by laminating polar thin foils on both sides of which a carrier foil (carrier thin layer 106) was removed was cut into 40 mm 80 mm to obtain a sample piece. The sample piece is read to two decimal places with a vernier caliper to calculate the area of the sample piece.

2. Perform a drying treatment at 80 ° C for 1 min. × 3 times in the horizontal drying line on the sample piece.

3. Measure the initial weight WO of the sample piece (but including the weight of the substrate).

4. Adjust the etchant.

4-1: Weigh 60 g of 95% sulfuric acid (Wako Pure Chemical Industries, Limited) and put in a 1L beaker.

4-2: The pure water is poured into a beaker using 4-1 to make 1000cc.

4-3: The mixture is stirred with a magnetic stirrer at 30 ° C ± 1 ° C for 3 minutes.

4-4: 20 cc of 34.5% aqueous hydrogen peroxide (manufactured by Kanto Kagaku Kogyo Co., Ltd.) is weighed and placed in a beaker used at 4-1, the temperature is adjusted to 1020 cc and the mixture is stirred at 30 ° C ± 1 ° C for 3 minutes. Thereby, an etching solution of 55.9 g / L of sulfuric acid and 19.6 cc / L of 34.5% aqueous hydrogen peroxide was obtained.

5. The sample piece is immersed in the above etching solution (liquid temperature: 30 DEG C +/- 1 DEG C, stirring condition: magnetic stirrer, 250 rpm).

6. Measure the weight W1 of the sample piece (including the weight of the substrate) every 30 seconds until the bulk part of the polar beater is completely etched.

7. Plot the etching weight (W0-W1) / (the immersion area on both sides which m = ^2), the etching time (seconds) and the etching weight (g / m ²⁾ in the Y-axis to the X-axis by calculating a. The slope K is calculated using the least squares method for 0 to 150 seconds.

Represents the conversion equation of the etching rate of the present embodiment.

Etch rate (㎛ / minute) = K (g / sec · m ²⁾ ÷ 8.92 (copper density g / cm ³⁾ × 60 (sec / min)

The difference in Vickers hardness of the copper foil layer 104 before and after the heat treatment at 230 deg. C for 1 hour is preferably 0 Hv or more and 50 Hv or less, and more preferably 0 Hv or more and 30 Hv or less. The difference in Vickers hardness of the copper foil layer 104 is set to be not more than the upper limit value so that the recrystallization of the copper foil layer 104 is progressed by heating to increase the crystal grain size to suppress the slowing of the etching rate, Or the like. In this case, the absolute value of the difference in Vickers hardness of the copper foil layer 104 before and after the heat treatment at 230 deg. C for 1 hour is preferably 0 Hv or more and 50 Hv or less, and more preferably 0 Hv or more and 30 Hv or less .

The copper foil layer 104 has a Vickers hardness of preferably 180 Hv or more and 240 Hv or less, more preferably 185 Hv or more and 235 Hv or less, after the heat treatment at 230 占 폚 for 1 hour. By setting the Vickers hardness after heating to 180 Hv or more, recrystallization of the beating layer (the copper foil layer 104) is promoted by heating to suppress the increase in crystal grain size and suppress the decrease in circuit linearity after etching. On the other hand, by setting the Vickers hardness after heating to 240 Hv or less, it is possible to suppress occurrence of cracks during operation due to the breakage of the beating layer due to the breakage of the beating layer, and it is possible to improve the cold and heat shock resistance of the formed fine interconnections.

In the present embodiment, the Vickers hardness can be measured by, for example, the following method.

That is, the Vickers hardness measurement is carried out at 23 占 폚 using an acrylic micro hardness meter (model number MVK-2H) in accordance with JIS Z 2244 in the following sequence. (1) A carrier foil with a carrier foil formed up to the copper foil layer is left in an oven (nitrogen atmosphere) heated at 230 캜 for 1 hour, and then cut into 10 × 10 mm square. (2) The indentations are imaged on the cut samples under the conditions of a load speed of 3 탆 / second, a test load of 5 gf and a holding time of 15 seconds, and the Vickers hardness is calculated from the indentation measurement results. (3) An average value obtained by measuring the Vickers hardness of any five points is taken as the Vickers hardness value of the present embodiment.

In addition, as a sample, a polarizing foil with a carrier foil not subjected to heat treatment may be used immediately after forming the copper foil layer.

In the copper foil layer 104, the grain size of the cross-section after the heat treatment at 230 占 폚 for 1 hour is preferably 2.0 占 퐉 or less, more preferably 0.5 占 퐉 or less, further preferably 0.25 占 퐉 or more and 0.5 占 퐉 or less to be. By reducing the grain size of the copper foil layer 104 to the upper limit value or less, deterioration in circuit linearity after etching can be suppressed. By setting the grain size of the copper foil layer 104 to be equal to or more than the lower limit value, the internal stress (tensile stress) before heating after the baking layer coating is prevented from becoming too high and the entire polar foil with the support is curled, Can be suppressed.

In the present embodiment, the grain size of the copper foil layer 104 can be measured by the following method.

That is, the grain size of the copper foil layer 104 was measured in accordance with JIS H 0501. The concrete procedure is as follows. First, the laminated plate (copper clad laminate 100) is processed by an FIB (convergent ion beam) processing apparatus and a SIM (Scanning Ion Microscope) observation photograph is taken. The grain size of the cross section of the photographed photograph is calculated from the standard photograph of the comparative method defined in JIS H 0501.

In the present embodiment, the thickness of the copper foil layer 104 (particularly, the bulk portion) is reduced by decreasing the crystal grain size of the copper foil layer 104, decreasing the change of the Vickers hardness after heating, The etching rate can be increased. In addition, although the etching rate of the coarse portion is usually slower than that of the bulk portion, for example, it is possible to increase the etching rate by decreasing the electrolytic density.

