WO2009144954A1 - Composition de résine thermodurcie et carte de câblage imprimé - Google Patents

Composition de résine thermodurcie et carte de câblage imprimé Download PDF

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Publication number
WO2009144954A1
WO2009144954A1 PCT/JP2009/002385 JP2009002385W WO2009144954A1 WO 2009144954 A1 WO2009144954 A1 WO 2009144954A1 JP 2009002385 W JP2009002385 W JP 2009002385W WO 2009144954 A1 WO2009144954 A1 WO 2009144954A1
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Prior art keywords
resin
epoxy
filler
epoxy resin
plating
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PCT/JP2009/002385
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English (en)
Japanese (ja)
Inventor
林亮
中居弘進
邑田勝人
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太陽インキ製造株式会社
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Publication of WO2009144954A1 publication Critical patent/WO2009144954A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating

Definitions

  • the present invention relates to a thermosetting resin composition suitable for forming a resin insulating layer excellent in adhesion (peel strength) to a conductor layer by ultraviolet treatment, a resin sheet comprising the thermosetting resin composition, and
  • the present invention relates to a printed wiring board in which a resin insulating layer is formed using these.
  • the adhesion between the conductor layer formed by plating and the resin insulating layer must satisfy the impact resistance test of the conductor circuit pattern and the mounted component. . Therefore, after the surface of the resin insulating layer is roughened (desmeared), plating is performed.
  • the roughening treatment is performed by etching the surface of the resin insulating layer using an oxidizing agent such as sodium permanganate or potassium permanganate.
  • High adhesion is obtained by an anchor effect due to the conductor layer entering into the recesses on the surface of the resin insulating layer formed into irregularities by the roughening treatment.
  • the etching solution easily enters the side surface of the conductor circuit pattern, thereby affecting the pattern accuracy and extremely fine.
  • the conductor circuit pattern cannot be formed with high accuracy.
  • Another problem is that the high-frequency signal transmission loss increases in the electrical characteristics of the wiring board due to the deterioration of the shape of the pattern side surface.
  • a method of performing a plating process after a pretreatment by ultraviolet irradiation is disclosed (for example, see Patent Documents 4 and 5).
  • a polar group such as a carboxyl group (—COOH), a carbonyl group (C ⁇ O), or an OH group is introduced to the resin surface by irradiating the resin insulating layer surface with ultraviolet rays before the electroless plating process.
  • the surface energy can be increased to activate the resin surface, whereby the polar groups on the activated resin surface are chemically bonded to the active metal particles that are the direct plating material, The adhesiveness with the metal film formed on the resin surface is strengthened.
  • Patent Document 6 a method for improving the adhesion between the conductor layer and the resin insulation layer by performing both plasma treatment and ultraviolet treatment on the resin insulation layer has been proposed (see Patent Document 6).
  • the ultraviolet wavelength used is 172 nm, it is easily absorbed by oxygen, nitrogen, etc., and it is necessary to perform treatment at a short distance from the irradiation lamp. For this reason, it becomes difficult to uniformly perform the processing without any unevenness on the processing surface.
  • JP-A-7-304931 (Claims) JP-A-7-304933 (Claims) JP-A-11-87927 (Claims) JP-A-8-253869 (Claims) JP-A-10-88361 (Claims) JP 2002-57456 A (Claims)
  • the present invention mainly solves the problems of the prior art described above in the production of a build-up type printed wiring board in which a resin insulation layer and a conductor layer are alternately stacked on a conductor layer of an inner layer circuit board.
  • the purpose of this is to form a conductor layer on the surface of the resin insulation layer by plating, and to perform resin pre-treatment by ultraviolet irradiation without using a conventional harmful oxidant.
  • thermosetting resin composition capable of suppressing the surface roughness of the layer to be extremely small, and improving adhesion between the resin insulating layer and the conductor layer, thereby enabling formation of an extremely fine conductor circuit pattern;
  • An object of the present invention is to provide a resin sheet made of the thermosetting resin composition, and a printed wiring board having excellent electrical characteristics in which a resin insulating layer is formed using these.
