WO2014014043A1 - 補強板一体型フレキシブルプリント基板 - Google Patents
補強板一体型フレキシブルプリント基板 Download PDFInfo
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- WO2014014043A1 WO2014014043A1 PCT/JP2013/069478 JP2013069478W WO2014014043A1 WO 2014014043 A1 WO2014014043 A1 WO 2014014043A1 JP 2013069478 W JP2013069478 W JP 2013069478W WO 2014014043 A1 WO2014014043 A1 WO 2014014043A1
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- reinforcing plate
- insulating film
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- 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
- H05K1/0277—Bendability or stretchability details
- H05K1/028—Bending or folding regions of flexible printed circuits
- H05K1/0281—Reinforcement details thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- 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
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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- 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
- H05K1/0274—Optical details, e.g. printed circuits comprising integral optical means
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- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/012—Flame-retardant; Preventing of inflammation
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- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/20—Details of printed circuits not provided for in H05K2201/01 - H05K2201/10
- H05K2201/2054—Light-reflecting surface, e.g. conductors, substrates, coatings, dielectrics
Definitions
- the present invention relates to a reinforcing plate-integrated flexible printed circuit board, and more particularly to a reinforcing plate-integrated flexible printed circuit board that has excellent electrical insulation reliability and does not peel off from the reinforcing plate during reflow mounting. is there.
- the flexible printed circuit board has a thickness of several tens to several hundreds of micrometers and is a highly flexible wiring board. It is necessary to reinforce to ensure a sufficient strength. For this reason, usually, a reinforcing plate is bonded and fixed to the back surface of the component mounting area of the flexible printed circuit board through a thermosetting adhesive so as to partially improve the strength (for example, Patent Documents). See 1-3.)
- the insulating film of the surface protective material for the flexible printed circuit board is colored black, and the insulating film is concealed, thereby concealing the circuit pattern and including the confidentiality contained in the circuit pattern. Attempts have been made to protect information (see, for example, Patent Documents 4 and 5).
- JP 2010-114185 A Japanese Published Patent Publication “JP 2010-6922 A” Japanese Published Patent Publication “JP 2011-61070 A” Japanese Patent Publication “Japanese Patent Laid-Open No. 2008-257045” Japanese Patent Publication “JP 2002-294131 A”
- Patent Document 1 focuses on a reinforcing plate having sufficient heat resistance (solder heat resistance) and provides a reinforcing plate that can be suitably used for a circuit connection portion or a mounting portion of a flexible printed circuit board.
- Patent Document 2 focuses on a thermosetting adhesive and provides an adhesive composition and an adhesive sheet having excellent storage stability, adhesiveness, solder heat resistance, and processability.
- the reinforcing plate and the thermosetting adhesive are elements constituting the reinforcing plate-integrated flexible printed board, even if only the individual characteristics of the reinforcing plate and the thermosetting adhesive are improved, The desired properties cannot be satisfied. For example, unless the adhesion between the flexible printed circuit board and the thermosetting adhesive is improved, the reinforcing plate integrated flexible printed circuit board does not exhibit good characteristics.
- Patent Document 3 focuses on the cover film layer, which is the outermost layer of the flexible printed circuit board, and increases the bonding area of the adhesive that bonds the flexible printed circuit board and the reinforcing plate by providing a groove in the cover film layer.
- a flexible printed wiring board with improved adhesive strength is provided.
- sand blasting, embossing, plasma treatment, and the like have been proposed as methods for providing a groove in the cover film layer, which may further increase manufacturing costs.
- the present inventors have focused on the insulating film, which is the outermost layer of the flexible printed circuit board, and have conducted intensive research on the flexible printed circuit board integrated with a reinforcing plate.
- Patent Document 4 and Patent Document 5 are all black and aim to obtain a photo-curing and high-resolution insulating film, so that the adhesion between the black insulating film and the reinforcing plate is improved. It is not an invention intended to be made. Therefore, according to Patent Document 4 and Patent Document 5, when a reinforcing plate is pasted on the black insulating film, in a reflow mounting process for mounting components on the flexible printed circuit board after pasting the reinforcing plate, There arises a problem that the reinforcing plate is peeled off from the black insulating film (hereinafter, this problem is referred to as reflow heat resistance).