The thickness of the copper foil layer 104 can be arbitrarily set according to the use. For example, the thickness of the copper foil layer 104 is preferably not less than 0.1 mu m and not more than 5 mu m, and more preferably not less than 1 mu m and not more than 4 mu m. By setting the film thickness of the copper foil layer 104 within the above range, a good microcircuit can be formed.

Then, as shown in Fig. 1 (c), through-holes 108 for interlayer connection penetrating from the upper surface to the lower surface of the copper clad laminate 100 are formed. For example, in the case of forming the through hole 108 having a diameter of 100 mu m or more, a means using a drill or the like is preferable from the viewpoint of productivity, In the case of forming the through holes 108 having a size of 100 μm or less, means using a gas laser such as carbon dioxide gas or excimer or a solid laser such as YAG is suitable.

In this embodiment, the catalyst nuclei are provided on the front surface of the copper foil layer 104 and on the inner wall surface of the through hole 108, although it is also possible to apply catalyst nuclei on at least the copper foil layer 104. The catalyst nucleus is not particularly limited, but for example, noble metal ions and palladium colloids can be used. Subsequently, an electroless plating layer is formed using the catalyst nuclei as nuclei. Before the electroless plating process, smear removal by a chemical solution, for example, is performed on the surfaces of the copper foil layer 104 and the through holes 108 You can do it. The desmear treatment is not particularly limited and includes a wet process using an oxidizing agent solution having an organic substance decomposing action and a plasma treatment for removing an organic substance residue by irradiating an active species (plasma, radical, etc.) A known method such as a dry method such as a method can be used. As the desmear treatment of the wet method, specifically, a method of performing swelling treatment on the surface of the resin, followed by etching by an alkali treatment, and then neutralization treatment can be given.

Subsequently, as shown in Fig. 1 (d), a thin electroless plated layer 110 is formed on the copper foil layer 104 provided with the catalyst nuclei and on the inner wall of the through hole 108 by electroless plating. The electroless plating layer 110 electrically connects the copper foil layer 104 on the upper surface of the insulating layer 102 and the copper foil layer 104 on the lower surface thereof. As the electroless plating, for example, copper sulfate, formalin, a complexing agent, sodium hydroxide and the like can be used. In addition, it is preferable that after the electroless plating, heat treatment at 100 to 250 캜 is performed to stabilize the plating film. And heat treatment at 120 to 180 캜 is particularly preferable in that a film capable of inhibiting oxidation can be formed. The average thickness of the electroless plating layer 110 may be as long as the following electroplating can be carried out. For example, about 0.1 to 1 占 퐉 is sufficient. The inside of the through hole 108 may be filled with a conductive paste or an insulating paste, or may be filled with an electric pattern plating.

1 (e), a resist layer 112 having a predetermined opening pattern is formed on the electroless plating layer 110 provided on the copper foil layer 104. Then, as shown in Fig. This opening pattern corresponds to the conductor circuit pattern described later. For this reason, the resist layer 112 is provided so as to cover the non-circuit forming area on the copper foil layer 104. In other words, the resist layer 112 is not formed in the conductor circuit forming region on the through hole 108 and on the copper foil layer 104. The resist layer 112 is not particularly limited and a known material can be used, and liquid and dry films can be used. In the case of fine wiring formation, it is preferable to use a photosensitive dry film or the like as the resist layer 112. In order to form the resist layer 112, for example, a photosensitive dry film is laminated on the electroless plating layer 110, the non-circuit forming area is exposed to light, and the unexposed area is dissolved and removed as a developer. In addition, the remaining cured photosensitive dry film becomes the resist layer 112. The thickness of the resist layer 112 is preferably equal to or greater than the thickness of the conductor (plating layer 114) to be plated thereafter.

Subsequently, as shown in Fig. 2 (a), a plating layer 114 is formed on at least the inside of the opening pattern of the resist layer 112 and the electroless plating layer 110 by an electroplating process. At this time, the copper foil layer 104 operates as a power supply layer. In this embodiment, the plating layer 114 may be continuously provided on the upper surface of the insulating layer 102, the inner wall of the through hole 108, and the lower surface thereof. Although the electroplating is not particularly limited, a known method used in a conventional printed wiring board can be used. For example, a method such as flowing a current through such a plating liquid in a state of being immersed in a plating liquid such as copper sulfate can be used . Although the thickness of the plating layer 114 is not particularly limited, it may be used as a circuit conductor. For example, it is preferably in the range of 1 to 100 mu m, more preferably in the range of 5 to 50 mu m. The plating layer 114 may be a single layer or a multilayer structure. The material of the plating layer 114 is not particularly limited, but copper, a copper alloy, a 42 alloy, nickel, iron, chromium, tungsten, gold, solder and the like can be used.

Subsequently, as shown in Fig. 2 (b), the resist layer 112 is removed using an alkaline removing solution, sulfuric acid, or a commercially available resist stripping solution.

Subsequently, as shown in Fig. 2 (c), the electroless plating layer 110 and the copper foil layer 104 other than the region where the plating layer 114 is formed are removed. As a method for removing the copper foil layer 104, for example, soft etching (flash etching) is used. This makes it possible to form a pattern of the conductor circuit 118 in which the copper foil layer 104 and the metal layer 116 (the electroless plated layer 110 and the plated layer 114) are laminated.