  • the resin insulating layer is used to form the resin insulating layer.
  • a thermosetting resin composition comprising a phenol resin, a filler, and a polyhydroxycarboxylic acid or a derivative thereof is provided.
  • the filler is preferably at least one of calcium carbonate and silica. Further, the blending amount of the filler is preferably 10 to 150 parts by mass with respect to 100 parts by mass of the total of the epoxy resin and the phenol resin. Furthermore, according to this invention, the said thermosetting resin composition was coated on the carrier film, and then the resin sheet formed by drying, or the sheet-like fibrous base material was impregnated with the thermosetting resin composition. Thereafter, a dried resin sheet is also provided.
  • the surface of the resin insulation layer formed from the cured product or resin sheet of the thermosetting resin composition is irradiated with ultraviolet rays, and then a conductor layer is formed by plating.
  • a printed wiring board characterized by the above is provided.
  • the plating treatment includes electroless plating and electrolytic plating.
  • thermosetting resin composition of the present invention comprises a bifunctional epoxy resin not containing a naphthalene skeleton and an epoxy resin not containing a naphthalene skeleton having an epoxy equivalent of 250 g / eq or more having 3 or more epoxy groups in one molecule. Since it contains a combination of at least one of a phenol resin, a filler, and a polyhydroxycarboxylic acid or a derivative thereof, the surface of the resin insulating layer formed from the composition is irradiated with ultraviolet rays, and then subjected to plating treatment to conduct a conductor.
  • thermosetting resin composition of the present invention and the resin sheet (dry film or prepreg) in a build-up system in which conductor circuit layers and insulating layers are alternately stacked, the adhesion strength of the plated conductor layer is high.
  • a multilayer printed wiring board on which an interlayer insulating layer excellent in heat resistance, electrical insulation and the like is formed can be produced.
  • a resin insulation layer formed from a thermosetting resin composition containing a combination of at least one epoxy resin not containing a skeleton and a phenol resin, a filler, and a polyhydroxycarboxylic acid or a derivative thereof has ultraviolet rays on its surface.
  • the adhesion strength of the conductor layer is remarkably increased despite the fact that it has excellent wettability with the plating solution and is a relatively flat surface.
  • the present inventors have found that it is optimal as an interlayer insulating layer of a plate and have completed the present invention.
  • the effect of irradiating the surface of the resin insulation layer with ultraviolet rays (polar groups such as carboxyl groups (—COOH), carbonyl groups (C ⁇ O), OH groups, etc. are introduced on the resin surface), and the surface energy increases.
  • the resin surface can be activated, whereby the polar group on the activated resin surface forms a chemical bond directly with the active metal particles that are the plating material, and the metal film formed on the resin surface
  • the polar groups of these compounds are likely to be present on the surface of the resin insulation layer. Excellent wettability with plating solution, improved penetration and adsorption of plating solution with respect to cured film, and extremely high adhesion strength of conductor layer despite its relatively flat surface. It made.
  • polyhydroxycarboxylic acid or a derivative thereof promotes the penetration of a plating solution, particularly a catalyst solution, due to the presence of its functional group (hydroxyl group, carboxyl group, amide group, ester group, etc.), and also has the effect of the above ultraviolet irradiation.
  • the naphthalene skeleton needs to contain no naphthalene skeleton because the naphthalene skeleton is likely to inhibit the penetration of the plating solution into the cured film. Moreover, even if it does not contain a naphthalene skeleton, in the case of a trifunctional or higher polyfunctional epoxy resin having an epoxy equivalent of 250 g / eq or less, the crosslink density becomes too high and the penetration of the plating catalyst is hindered. Since it is easy to deteriorate, it is not preferable.
  • the crosslink density is relatively high during thermosetting compared to the case of using dicyandiamide, which is conventionally used, and the glass transition point Tg is compared. Therefore, a cured product having high water absorption and excellent toughness can be obtained.