- the present inventors are composed of (A) a reinforcing plate, (B) a thermosetting adhesive, (C) an insulating film, and (D) a film with a wiring pattern.
- the flexible printed circuit board integrated with a reinforcing plate has excellent electrical insulation reliability and does not peel off from the reinforcing plate during reflow mounting.
- the present invention has been achieved based on such findings.
- the present invention can solve the above problems by the following reinforcing plate-integrated flexible printed circuit board.
- the present invention is a flexible printed board integrated with a reinforcing plate configured in the order of (A) a reinforcing plate, (B) a thermosetting adhesive, (C) an insulating film, and (D) a film with a wiring pattern.
- the (C) insulating film contains at least (a) a binder polymer, and (b) a black colorant having a reflective region in the infrared region.
- the reinforcing plate-integrated flexible printed board of the present invention is configured in the order of (A) a reinforcing plate, (B) a thermosetting adhesive, (C) an insulating film, and (D) a film with a wiring pattern.
- the flexible printed board integrated with a reinforcing plate of the present invention is a reinforcing plate integrated type configured in the order of (A) a reinforcing plate, (B) a thermosetting adhesive, (C) an insulating film, and (D) a film with a wiring pattern.
- Any flexible printed circuit board may be used as long as the (C) insulating film contains at least (a) a binder polymer and (b) a black colorant having a reflective region in the infrared region. .
- the present inventors have found that the reinforcing plate-integrated flexible printed board of the present invention is excellent in various characteristics. This is presumed to be due to the following reasons.
- the problem that the reinforcing plate peels off during the reflow mounting process is as follows. This is a newly discovered problem when earnestly researching a flexible printed circuit board integrated with a reinforcing plate using a black insulating film.
- the heating method of the reflow mounting process is a method of heating with an infrared heater, so that the surface temperature of the black insulating film is that of the black insulating film due to infrared absorption of the black colorant contained in the black insulating film.
- the present inventors speculate that outgassing during the reflow mounting process can be suppressed by using a black colorant having a reflective region in the infrared region, which is the component (b) in the present invention, as the black colorant. To do. Furthermore, since the black colorant which is the component (b) in the present invention has a higher insulating property than carbon black or the like generally used as a black colorant, the obtained reinforcing plate-integrated flexible printed board is electrically The present inventors speculate that the insulation reliability is also excellent.
- A a reinforcing plate
- B a thermosetting adhesive
- C an insulating film
- D a film with a wiring pattern, other components, and a reinforcing plate-integrated flexible printed board
- FIG. 1 is a configuration diagram of a flexible printed board integrated with a reinforcing plate of the present invention, but the present invention is not limited to this.
- (C) insulating film (4) is formed on the upper surface and lower surface of (D) film with wiring pattern (3) consisting of wiring pattern (2) and base film (1), and flexible.
- a printed circuit board (5) is obtained.
- (A) the reinforcing plate (6) is placed on the upper surface of the film (3) via (B) the thermosetting adhesive (7) (C) on the insulating film (4)
- the reinforcing plate-integrated flexible printed board of the present invention can be obtained.
- the (A) reinforcing plate in the present invention is not particularly limited as long as it is a material that can be used for the purpose of reinforcing the flexible printed circuit board. However, depending on the use of the flexible printed circuit board, the material of the (A) reinforcing plate may be used properly.
- the reinforcing plate (A) include a thick reinforcing plate material and a thin reinforcing plate material. Thick reinforcing plate materials include, for example, paper phenol, glass epoxy plate, and thin reinforcing plate materials include, for example, polyimide film and polyester film. Other thin reinforcing plate materials include metal plates (copper plates). , Aluminum plate).
- a reinforcing plate-integrated flexible printed board having excellent heat resistance and flexibility can be obtained.
- the polyimide film can be selected as appropriate, but the thickness of the polyimide film is preferably 75 ⁇ m to 225 ⁇ m, and examples thereof include the product name Apical 125 NPI (thickness 125 ⁇ m) manufactured by Kaneka Corporation.
- Apical 125 NPI thickness 125 ⁇ m
- strength required in order to support the film with a (D) wiring pattern may not be obtained.
- the thickness of the polyimide film is larger than 225 ⁇ m, the thickness of the entire reinforcing plate-integrated flexible printed board becomes too large, which may be contrary to the trend of downsizing and weight reduction.