Here, the etching solution used in the soft etching of this embodiment will be described below. Although the etching solution is not particularly limited, when a conventional diffusion rate type etching solution is used, the fine part of the wiring tends to deteriorate the circuit formability because the exchange of the solution is bad anyhow. For this reason, it is preferable to use a type in which the reaction between copper and the etching solution progresses at a reaction rate rather than a diffusion rate. If the reaction between copper and the etching solution is reaction rate, the etching rate does not change even if the diffusion is further strengthened. That is, there is no difference in etching speed between a place where the liquid exchange is good and a place where the liquid exchange is good. As the reaction rate-controlling etchant, for example, hydrogen peroxide and an acid containing no halogen element as a main component can be cited. Since hydrogen peroxide is used as an oxidizing agent, it is possible to strictly control the etching rate by controlling the concentration thereof. Further, when the halogen element is mixed into the etching solution, the dissolution reaction tends to become diffusion rate. As the acid which does not contain halogen, nitric acid, sulfuric acid, organic acid and the like can be used, but sulfuric acid is preferable because it is inexpensive. When sulfuric acid and hydrogen peroxide are the main components, it is preferable to set the concentration to 5 to 300 g / L and 5 to 200 g / L, respectively, from the viewpoints of the etching rate and the stability of the solution. For example, ammonium persulfate, sodium persulfate, sodium persulfate, and the like.

Various etching methods can be employed. For example, the copper clad laminate 100 may be immersed in an etchant immersed in a liquid flow container such as a beaker, or the etchant may be applied to the copper foil layer 104 by a shower method.

As described above, by appropriately selecting the etching rate of the copper foil layer 104, the conductor circuit 118 having a desired shape can be obtained. Thus, the printed circuit board 200 on which the conductor circuit 118 is formed on both surfaces of the insulating layer 102 is obtained.

2 (d-1), the solder resist layer 120 may be formed so as to cover the insulating layer 102 and a part of the conductor circuit 118. The solder resist layer 120 may include, for example, a filler or a substrate having excellent insulating properties, and a heat-resistant resin composition such as a photosensitive resin, a curable resin, and a thermoplastic resin is used. The first plating layer 122 and the second plating layer 124 may be further formed on the conductor circuit 118 on which the openings of the solder resist layer 120 are provided. Thus, the metal layer 116 may have a multilayer structure of two or more. As the first plating layer 122 and the second plating layer 124, a gold plating layer may be employed. As a method of gold plating, a conventionally known method may be employed. For example, electroless nickel plating is performed on the plating layer 114 in an amount of 0.1 to 10 mu m, substitution gold plating is performed in a range of 0.01 to 0.5 mu m And electroless gold plating is performed at about 0.1 to 2 탆. Thus, the printed wiring board 202 shown in Fig. 2 (d-1) is obtained.

As shown in Fig. 2 (d-2), the first plating layer 122 and the second plating layer 124 may be formed around the conductor circuit 118 without forming the solder resist layer 120 . As the first plating layer 122 and the second plating layer 124, for example, a laminate of a nickel plating layer and a gold plating layer may be employed. Thus, the printed wiring board 204 shown in Fig. 2 (d-2) is obtained.

A semiconductor device (not shown) may be mounted on these printed wiring boards 200, 202, and 204 to obtain a semiconductor device.

(Second Embodiment)

Next, a method for manufacturing a printed wiring board according to the second embodiment will be described.

Figs. 3 to 5 are cross-sectional views showing the sequence of manufacturing steps of the method for manufacturing a printed wiring board according to the third embodiment. Fig. The method for manufacturing a printed wiring board according to the third embodiment is the same as the method for manufacturing a printed wiring board according to the third embodiment except that the printed wiring boards 200, 202 and 204 obtained in the second embodiment are used as an inner layer circuit board, will be.

First, the printed wiring board 200 obtained in Fig. 2 (c) is employed as the inner-layer circuit board. And the inner layer circuit (conductor circuit 118) of the printed wiring board 200 is roughened. Here, the coarsening treatment means that chemical treatment and plasma treatment are performed on the surface of the conductor circuit. The roughening treatment may be, for example, a blackening treatment using oxidation-reduction or a chemical solution treatment using a known roughening agent-hydrogen peroxide-based roughening solution. This makes it possible to improve the adhesion between the interlayer insulating material constituting the insulating layer 130 and the conductor circuit 118 of the printed wiring board 200. The inner layer circuit board is not particularly limited in place of the printed wiring board 200 obtained in the second embodiment, but may be formed by a plated-through hole method, a build-up method, or the like, A printed wiring board may also be used. The conductor circuit layer to be an inner layer circuit may be formed by a conventionally known circuit forming method. In the multilayered printed circuit board, a through hole is formed by performing a drilling process, a laser process, or the like on the laminate (the laminate obtained by laminating a plurality of prepregs) which becomes the core layer and the metal laminate plate, The inner layer circuit may be electrically connected.

Subsequently, as shown in Fig. 3A, an insulating layer 130 (prepreg) and a copper foil layer 105 with a carrier thin layer 107 (a carrier) are formed on both sides of the printed circuit board 200, Thinly attached foil). Subsequently, as shown in Fig. 3 (b), the multilayer body in which these are superimposed is heated and pressed to form a multilayer laminate. Subsequently, as shown in Fig. 3 (c), the carrier foil layer 107 is peeled off.

3 (d), the insulating layer 130 and a portion of the copper foil layer 105 are removed to form a hole 109. Next, as shown in Fig. And a part of the surface of the conductor circuit 118 is exposed on the bottom surface of the hole 109. The method for forming the hole 109 is not particularly limited. For example, a method of forming a blind via hole having an air hole diameter of 100 탆 or less using a gas laser such as carbon dioxide gas or excimer or a solid laser such as YAG have. 3 (d), the hole 109 is shown as a non-through hole, but it may be a through hole. In the case of through holes, laser irradiation or a drilling machine may be used.