  • the inside of the insulating layer with improved durability against thermal stress and the surface of the insulating layer with good catalyst liquid permeability during plating, it is formed as a highly reliable multilayer printed wiring board. This can greatly contribute to the coexistence of fine circuit formation of the conductor layer.
  • the epoxy resin includes an epoxy resin having two epoxy groups in one molecule and an epoxy resin having three or more epoxy groups in one molecule and having an epoxy equivalent of 250 g / eq or more.
  • Any epoxy compound that is selected from the above and does not contain a naphthalene skeleton can be used.
  • the bifunctional epoxy resin include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, Biphenol type epoxy resins and the like are listed.
  • Examples of the tri- or higher functional epoxy resins include phenol novolac type epoxy resins, alkylphenol novolac type epoxy resins, bisphenol A novolac type epoxy resins, dicyclopentadiene type epoxy resins, glycidyl amine type epoxy resins, Trihydroxyphenylmethane type epoxy resin, tetraphenylol ethane type epoxy resin, diglycidyl phthalate resin, aromatic alcohols having phenols and phenolic hydroxyl groups Examples include epoxidized products of condensates with hydrides, bromine atom-containing epoxy resins and phosphorus atom-containing epoxy resins, triglycidyl isocyanurate and other epoxy resins, alicyclic epoxy resins, and the like. These can be used alone or in combination of two or more. Moreover, you may contain the monofunctional epoxy resin as a reactive diluent.
  • the epoxy resin as described above may be used alone, but it is preferable to use a combination of two or more.
  • a liquid epoxy resin and a solid epoxy resin are used in combination at room temperature, a low molecular weight
  • the liquid epoxy resin contributes to improving the flexibility and adhesion of the resulting cured film
  • the solid epoxy resin contributes to raising the glass transition point. By adjusting these ratios, the above characteristics can be obtained. It is possible to adjust the balance.
  • Epoxy resins having an epoxy equivalent of more than 200 g / eq have little cure shrinkage and are effective in preventing warpage of the substrate and imparting flexibility to the cured product.
  • the melt viscosity at the time of heating lamination and leveling can be increased, which is effective in controlling the amount of resin oozing after molding.
  • an epoxy resin having an epoxy equivalent of 200 g / eq or less has high reactivity and gives mechanical strength to the cured product.
  • the melt viscosity at the time of heat lamination is low, it contributes to the filling property of the resin composition into the gaps between the inner layer circuits and the followability to the rough surface of the copper foil.
  • a phenol resin is used as an epoxy resin curing agent used as an essential component together with the epoxy resin.
  • the phenol resin include a phenol novolak resin, an alkylphenol novolak resin, a triazine structure-containing phenol novolak resin, a bisphenol A novolak resin, a dicyclopentadiene structure-containing phenol resin, a xylok type phenol resin, a terpene-modified phenol resin, and polyvinyl.
  • examples include phenols, naphthalene structure-containing phenolic curing agents, and fluorene structure-containing phenolic curing agents. These can be used alone or in combination of two or more.
  • a suitable proportion of the phenol resin is such that the phenolic hydroxyl group of the phenol resin is 0.2 to 1.2 equivalent, preferably 0.3 to 0.9 equivalent per equivalent of epoxy group of the epoxy resin. .
  • the amount is less than 0.2 equivalent, the properties of the obtained cured product are inferior, and sufficient adhesion to the substrate cannot be obtained.
  • it exceeds 1.2 equivalents the proportion of the phenol resin remaining without participating in the reaction with the epoxy resin is increased, and this tends to lead to a decrease in physical properties of the cured film, which is not preferable.
  • a curing accelerator can be used as necessary.
  • the curing accelerator include triethylamine, tributylamine, dimethylbenzylamine, diethylbenzylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4 Tertiary amines such as methyl-N, N-dimethylbenzylamine, quaternary ammonium salts such as benzyltrimethylammonium chloride and benzyltriethylammonium chloride, phosphines such as triethylphosphine and triphenylphosphine, n-butyltriphenylphosphonium Phosphonium salts such as bromide, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimi
  • inorganic fillers include barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, and aluminum nitride.