- the (B) thermosetting adhesive in the present invention may be a general thermosetting adhesive and can be appropriately selected.
- Examples of the (B) thermosetting adhesive include epoxy, acrylic or acrylic / epoxy thermosetting adhesives.
- Examples of the epoxy thermosetting adhesive include trade names D3410 and D3411 manufactured by Sony Chemical & Information Device Co., Ltd.
- examples of the acrylic thermosetting adhesive include trade name products “Piralux LF0100” and “Piralux FR0100” manufactured by DuPont.
- Examples of the acrylic / epoxy thermosetting adhesive include trade names D3450 and D3451 manufactured by Sony Chemical & Information Device Co., Ltd.
- thermosetting adhesive in this invention, the pressurization and thermoforming method using a hot press is mentioned.
- the hot press temperature is 100 to 180 ° C.
- the hot press pressure is 0.5 to 5.0 kgf / cm 2
- the thermosetting adhesive can be processed by heating and pressing under conditions of time of 10 to 90 minutes. It is preferable to control the pressurization / thermoforming conditions within the above range because the adhesion between the reinforcing plate and the insulating film can be improved.
- the insulating film (C) in the present invention is an insulating film having a thickness of 5 to 100 ⁇ m, and is obtained by curing the resin composition.
- the thickness of the (C) insulating film in the present invention can be measured by any method, but can be measured by a method based on JIS K 5400 3.5, for example.
- the thickness of the insulating film it is preferable to control the thickness of the insulating film within the above range because (C) the insulating reliability of the insulating film is excellent. If the thickness of the insulating film is less than 5 ⁇ m, the electrical insulation reliability of the (C) insulating film may be reduced. If the thickness of the insulating film is greater than 100 ⁇ m, the (C) insulating film There is a risk that the flexibility of the machine is reduced.
- the (C) insulating film in the present invention preferably contains at least (a) a binder polymer, and (b) a black colorant having a reflective region in the infrared region.
- the (C) insulating film is black by containing the component (b), prevents the reinforcing plate from being peeled off during the reflow mounting process, and is provided with an integrated reinforcing plate that is provided with electrical insulation reliability. It is preferable because a flexible printed circuit board can be obtained.
- the (a) binder polymer in the present invention is a polymer that is soluble in an organic solvent and has a weight average molecular weight of 1,000 or more and 1,000,000 or less in terms of polyethylene glycol.
- the organic solvent is not particularly limited, and examples thereof include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N, N-dimethylacetamide, Examples include acetamide solvents such as N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, hexamethylphosphoramide, and ⁇ -butyrolactone. Furthermore, if necessary, these organic polar solvents and aromatic hydrocarbons such as xylene or toluene can be used in combination.
- organic solvent examples include methyl monoglyme (1,2-dimethoxyethane), methyl diglyme (bis (2-methoxyethyl) ether), methyl triglyme (1,2-bis (2-methoxyethoxy).
- the solubility of the organic solvent which is an index for judging whether or not the binder polymer is soluble in the organic solvent, is measured by measuring the weight part of the binder polymer dissolved in 100 parts by weight of the organic solvent. Can do. If the weight part of the binder polymer dissolved with respect to 100 parts by weight of the organic solvent is 5 parts by weight or more, it can be determined that the binder polymer is soluble in the organic solvent.
- the method for measuring the solubility of the organic solvent is not particularly limited. For example, 5 parts by weight of a binder polymer is added to 100 parts by weight of the organic solvent, stirred at 40 ° C. for 1 hour, and then cooled to room temperature (25 ° C.). And leaving it for 24 hours or longer. And it is judged that a binder polymer is soluble with respect to an organic solvent by confirming that there is no generation
- the weight average molecular weight of the component (a) in the present invention can be measured, for example, under the following measurement conditions.
- the weight average molecular weight of the component (a) within the range of 1,000 to 1,000,000 in terms of polyethylene glycol, (C) flexibility and chemical resistance of the obtained insulating film (C) Is preferable because it is excellent.
- the weight average molecular weight is less than 1,000, the flexibility and chemical resistance of the (C) insulating film may be feared.
- the weight average molecular weight is larger than 1,000,000, the resin composition Viscosity may increase.