Subsequently, as shown in Fig. 4 (a), a thin electroless plated layer 111 is formed on the conductor circuit 118 to which the catalyst nuclei are applied, on the inner wall of the hole 109 and on the copper foil layer 105 . The electroless plating layer 111 is formed in the same manner as the electroless plating layer 110 described above. Prior to this electroless plating, a desmear treatment such as smear removal by a chemical liquid may be performed as described above. The thickness of the electroless plating layer 110 may be any thickness as long as the following electroplating can be performed. The inside of the hole 109 (blind via hole) may be filled with a conductive paste or an insulating paste, or may be filled with an electric pattern plating.

Subsequently, a resist layer 113 having an opening pattern corresponding to the conductive circuit pattern is formed on the electroless plating layer 110. In other words, the resist layer 113 is formed to mask the non-circuit forming portion. As the resist layer 113, the same material as the resist layer 112 described above can be used. It is preferable that the thickness of the resist layer 113 is equal to or greater than the thickness of the conductor circuit to be plated thereafter.

Then, as shown in Fig. 4 (c), a plating layer 132 is formed in the opening pattern of the resist layer 113. Next, as shown in Fig. The plating layer 132 may be formed on the conductor circuit 118 inside the hole 109 or on the electroless plating layer 111 in the opening pattern. The electroplating for forming the plating layer 132 may be the same as the plating layer 114 described above. The thickness of the plating layer 132 may be used as a circuit conductor, and is preferably in the range of 1 to 100 mu m, more preferably in the range of 5 to 50 mu m.

Then, as shown in Fig. 5 (a), the resist layer 113 is peeled off in the same manner as the resist layer 112 described above. Subsequently, as shown in Fig. 5B, the copper foil layer 105 and the electroless plated layer 111 are removed by soft etching (flash etching) in the same manner as the above-described copper foil layer 104 described above. Thus, a conductor circuit pattern composed of the copper foil layer 105, the electroless plating layer 111, and the plating layer 132 can be formed. In addition, vias and pads electrically connected to the conductor circuit 118 can be formed on the conductor circuit 118 by the plating layer 132. [ Thus, the printed wiring board 201 is obtained.

5 (c-1), a solder resist layer 121 may be formed on the insulating layer 130, on the plating layer 132 of the conductor circuit pattern, and on the plating layer 132 of the pad . As the solder resist layer 121, the same material as that of the above-described solder resist layer 120 can be used. A first plating layer 123 and a second plating layer 125 may be additionally formed on the plating layer 132 provided with the openings of the solder resist layer 121 such as a nickel plating layer and a gold plating layer . Thus, the printed wiring board 203 shown in Fig. 5 (c-1) is obtained.

5 (c-2), the first plating layer 123 and the second plating layer 125 described above are formed around the conductor circuit pattern and around the pad without forming the solder resist layer 121 . Thus, the printed wiring board 205 shown in Fig. 5 (c-2) is obtained. Also in the second embodiment, the same effects as those of the first embodiment can be obtained.

(Third Embodiment)

Next, the manufacturing process of the printed wiring board 101 of the third embodiment will be described in detail.

As shown in Fig. 6 (a), a copper clad laminate 10 is prepared. Subsequently, as shown in Fig. 6 (b), the carrier foil layer 106 is removed from the copper clad laminate 10 with the carrier foil removed. Subsequently, a resist layer 112 having a predetermined opening pattern is formed on the copper foil layer 104 left as shown in Fig. 6 (c). A plating layer (metal layer 115) is formed in the opening pattern of the resist layer 112 and on the copper foil layer 104 by a plating process (Fig. 6 (d)). Subsequently, the resist layer 112 is removed as shown in Fig. 6 (e). Thus, a predetermined pattern of the metal layer 115 can be selectively formed on the copper foil layer 104. 6 (f), the copper foil layer 104 in the region not covered with the metal layer 115 is removed by, for example, soft-etching. After the step of removing the copper foil layer 104, the pattern of the conductor circuit 119 can be formed by the copper foil layer 104 and the metal layer 115 remaining. The printed wiring board 101 of the third embodiment is obtained by the above process. The same effects as those of the first embodiment can be obtained also in the third embodiment.

(Fourth Embodiment)

Next, the manufacturing process of the printed wiring board 101 of the fourth embodiment will be described in detail.

First, as shown in Fig. 7 (a), a copper clad laminate 10 is prepared. In the copper clad laminate 10, the carrier foil layer 106 is bonded to both surfaces of the insulating layer 102 together with the copper foil layer 104. Subsequently, as shown in Fig. 7 (b), the carrier foil layer 106 is removed from the copper clad laminate with carrier foil 10. Subsequently, as shown in Fig. 7 (c), a metal layer 115 (plating layer) is formed on the entire surface of the copper foil layer 104 by a plating process. Subsequently, as shown in Fig. 7 (d), a resist layer 112 having a predetermined opening pattern is formed on the planar metal layer 115. Then, as shown in Fig. Subsequently, as shown in Fig. 7 (e), the metal layer 115 and the copper foil layer 104 in the opening pattern of the resist layer 112 are removed by, for example, etching. Thereafter, as shown in Fig. 7 (f), the resist layer 112 is removed. As a result, a pattern of the conductor circuit 119 composed of the copper foil layer 104 and the metal layer 115 can be formed. By the above process, the printed wiring board 101 of the fourth embodiment is obtained. The same effects as those of the first embodiment can be obtained also in the fourth embodiment.

As described above, according to the present embodiment, it is possible to provide a printed wiring board manufacturing method and a printed wiring board which are excellent in fine circuit processing of the carrier foil-equipped electrostatic chuck, fine pattern shape, and insulation reliability.