  • extender pigments such as copper, tin, zinc, nickel, silver, palladium, aluminum, iron, cobalt, gold and platinum.
  • These inorganic fillers also suppress the curing shrinkage of the coating film and contribute to improving properties such as adhesion and hardness.
  • calcium carbonate and silica, particularly calcium carbonate are preferable.
  • These fillers are preferably spherical fillers from the viewpoint that they can be blended in a high proportion in the composition, and the average particle diameter is preferably 0.1 ⁇ m to 3 ⁇ m.
  • the blending amount of the filler is 10 to 150 parts by mass, preferably 20 to 150 parts by mass, with respect to 100 parts by mass of the total of the epoxy resin and the phenol resin.
  • the blending amount of the filler is less than the above range, it becomes difficult to obtain good adhesion strength with the conductor circuit layer.
  • it exceeds the above range the fluidity of the composition is deteriorated, and the strength of the cured film is low. It is not preferable because it tends to decrease.
  • polyhydroxycarboxylic acid or its derivative is not limited to a specific compound, but an amide or ester of polyhydroxycarboxylic acid can be suitably used.
  • examples of commercially available products include BYK-405 (polyhydroxycarboxylic acid amide), BYK-LPR6795 (polyhydroxycarboxylic acid ester) manufactured by Big Chemie Japan.
  • the blending amount of the polyhydroxycarboxylic acid or derivative thereof is suitably from 0.1 to 15 parts by weight, preferably from 0.3 to 10 parts by weight, based on 100 parts by weight of the total of the epoxy resin and the phenol resin. .
  • the blending amount of the polyhydroxycarboxylic acid or its derivative is less than the above range, it becomes difficult to obtain good adhesion strength with the conductor circuit layer.
  • the conductor circuit layer Further improvement of the adhesion strength with the resin cannot be expected, which is not preferable in terms of economy.
  • the softening point of a cured film falls and heat resistance etc. become easy to fall, it is unpreferable.
  • thermosetting resin composition of the present invention can contain an organic solvent in order to dissolve the solid resin or adjust the viscosity of the composition, if necessary.
  • Organic solvents include ordinary solvents such as ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and cellosolves such as cellosolve and butylcellosolve.
  • Carbitols such as carbitol and butyl carbitol
  • aromatic hydrocarbons such as toluene and xylene
  • dimethylformamide dimethylacetamide and the like
  • thermosetting resin composition of the present invention may further include a known and commonly used colorant such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc. , Known and commonly used thickeners such as asbestos, olben, benton, fine silica, etc., defoamers and / or leveling agents such as silicones, fluorines and polymers, thiazoles, triazoles, silane coupling agents, etc. Adhesiveness imparting agents, titanate-based, and aluminum-based commonly used additives can be used.
  • a known and commonly used colorant such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc.
  • Known and commonly used thickeners such as asbestos, olben, benton, fine silica, etc., defoamers and
  • thermosetting resin composition of the present invention may be provided as a coating material whose viscosity is appropriately adjusted, or the thermosetting resin composition is applied onto a carrier film (support base film), and a solvent is used. It is good also as a dried resin sheet (dry film). Furthermore, it is good also as a resin sheet (prepreg sheet
  • the carrier film include polyolefin such as polyethylene and polyvinyl chloride, polyester such as polyethylene terephthalate, polycarbonate and polyimide, and metal foil such as release paper, copper foil, and aluminum foil.
  • the carrier film may be subjected to a mold release treatment in addition to the mud treatment and the corona treatment.
  • the coating material, dry film, or prepreg using the thermosetting resin composition is directly coated on the inner circuit board on which the circuit is formed and dried or cured, or the dry film is laminated by heating to be integrally formed. Then, it may be cured in an oven or cured by a hot plate press. In the case of a prepreg, it is placed on an inner circuit board, sandwiched between metal plates through a release film, and pressed by pressing and heating.
  • the method of laminating or hot plate pressing is preferable because unevenness due to the inner layer circuit is eliminated when heated and melted and is cured as it is, so that a multilayer plate having a flat surface state is finally obtained. Further, when laminating or hot plate pressing the base material on which the inner layer circuit is formed and the dry film or prepreg of the thermosetting resin composition of the present invention, the copper foil or the base material on which the circuit is formed may be laminated at the same time. it can.