- polyurethane-type resin poly (meth) acrylic-type resin, polyvinyl-type resin, polystyrene-type resin, polyethylene-type resin, polypropylene-type resin, polyimide-type resin, polyamide Resin, polyacetal resin, polycarbonate resin, polyester resin, polyphenylene ether resin, polyphenylene sulfide resin, polyether sulfone resin, polyether ether ketone resin, and the like.
- the above can be used in combination.
- the component (a) in the present invention when a polyurethane resin or a poly (meth) acrylic resin, which is a resin containing a urethane bond in the molecule, is used, (C) the insulating film has flexibility and breakage resistance. This is preferable because (C) the warpage of the insulating film is reduced.
- the polyurethane resin which is a resin containing a urethane bond in the molecule in the present invention, is soluble in an organic solvent and contains a repeating unit containing at least one urethane bond in the molecule. Is a polymer of 1,000 to 1,000,000 in terms of polyethylene glycol.
- the polyurethane resin which is a resin containing a urethane bond in the molecule in the present invention, can be obtained by any reaction.
- the following general formula (1) the following general formula (1)
- R 1 and X 1 each independently represent a divalent organic group, and n represents an integer of 1 or more
- the diol compound in the present invention is not particularly limited as long as it is a structure represented by the above general formula (1).
- (C) insulating film It is preferable because the elastic modulus is lowered, flexibility and folding resistance are improved, and warping of the insulating film is reduced.
- the diisocyanate compound in the present invention is not particularly limited as long as it is a structure represented by the above general formula (2).
- the blending amount of the diol compound and the diisocyanate compound is determined by the ratio of the number of hydroxyl groups to the number of isocyanate groups (isocyanate group / hydroxyl group). , 0.5 or more and 2.0 or less, and the reaction is carried out without solvent or in an organic solvent.
- the reaction with the diisocyanate compound is performed by mixing two or more kinds of diol compounds with each other. It may be performed later or each diol compound and diisocyanate compound may be reacted separately.
- the isocyanate group at the terminal of the obtained resin is further reacted with another diol compound, and the product after the reaction is further reacted with the diisocyanate compound. May be. The same applies when two or more types of diisocyanate compounds are used.
- a desired polyurethane-based resin containing a urethane bond in the molecule can be produced.
- the reaction temperature between the diol compound and the diisocyanate compound is preferably 40 to 160 ° C., more preferably 60 to 150 ° C. If it is less than 40 ° C., the reaction time becomes too long. If it exceeds 160 ° C., a three-dimensional reaction occurs during the reaction and gelation tends to occur.
- the reaction time between the diol compound and the diisocyanate compound can be appropriately selected depending on the scale of the batch or the reaction conditions employed. If necessary, the reaction may be performed in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, cobalt, or a metalloid compound.
- the reaction between the diol compound and the diisocyanate compound can be performed without a solvent, but in order to control the reaction, it is desirable to perform the reaction in an organic solvent system.
- organic solvent used here is not specifically limited, For example, what was illustrated above can be used.
- the amount of the organic solvent used for the reaction between the diol compound and the diisocyanate compound is desirably an amount such that the solute weight concentration in the reaction solution, that is, the solution concentration is 5% by weight or more and 90% by weight or less. More preferably, the solute weight concentration in the reaction solution is 10 wt% or more and 80 wt% or less.
- the solution concentration is less than 5% by weight, the polymerization reaction is unlikely to occur and the reaction rate is lowered, and a desired structural substance may not be obtained.
- the solution concentration is larger than 90% by weight, the viscosity of the reaction solution becomes high and the reaction may become non-uniform.
- the polyurethane-based resin having a urethane bond in the molecule in the present invention preferably further contains at least one organic group selected from the group consisting of a (meth) acryloyl group, a carboxyl group, and an imide group.
- the (meth) acryloyl group is an acryloyl group and / or a methacryloyl group.
- the photosensitivity of the resin composition is improved. Is possible.
- the solubility of the resin composition in a developing solution of a dilute alkaline aqueous solution used when forming a fine pattern is improved, so that a fine pattern can be formed by developing in a short time.
- it contains an imide group (C) the heat resistance of the insulating film and the electrical insulation reliability under high temperature and high humidity conditions are improved.