The method of manufacturing a printed wiring board of the present embodiment can be applied not only to the case where the conductor circuit layer is formed on both surfaces of the substrate for a printed wiring board but also when the conductor circuit layer is formed only on one surface of the substrate for a printed wiring board. As shown in Fig. 2 (c), the multilayer printed wiring board of the third embodiment can also be applied to a double-sided printed wiring board as an inner-layer circuit board. Therefore, according to the method for producing a printed wiring board of the present embodiment, any of a single-sided printed wiring board, a double-sided printed wiring board and a multilayer printed wiring board can be produced.

Example

Hereinafter, a copper clad laminate with a carrier foil according to the present invention and a copper clad laminate using the copper foil and a method for producing a printed wiring board of the present invention will be described. Here, the case where an electrolytic copper foil is used for the carrier foil will be mainly described. The present invention will be described in detail based on examples and comparative examples, but the present invention is not limited thereto.

Unless specifically stated otherwise, " parts " and "% "

1. Manufacture of pole foil with carrier foil

Hereinafter, the production of the pole foil with a carrier foil will be described.

(Production Example 1)

As a carrier foil (supporting metal foil), a peeling layer and a thin polar thin foil layer were sequentially formed on the glossy surface of an electrolytic copper foil having a thickness of 18 mu m. The manufacturing conditions are as follows.

First, the carrier foil was immersed in an acid cleaning bath (sulfuric acid: 30 g / L) for 5 seconds to remove oil and oxidation film on the surface. Subsequently, a current density of 20 A / dm ^{2 (} 30 g / L) was measured using a separation layer forming system (30 g / L of nickel sulfate hexahydrate, 3 g / L of sodium molybdate dihydrate, 30 g / L of tri- For 5 seconds to form a release layer on the glossy surface of the carrier foil. Subsequently, a bulk portion (hereinafter referred to as a bulk copper layer) was formed on the release layer. The bulk copper layer was formed as follows. First, electrolytic treatment was carried out for 15 seconds at a current density of 2.0 A / dm ² using a plating bath (80 g / L of copper pyrophosphate, 320 g / L of potassium pyrophosphate, 2 ml / L of ammonia water and 40 캜 of liquid temperature) To form a first bulk copper layer. Subsequently, a plating bath (copper sulfate pentahydrate: 160 g / L, sulfuric acid: 100 g / L, gelatin (Nippon Company, trade name: PBH, weight average molecular weight (MW) 5000: 15 ppm, chloride ion: And electrolytically treated at a current density of 3.5 A / dm ² for 150 seconds to form a second bulk copper layer on the first bulk copper layer. As a result, a bulk copper layer was formed. Then, the plating bath (copper sulfate pentahydrate: 150g / L, sulfuric acid: 100g / L, liquid temperature of 30 ℃) the use to deliver 70 seconds after electrolytic 3 seconds with a current density of 30A / dm ² treated with a current density of 5A / dm ² treatment And a harmonious part (hereinafter referred to as a coarsened copper layer) was formed on the bulk copper layer. Subsequently, electrolytic treatment was carried out for 2.5 seconds at a current density of 0.5 A / dm ² using a rust-inhibiting treatment tank (sodium bichromate dihydrate: 3.5 g / L, liquid temperature 28 ° C) and rust-proofing treatment. Subsequently, it was immersed in an aqueous solution of 1% by weight of N-phenylaminopropyltrimethoxysilane, and the surface was treated. Then, it was dried at 80 DEG C for 10 minutes. Thus, a carrier foil with a carrier foil according to Production Example 1 was formed.

(Production Example 2)

A polar foil with a carrier foil was formed in the same manner as in Production Example 1 except for the production conditions of the bulk copper layer.

In this example, the bulk copper layer was formed as follows. First, electrolytic treatment was carried out at a current density of 2.0 A / dm ² for 15 seconds using a plating bath (30 g / L of copper sulfate pentahydrate, 3 g of sodium citrate dihydrate: 40 g / L, liquid temperature 40 캜) A copper layer was formed. Subsequently, a plating bath (copper sulfate pentahydrate: 160 g / L, sulfuric acid: 100 g / L, gelatin (Nippon Company, trade name PBF, weight average molecular weight (MW) 3000: 20 ppm, chloride ion: And subjected to electrolytic treatment at a current density of 3.5 A / dm ² for 150 seconds to form a second bulk copper layer on the first bulk copper layer. As a result, a bulk copper layer was formed.

(Production Example 3)

A polar foil with a carrier foil was formed in the same manner as in Production Example 1 except for the production conditions of the bulk copper layer.

In this example, the bulk copper layer was formed as follows. First, electrolytic treatment was carried out at a current density of 2.0 A / dm ² for 15 seconds using a plating bath (30 g / L of copper sulfate pentahydrate, 3 g of sodium citrate dihydrate: 40 g / L, liquid temperature 40 캜) A copper layer was formed. Thereafter, a plating bath (copper sulfate pentahydrate: 160 g / L, sulfuric acid: 100 g / L, gelatin (Nippon Company, trade name PA-10, weight average molecular weight (MW) 1000: 25 ppm, chloride ion: At a current density of 3.5 A / dm ² for 150 seconds to form a second bulk copper layer on the first bulk copper layer. As a result, a bulk copper layer was formed.

(Production Example 4)

A polar foil with a carrier foil was formed in the same manner as in Production Example 1 except for the production conditions of the bulk copper layer.

In this example, the bulk copper layer was formed as follows. First, electrolysis was carried out at a current density of 2.0 A / dm ² for 15 seconds using a plating bath (30 g / L of copper sulfate pentahydrate, 5 g / L of nickel sulfate hexahydrate, 5 g / L of tri-sodium citrate dihydrate: 40 g / And a first bulk copper layer was formed on the release layer. Then, a plating bath (copper sulfate pentahydrate: 160 g / L, sulfuric acid: 100 g / L, gelatin (Nippon Company, product name: PA-10, weight average molecular weight (MW) 1000: 35 ppm, chloride ion: At a current density of 3.5 A / dm ² for 150 seconds to form a second bulk copper layer on the first bulk copper layer. As a result, a bulk copper layer was formed.