  • Holes are made in the substrate thus obtained with a semiconductor laser such as a CO 2 laser or a UV-YAG laser or a drill.
  • the hole is a through hole (through hole) that is intended to connect the front and back of the substrate, but it is also a partial hole (conformal via) that is intended to connect the inner layer circuit and the circuit on the surface of the interlayer insulating layer. either will do.
  • the surface of the resin insulation layer is preferably irradiated with ultraviolet light having an irradiation intensity of at least 10 mW / cm 2 .
  • the dominant wavelength of the ultraviolet light is 150 nm to 310 nm or less, preferably 150 to 260 nm or less, and more preferably about 150 to 200 nm.
  • the wavelength of ultraviolet rays is composed of two types of about 184 nm and about 254 nm.
  • a low-pressure mercury lamp excimer laser, barrier discharge lamp, dielectric barrier discharge lamp, microwave electrodeless discharge lamp, transient discharge lamp, or the like can be used.
  • a low-pressure mercury lamp excimer laser, barrier discharge lamp, dielectric barrier discharge lamp, microwave electrodeless discharge lamp, transient discharge lamp, or the like
  • a dominant wavelength of 184.9 nm and 253.7 nm is particularly effective.
  • Ar2 * (126 nm), Kr2 * (146 nm), F2 * (153 nm), ArBr * (165 nm), Xe2 * (172 nm), ArCl * (175 nm), ArF (193 nm), KrBr * (207 nm), KrCl * (222 nm), KrF (248 nm), Xel * (253 nm), Cl2 * (259 nm), XeBr * (283 nm), Br2 * (289 nm), XeCl * (308 nm) ) Is preferred.
  • Xe2 * and KrCl * are preferable because they are stable and have a relatively small wavelength and large energy, so that the surface modification effect is large.
  • the irradiation time of the ultraviolet light varies depending on the resin material used and the intensity (irradiation amount) of the ultraviolet light, but in the range of about 10 seconds to 30 minutes (when the intensity of the ultraviolet light is about 5 to 20 mW / cm 2 ). Can be adjusted as appropriate, and is preferably about 20 seconds to 10 minutes.
  • the irradiation with ultraviolet light may be performed a plurality of times before the conductor layer is formed by electroless plating.
  • a circuit is formed on the surface of the film treated with ultraviolet rays by a subtractive method or a semi-additive method.
  • a heat treatment called annealing at about 80 to 180 ° C. for about 10 to 60 minutes for the purpose of removing stress from the metal and improving the strength. May be applied.
  • the metal plating used here is not particularly limited, such as copper, tin, solder, nickel, etc., and can be used in combination.
  • Electroless copper plating is for forming a power supply layer for performing electrolytic copper plating, and is usually formed to a thickness of about 0.1 to 2.0 ⁇ m.
  • copper plating has the difficulty that adhesiveness with resin is low compared with nickel plating etc., when performing copper plating on the surface of the resin insulation layer formed according to the present invention, and forming a conductor layer Excellent adhesion strength can be obtained by the above-described action.
  • the electroless plating and electrolytic plating performed on the surface of the resin insulating layer may be any known method, and is not limited to a specific method, but the catalyst in the electroless plating treatment step is a palladium-tin mixed catalyst, The primary particle size of the catalyst is preferably 10 nm or less. Moreover, it is preferable that the plating composition of the electroless plating treatment step contains hypophosphorous acid as a reducing agent.
  • the electroless plating is described in, for example, the above-mentioned Patent Documents 4 and 6 and Japanese Patent Application Laid-Open No. 2000-212762.
  • a desired multilayer printed wiring board can be obtained by repeating the formation of the resin insulating layer and the conductor circuit layer several times as necessary as described above.
  • thermosetting resin composition was obtained, respectively.