- a polyurethane-based resin containing a (meth) acryloyl group and containing a urethane bond in the molecule can be obtained by any reaction.
- the following general formula (4) in addition to the diol compound and the diisocyanate compound, the following general formula (4)
- R 2 represents an m + 1 valent organic group
- R 3 represents hydrogen or an alkyl group
- m represents an integer of 1 to 3
- X 2 represents an l + 1 valent organic group
- X 3 represents hydrogen or an alkyl group
- l represents an integer of 1 to 3
- a compound containing at least one (meth) acryloyl group
- the compound containing a hydroxyl group and at least one (meth) acryloyl group in the present invention is not particularly limited as long as it is a structure represented by the general formula (4).
- 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-1-acryloxy-3-methacryloxypropane, o-phenylphenol Glycidyl ether (meth) acrylate, polyethylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, 1,4-cyclohexanedimethano Rumono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 2- (4-hydroxyphenyl) ethyl (meth)
- the isocyanate group and the compound containing at least one (meth) acryloyl group in the present invention are not particularly limited as long as it is a structure represented by the above general formula (5).
- 2- (meth) acryloyloxy examples thereof include ethyl isocyanate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, 2- (2-methacryloyloxyethyloxy) ethyl isocyanate, and these can be used alone or in combination of two or more.
- a polyurethane resin containing a carboxyl group and containing a urethane bond in the molecule can be obtained by an arbitrary reaction.
- the following general formula (6) in addition to the diol compound and the diisocyanate compound, the following general formula (6)
- R 4 represents a trivalent organic group
- the compound containing two hydroxyl groups and one carboxyl group in the present invention is not particularly limited as long as it is a structure represented by the general formula (6).
- 2,2-bis (hydroxymethyl) propionic acid 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxymepropyl) propionic acid, 2,3-dihydroxy-2-methylpropionic acid, 2,2-bis (hydroxymethyl) ) Butanoic acid, 2,2-bis (2-hydroxyethyl) butanoic acid, 2,2-bis (3-hydroxypropyl) butanoic acid, 2,3-dihydroxybutanoic acid, 2,4-dihydroxy-3,3- Dimethylbutanoic acid, 2,3-dihydroxyhexadecanoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydride Carboxymethyl benzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-d
- the photosensitive resin composition has excellent photosensitivity. Therefore, it is preferable.
- the polyurethane-based resin containing the imide group and containing a urethane bond in the molecule can be obtained by any reaction.
- the following general formula (7) in addition to the diol compound and the diisocyanate compound, the following general formula (7)
- the tetracarboxylic dianhydride in the present invention is not particularly limited as long as it is a structure represented by the general formula (7).
- 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride Pyromellitic dianhydride, 3,3 ′, 4,4′-oxydiphthalic dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2, 2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3 , 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro
- the poly (meth) acrylic resin in the present invention is a polymer that is soluble in an organic solvent, and contains a repeating unit obtained by copolymerizing (meth) acrylic acid and / or (meth) acrylic acid ester derivatives.
- the polymer has a weight average molecular weight of 1,000 or more and 1,000,000 or less in terms of polyethylene glycol.
- (meth) acryl is methacryl and / or acrylic.
- the poly (meth) acrylic resin in the present invention can be obtained by an arbitrary reaction.
- a (meth) acrylic acid and / or a (meth) acrylic ester derivative is used as a radical polymerization initiator in a solvent. It is obtained by reacting in the presence.
- (meth) acrylic acid ester derivative for example, (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid propyl, (meth) acrylic acid butyl, Isobutyl acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, (meth) acrylic acid Examples include decyl, dodecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, and the like.
- radical polymerization initiator examples include azo compounds such as azobisisobutyronitrile, azobis (2-methylbutyronitrile), 2,2′-azobis-2,4-dimethylvaleronitrile, and t-butyl.
- Organic peroxides such as hydroperoxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, peroxides Hydrogen etc. are mentioned, These can be used individually or in combination of 2 or more types.
- the amount of the radical polymerization initiator used is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the monomer used.
- the amount of the radical polymerization initiator used is less than 0.001 part by weight, the reaction is difficult to proceed, and when it is more than 5 parts by weight, the molecular weight may be lowered.