(Production Example 5)

A polar foil with a carrier foil was formed in the same manner as in Production Example 1 except for the production conditions of the bulk copper layer.

In this example, the bulk copper layer was formed as follows. First, electrolysis was carried out at a current density of 2.0 A / dm ² for 15 seconds using a plating bath (30 g / L of copper sulfate pentahydrate, 5 g / L of nickel sulfate hexahydrate, 5 g / L of tri-sodium citrate dihydrate: 40 g / And a first bulk copper layer was formed on the release layer. Subsequently, a plating bath (copper sulfate pentahydrate: 160 g / L, sulfuric acid: 100 g / L, gelatin (Nippon Company, trade name: PBH, weight average molecular weight (MW) 5000: 30 ppm, chloride ion: And subjected to electrolytic treatment at a current density of 3.5 A / dm ² for 150 seconds to form a second bulk copper layer on the first bulk copper layer. As a result, a bulk copper layer was formed.

(Production Example 6)

As a carrier foil (supporting metal layer), a release layer and a thin polar thin foil layer were sequentially formed on the glossy surface of an electrolytic copper foil having a thickness of 18 mu m. The manufacturing conditions are as follows.

First, the carrier foil was immersed in an acid cleaning tank (sulfuric acid: 50 g / L) for 15 seconds to remove oil and oxide films on the surface. Subsequently, the substrate was immersed for 15 seconds in a formation bath of a release layer (carboxybenzotriazole solution: reagent, solution temperature 40 ° C) for 15 seconds to form a release layer on the glossy surface of the carrier foil. Subsequently, a plating bath (copper sulfate pentahydrate: 150 g / L, sulfuric acid: 150 g / L, gelatin (Nippon Company, trade name: PBH, weight average molecular weight (MW) 5000: 15 ppm, chloride ion: And subjected to electrolytic treatment at a current density of 10 A / dm ² for 180 seconds to form a bulk copper layer on the release layer. Then, the plating bath (copper sulfate pentahydrate: 150g / L, sulfuric acid: 100g / L, liquid temperature of 30 ℃) the use to deliver 70 seconds after electrolytic 3 seconds with a current density of 30A / dm ² treated with a current density of 5A / dm ² treatment And a coarse copper layer was formed on the bulk copper layer. Subsequently, electrolytic treatment was carried out for 2.5 seconds at a current density of 0.5 A / dm ² using a rust-inhibiting treatment tank (sodium bichromate dihydrate: 3.5 g / L, liquid temperature 28 ° C) and rust-proofing treatment. Subsequently, it was immersed in an aqueous solution of 1% by weight of N-phenylaminopropyltrimethoxysilane, and the surface was treated. Then, it was dried at 80 DEG C for 10 minutes. Thus, a carrier foil with a carrier foil according to Production Example 6 was formed.

(Production Example 7)

A polar foil with a carrier foil was formed in the same manner as in Production Example 1 except for the production conditions of the bulk copper layer.

In this example, the bulk copper layer was formed as follows. First, electrolytic treatment was carried out at a current density of 2.0 A / dm ² for 15 seconds using a plating bath (30 g / L of copper sulfate pentahydrate, 3 g of sodium citrate dihydrate: 40 g / L, liquid temperature 40 캜) A copper layer was formed. Subsequently, electrolytic treatment was conducted for 150 seconds at a current density of 3.5 A / dm ² using a plating bath (copper sulfate pentahydrate: 160 g / L, sulfuric acid: 100 g / L, chloride ion: A second bulk copper layer was formed. As a result, a bulk copper layer was formed.

(Preparation Example 8)

A polar foil with a carrier foil was formed in the same manner as in Production Example 1 except for the production conditions of the bulk copper layer.

In this example, the bulk copper layer was formed as follows. First, electrolytic treatment was carried out at a current density of 2.0 A / dm ² for 15 seconds using a plating bath (30 g / L of copper sulfate pentahydrate, 3 g of sodium citrate dihydrate: 40 g / L, liquid temperature 40 캜) A copper layer was formed. Subsequently, using a plating bath (copper sulfate pentahydrate: 160 g / L, sulfuric acid: 100 g / L, gelatin (Nippon Company, trade name: PBF, weight average molecular weight (MW) / dm < ^{2 >} for 150 seconds to form a second bulk copper layer on the first bulk copper layer. As a result, a bulk copper layer was formed.

(Preparation Example 9)

A polar foil with a carrier foil was formed in the same manner as in Production Example 1 except for the production conditions of the bulk copper layer.

In this example, the bulk copper layer was formed as follows. First, electrolytic treatment was carried out at a current density of 2.0 A / dm ² for 15 seconds using a plating bath (30 g / L of copper sulfate pentahydrate, 3 g of sodium citrate dihydrate: 40 g / L, liquid temperature 40 캜) A copper layer was formed. Subsequently, using a plating bath (copper sulfate pentahydrate: 160 g / L, sulfuric acid: 100 g / L, gelatin (Nippon Company, trade name AP, weight average molecular weight (MW) 8000): 30 ppm, chloride ion: And subjected to electrolytic treatment at a current density of 3.5 A / dm ² for 150 seconds to form a second bulk copper layer on the first bulk copper layer. As a result, a bulk copper layer was formed.

(Preparation Example 10)

A polar foil with a carrier foil was formed in the same manner as in Production Example 1 except for the production conditions of the bulk copper layer.