  • Test board production process Each thermosetting resin composition obtained as described above was applied to a 1.6 mm thick FR-T substrate (etch-out substrate, pretreatment: buffing) with an applicator.
  • UV treatment process The test substrate obtained as described above was subjected to ultraviolet treatment under the following conditions using an ultraviolet cleaning reformer (manufactured by Sen Engineering Co., Ltd., power source: UVE-200J, light source: PL16-110D).
  • Electroless copper plating and electrolytic copper plating process The test substrate treated with ultraviolet rays as described above is subjected to electroless copper plating for 30 minutes under the following conditions to obtain an electroless copper plating film having a thickness of about 0.3 ⁇ m, and then electrolysis is performed on the electroless copper plating. Copper plating was performed until the thickness was about 20 ⁇ m.
  • Pretreatment process After degreasing the test substrate, the CLEANER-CONDITIONER 231 (100 ml / l) manufactured by Rohm and Haas was used to perform the cleaner / conditioner process at 60 ° C. for 5 minutes, followed by a water washing process at 25 ° C. for 1 minute and hydrochloric acid (50 ml / liter). l) Pre-dip process at 25 ° C.
  • Electroless copper plating bath composition copper sulfate (hexahydrate) 8 g / l, sodium citrate (dihydrate) 14 g / l, sodium hypophosphite (monohydrate) 57 g / l, boric acid 31 g / l, ⁇ bath conditions> bath temperature 60 ° C., pH 8.0 to 11.0.
  • Current density of electrolytic copper plating 1 A / dm 2 .
  • the test substrate plated as described above was measured for adhesion (peel strength) between the conductor layer and the resin insulating layer.
  • the peel strength was measured by using AGS-G 100N manufactured by Shimadzu Corporation as a peel strength measuring device under the condition of a peel speed of 50 mm / min according to JIS C 6481 and evaluated according to the following criteria. In addition, the measurement was performed twice and the average value thereof was used. The results are also shown in Table 1. Evaluation criteria: A: Peel strength is 3 N / cm or more. ⁇ : Peel strength is 2 N / cm or more and less than 3 N / cm. X: Peel strength is less than 2 N / cm.
  • Example 7 As shown in Table 2 below, the main component and the curing agent are mixed together in various formulations with different filler contents, kneaded and dispersed with a three-roll mill, and about 30 dPa ⁇ The viscosity was adjusted to s (rotary viscometer, 25 ° C.) to obtain thermosetting resin compositions. Next, test substrates were prepared in the same manner as in Examples 1 to 6, and the adhesion (peel strength) between the conductor layer and the resin insulating layer was measured in the same manner. The results are also shown in Table 2.
  • Example No. containing a filler was used.
  • the peel strength was high and the adhesiveness between the conductor layer and the resin insulating layer was excellent.
  • the peel strength was low and the adhesion was poor. From this, it can be seen that the inclusion of the filler is essential in order to improve the adhesion between the conductor layer and the resin insulating layer.
  • Example 8 As shown in Table 3 below, the components of the main agent and the curing agent are mixed together in various formulations with different contents of the polyhydroxycarboxylic acid derivative, kneaded and dispersed in a three-roll mill, and added to the solvent (cyclohexanone). The viscosity was adjusted to about 30 dPa ⁇ s (rotary viscometer, 25 ° C.) to obtain a thermosetting resin composition. Next, test substrates were prepared in the same manner as in Examples 1 to 6, and the adhesion (peel strength) between the conductor layer and the resin insulating layer was measured in the same manner. The results are also shown in Table 3.
  • Example No. 1 containing a polyhydroxycarboxylic acid derivative was used.
  • the peel strength was high and the adhesiveness between the conductor layer and the resin insulating layer was excellent, but no polyhydroxycarboxylic acid derivative was contained.
  • the peel strength was low and the adhesion was poor. From this, it can be seen that the inclusion of the polyhydroxycarboxylic acid derivative is essential in order to improve the adhesion between the conductor layer and the resin insulating layer.
  • Examples 9 to 11 and Comparative Examples 1 to 3 As shown in Table 4 below, the components of the main agent and the curing agent were mixed together in various formulations with different types of epoxy resin, kneaded and dispersed with a three roll mill, and about 30 dPa ⁇ The viscosity was adjusted to s (rotary viscometer, 25 ° C.) to obtain thermosetting resin compositions. Next, test substrates were prepared in the same manner as in Examples 1 to 6, and the adhesion (peel strength) between the conductor layer and the resin insulating layer was measured in the same manner. The results are also shown in Table 4.
  • thermosetting resin composition that enables the formation of a conductor layer having high adhesion strength with the resin insulating layer
  • thermosetting The resin sheet which consists of a resin composition, and the printed wiring board by which a resin insulating layer is formed using these can be provided.

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  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Epoxy Resins (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur une composition de résine thermodurcie qui peut former une couche conductrice présentant une force d'adhésion élevée avec une couche d'isolation en résine lorsqu'une couche conductrice est formée sur la surface d'une couche d'isolation en résine par un procédé de placage, sur une feuille de résine composée de la composition de résine thermodurcie et sur une carte de câblage imprimé qui forme une couche d'isolation en résine à l'aide de la composition et de la feuille. Dans la fabrication d'une carte de câblage imprimé qui forme une couche conductrice par un procédé de placage après que de la lumière ultraviolette a irradié la surface d'une couche d'isolation en résine, la composition de résine thermodurcie utilisée pour former la couche d'isolation en résine comprend au moins une résine parmi l'une ou l'autre d'une résine époxyde bifonctionnelle ne comprenant pas un squelette de naphtalène ou d'une résine époxyde ne comprenant pas un squelette de naphtalène qui a un équivalent d'époxy supérieur à 250 g/éq. avec trois ou plus de trois bases époxy dans une molécule et comprend une résine phénolique, une charge et un acide polyhydroxycarboxylique ou un dérivé de celui-ci.
PCT/JP2009/002385 2008-05-29 2009-05-29 Composition de résine thermodurcie et carte de câblage imprimé WO2009144954A1 (fr)

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JP5630241B2 (ja) * 2010-02-15 2014-11-26 日立化成株式会社 絶縁樹脂、配線板及び配線板の製造方法
JP5797883B2 (ja) * 2010-06-07 2015-10-21 住友電気工業株式会社 プリント配線板用基板
KR101807901B1 (ko) * 2010-08-10 2017-12-11 히타치가세이가부시끼가이샤 수지 조성물, 수지 경화물, 배선판 및 배선판의 제조 방법
KR101116181B1 (ko) * 2010-09-29 2012-03-06 주식회사 두산 성형성이 우수한 에폭시수지를 포함한 적층체 및 그 제조방법
TW201307470A (zh) * 2011-05-27 2013-02-16 Taiyo Ink Mfg Co Ltd 熱硬化性樹脂組成物、乾燥膜及印刷配線板
JP5983141B2 (ja) * 2012-07-24 2016-08-31 東レ株式会社 積層フィルム

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JP2003096368A (ja) * 2001-09-26 2003-04-03 Tamura Kaken Co Ltd レジストインキ組成物及びプリント配線板
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JP2001181375A (ja) * 1999-10-13 2001-07-03 Ajinomoto Co Inc エポキシ樹脂組成物並びに該組成物を用いた接着フィルム及びプリプレグ、及びこれらを用いた多層プリント配線板及びその製造法
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JP2003096368A (ja) * 2001-09-26 2003-04-03 Tamura Kaken Co Ltd レジストインキ組成物及びプリント配線板
JP2005048117A (ja) * 2003-07-31 2005-02-24 Taiyo Ink Mfg Ltd 硬化性組成物
JP2005241977A (ja) * 2004-02-26 2005-09-08 Taiyo Ink Mfg Ltd 光硬化性・熱硬化性樹脂組成物及びそれを用いたプリント配線板
JP2008133426A (ja) * 2006-10-26 2008-06-12 Hitachi Chem Co Ltd インク、液晶表示装置用スペーサの形成方法及び液晶表示装置
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KR20110033114A (ko) 2011-03-30

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