In this example, the bulk copper layer was formed as follows. First, electrolytic treatment was carried out at a current density of 2.0 A / dm ² for 15 seconds using a plating bath (30 g / L of copper sulfate pentahydrate, 3 g of sodium citrate dihydrate: 40 g / L, liquid temperature 40 캜) A copper layer was formed. Subsequently, a plating bath (copper sulfate pentahydrate: 160 g / L, sulfuric acid: 100 g / L, gelatin (Nippon Company, trade name PBF, weight average molecular weight (MW) 3000: 5 ppm, chloride ion: And subjected to electrolytic treatment at a current density of 3.5 A / dm ² for 150 seconds to form a second bulk copper layer on the first bulk copper layer. As a result, a bulk copper layer was formed.

2. Manufacture of resin varnish

20 parts by weight of a naphthylene ether type epoxy resin (HP-6000, manufactured by DIC), 5 parts by weight of a naphthalene type epoxy resin (HP4032D, manufactured by DIC Corporation), a cyanate resin (PT- , 7 parts by weight of silica particles (NSS-5N manufactured by TOKUYAMA CORPORATION, average particle size 70 nm), 7 parts by weight of bismaleimide resin (BMI-70 made by KEIKA SEIKO CO., LTD.), 35.5 parts by weight of a silicone oil (SO-25R, average particle diameter 0.5 占 퐉), 7.5 parts by weight of silicone particles (KMP600, average particle diameter 5 占 퐉, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.01 parts by weight of zinc octylate, Ltd., KBM-403E) were dissolved and mixed in methyl ethyl ketone. Then, the mixture was stirred using a high-speed stirrer and adjusted to a non-volatile content of 70% by weight to prepare a resin varnish.

3. Preparation of prepreg

The resin varnish prepared above was impregnated and impregnated with glass woven fabric (Nitoboseki, T glass woven fabric, WTX-1078, flatness of 48 g / m ² , thickness of 45 탆) For 2 minutes to obtain a prepreg having a thickness of 0.05 mm.

4. Manufacture of copper clad laminate

Four sheets of the obtained prepregs were superimposed on each other, and a polar beater with a carrier foil (2 mu m) was superimposed on both sides thereof. The laminate was heated at a pressure of 3 MPa and a temperature of 200 DEG C for 60 minutes (after reaching 200 DEG C, Thereby obtaining a copper clad laminate having copper foils on both sides. In addition, the carrier foil-attached ultra-violet foil used in each of the Examples and Comparative Examples is as shown in Tables 1 and 2.

5. Evaluation

The following evaluations were carried out using the carrier-adhered polar beats obtained in the respective Examples and Comparative Examples. The evaluation items are shown together with the contents, and the obtained results are shown in Tables 1 and 2.

(1) Measurement of Vickers hardness

The Vickers hardness was measured in accordance with JIS Z 2244 in the following procedure at 23 캜 using an acrylic hardness tester (Model No. MVK-2H). As a steady-state sample, a carrier-adhered polarizing foil immediately after forming the bulk copper layer was used. As a sample after the heat treatment, the carrier-adhered polar beats having been formed up to the bulk copper layer were left in an oven (nitrogen atmosphere) heated to 230 占 폚 and used for one hour. The measurement conditions were indentations under the conditions of a loading speed of 3 탆 / second, a test load of 5 gf and a holding time of 15 seconds, and Vickers hardness was calculated from indentation measurement results to determine the average value of arbitrary five points of Vickers hardness As the value of the condition.

(2) Etching rates (V1, V2)

1. A substrate having laminated on both sides thereof a polar beater having the carrier foil removed is cut into a size of 40 mm x 80 mm to obtain a sample piece. The sample piece is read to two decimal places with a vernier caliper to calculate the area of the sample piece.

2. A drying treatment at 80 ° C for 1 minute x 3 times in a horizontal drying line is performed on the sample piece.

3. Measure the initial weight WO of the sample piece (but including the weight of the substrate).

4. Adjust the etchant.

4-1: Weigh 60 g of 95% sulfuric acid (Wako Pure Chemical Industries, Limited) and put in a 1L beaker.

4-2: The pure water is poured into a beaker using 4-1 to make 1000cc.

4-3: Using a magnetic stirrer, stir at 30 ° C ± 1 ° C for 3 minutes.

4-4: 20 cc of 34.5% aqueous hydrogen peroxide (manufactured by Kanto Kagaku Kogyo Co., Ltd.) is weighed and placed in a beaker used at 4-1, the temperature is adjusted to 1020 cc and the mixture is stirred at 30 ° C ± 1 ° C for 3 minutes. Thereby, an etching solution of 55.9 g / L of sulfuric acid and 19.6 cc / L of 34.5% aqueous hydrogen peroxide was obtained.

5. The sample piece is immersed in the above etching solution (liquid temperature 30 ° C ± 1 ° C, stirring conditions: magnetic stirrer, 250rpm).

6. Measure the weight W1 of the sample piece (including the weight of the substrate) every 30 seconds until the bulk layer of the polar beater is completely etched.

7. Plot the etching weight (W0-W1) / (the immersion area on both sides which m = ^2), the etching time (seconds) and the etching weight (g / m ²⁾ in the Y-axis to the X-axis by calculating a. (G / cm ² ) ÷ 8.92 (copper specific gravity g / cm ³ ) × 60 (μm / min) from the slope K1 calculated using the least squares method for 0 to 150 seconds (Seconds / minute).

8. Then, the weight W2 of the sample piece (including the weight of the substrate) is measured every 10 seconds until the coarse copper layer of the polar beater is completely etched.

9. Plot the etching weight (W0-W2) / etching mass (g / m ²⁾ of the etching time (seconds), Y axis in the calculation (in which both sides of the immersion area = m ^2), and the X-axis. (G / cm ² ) ÷ 8.92 (copper specific gravity g / cm ³ ) × 60 (μm / min) from the slope K2 calculated using the least squares method for 0 to 30 seconds (Seconds / minute).

(3) Evaluation method of unevenness

Copper residue between wiring lines was binarized (image processing software; Image Pro Prus ver. 5 (manufactured by Media Cybernetics Inc.)) using an SEM image (2000 times) obtained by observing the printed wiring board obtained in (4) 1) to calculate the residual copper degree.

The symbols in Table 1 and Table 2 are as follows.

A: not more than 2

A: greater than 2 and less than 10

X: 10 or more

(4) insulation between thin wires

1. The surface of the substrate on which the carrier foil was removed and laminated on both surfaces thereof was soft-etched with a chemical polishing liquid (manufactured by Mitsubishi Gas Chemical Company, trade name: CPB-60) for 5 seconds at 23 占 폚, . Subsequently, an ultraviolet photosensitive dry film (Sun Port UFG-255, manufactured by Asahi Kasei Corporation) having a thickness of 25 mu m was bonded onto the substrate with a hot-roll laminator. Subsequently, a glass mask (topic article) in which a pattern with a minimum line width / line-to-line spacing of 20/20 占 퐉 was drawn was aligned. Subsequently, the dry film was exposed to light using an exposure apparatus (Ono measuring instrument EV-0800) using the glass mask and developed with a sodium carbonate aqueous solution. Thereby, a resist mask was formed.

2. Next, a copper wiring pattern having a thickness of about 20 탆 was formed by performing electrolytic copper plating (81-HL, made by Okuno Seiyaku Co., Ltd.) at 3A / dm ² for 25 minutes using a thin layer of ultrasonic vibration as a feed layer electrode. Subsequently, the resist mask was peeled off with a monoethanolamine solution (R-100 manufactured by Mitsubishi Gas Chemical Company) using a peeling machine.

3. The ultrathin thin layer as the feed layer was removed by flash etching (liquid having the same etching rate) to form a pattern of L / S = 20/20 占 퐉 (pattern etching). Thus, a printed wiring board was obtained.

4. An insulating resin sheet (BLA-3700GS made by Sumitomo Bakery Co., Ltd.) was laminated as a test sample in place of the solder resist, and the sample was cured at a temperature of 220 캜 under conditions of a temperature of 130 캜, a humidity of 85% Were evaluated for continuous wet insulation resistance. Also, the resistance value was 10 ⁶ Ω or less.

The codes are as follows.

◎: No breakdown for 300 hours

○: Failure in less than 150-300 hours

X: Failure in less than 150 hours

(5) Wiring shape (or circuit linearity)

1. The sample was the printed wiring board obtained in (4) above.

2. Using a microscope, the outline of the circuit base was observed when the circuit after etching was observed directly above. Further, the wiring shape when the cross section of the circuit after etching was observed using a microscope was evaluated.

The codes are as follows.

A: The outline of the circuit base portion is seen as a straight line when observing from above. In addition, there is no widening of the base end in the cross section.

O: When observing directly above, the contour of the circuit base portion appears as a straight line. Also, the base end is small in cross-section.

X: There is a portion where the contour of the circuit base portion appears as a curved line when observed directly above. In addition, the base end is larger in cross-section.

(6) grain boundary grain diameter (占 퐉)

The grain boundary diameter was measured according to JIS H 0501. The order is as follows.

1. A substrate on which polar thin foils having carrier foils removed are laminated on both sides is processed by using an FIB (convergent ion beam) processing apparatus, and then a SIM (Scanning Ion Microscope) observation photograph is taken.

2. Calculate the grain size of the cross section of the photographed picture from the standard photograph of the comparative method specified in JIS H 0501. In addition, in the annex of this standard, the grain size observed at 75 times is only 0.010 mm, so the most similar figure and the magnification at the time of observation are taken into account.

Needless to say, the above-described embodiment and a plurality of modified examples can be combined within a range in which the content is not contradictory. While the structure and the like of each part have been specifically described in the above-described embodiments and modifications, the structure and the like can be changed into various types within the scope of satisfying the present invention.

This application claims priority based on Japanese Patent Application No. 2012-059742, filed on March 16, 2012, the entire disclosure of which is incorporated herein by reference.

Claims (6)

A laminated board for use in an element mounting board obtained by forming a conductor circuit by etching an insulating layer and a copper foil located on at least one side of the insulating layer,
The etching rate of the copper foil under the condition of immersing the laminate in an etching solution of sulfuric acid / hydrogen peroxide system consisting of 55.9 g / L of sulfuric acid and 19.6 cc / L of 34.5% hydrogen peroxide and having a liquid temperature of 30 ° C ± 1 ° C Of 0.68 탆 / min or more and 1.25 탆 / min or less. The method according to claim 1,
The difference in Vickers hardness of the copper foil before and after the heat treatment under the following conditions is 0Hv to 50Hv.
Condition: The heating temperature was 230 占 폚 and the heating time was 1 hour. The method according to claim 1,
Wherein the thickness of the copper foil is 0.1 占 퐉 or more and 5 占 퐉 or less. The method according to claim 1,
Wherein the Vickers hardness of the copper foil after the heat treatment at 230 占 폚 for 1 hour is 180 Hv or more and 240 Hv or less. The method according to claim 1,
And a cross-sectional grain size of the copper foil after the heat treatment at 230 占 폚 for 1 hour is 2.0 占 퐉 or less. A step of preparing a laminate including an insulating layer and a copper foil located on at least one side of the insulating layer;
And forming a conductor circuit by selectively removing the copper foil,
Wherein the laminated board is the laminated board according to any one of claims 1 to 5.

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