- the amount of solvent used in the reaction for synthesizing the poly (meth) acrylic resin is preferably an amount such that the solute weight concentration in the reaction solution, that is, the solution concentration is 5% by weight or more and 90% by weight or less. 20% by weight or more and 70% by weight or less is more preferable.
- the solution concentration is less than 5%, the polymerization reaction is difficult to occur and the reaction rate is decreased, and a desired structural substance may not be obtained.
- the solution concentration is more than 90% by weight, the reaction solution has a high viscosity. And the reaction may become non-uniform.
- the reaction temperature for synthesizing the poly (meth) acrylic resin is preferably 20 to 120 ° C., more preferably 50 to 100 ° C. When the temperature is lower than 20 ° C., the reaction time becomes too long, and when it exceeds 120 ° C., gelation due to rapid progress of reaction or three-dimensional crosslinking accompanying side reaction may be caused.
- the reaction time for the synthesis of the poly (meth) acrylic resin can be appropriately selected depending on the scale of the batch or the reaction conditions employed.
- the polyimide resin is a polymer having a repeating unit containing at least one imide group in the molecule and having a weight average molecular weight of 1,000 or more and 1,000,000 or less in terms of polyethylene glycol.
- the polyimide resin in the present invention can be obtained by any reaction.
- the following general formula (7) the following general formula (7)
- the tetracarboxylic dianhydride in the present invention is as described above.
- the diamino compound in the present invention is not particularly limited.
- the reaction between the tetracarboxylic acid anhydride and the diamino compound can be performed by any method.
- the tetracarboxylic acid anhydride and the diamino compound can be reacted by the method shown below.
- Method 1 A diamino compound is added to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent and reacted to prepare a polyamic acid solution.
- the total addition amount of the diamino compound is added so as to be a ratio of 0.50 to 1.50 mol per 1 mol of tetracarboxylic dianhydride.
- the resulting polyamic acid solution is heated to 100 ° C. or higher and 300 ° C. or lower, more preferably 150 ° C. or higher and 250 ° C. or lower to imidize. Do.
- Method 2 A polyamic acid solution is prepared in the same manner as in Method 1 above.
- a catalyst for imidization preferably pyridine, picoline, isoquinoline, trimethylamine, triethylamine, tributylamine, etc. are used
- a dehydrating agent such as acetic anhydride
- the imidization is carried out by heating to 180 ° C or lower.
- Method 3 A polyamic acid solution is prepared in the same manner as in Method 1 above.
- the polyamic acid solution is placed in a vacuum oven heated to 100 ° C. or higher and 250 ° C. or lower, and imidized by drawing a vacuum while heating and drying.
- the black colorant having a reflective region in the infrared region is a material having an effect of coloring other materials such as black dyes and black pigments black, and has a wavelength region of 800 nm to 2000 nm which is an infrared region. Any material having a reflectivity of 5% or more may be used. Although it does not specifically limit as a measuring method of the reflectance of the black colorant which has a reflection area
- the reflectance of the black colorant having a reflective region in the infrared region can be measured by a Japanese spectrophotometer U-4100 with a measurement sample introduced into the cell.
- the black pigment having a reflective region in the infrared region is not particularly limited.
- Specific examples of the metal composite oxide include trade names manufactured by Kawamura Chemical Co., Ltd., AB820 black, AG235 black, trade names manufactured by Asahi Chemical Industry Co., Ltd., Black 6350, Black 6301, Black 6302, Black 6303, and the like.
- black pigment having a reflective region in the infrared region examples include organic pigments such as aniline compounds, anthraquinone compounds, and perylene compounds. Specifically, for example, trade names manufactured by BASF, Palogen Black S0084, Lumogen Black FK4280, Lumogen Black FK4281, etc. are mentioned. These can be used alone or in combination of two or more.
- the metal composite oxide is more preferably a metal composite oxide containing iron, chromium, manganese or bismuth from the viewpoint of insulation.
- the organic pigment is more preferably a perylene compound from the viewpoint of insulation.
- the content of the component (b) is preferably 0.1 to 30 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the component (a).
- the blackness and concealment property of the obtained (C) insulating film are excellent.
- the content of the component (b) is less than 0.1 parts by weight with respect to 100 parts by weight of the component (a)
- the component (b) When there is more content than 30 weight part with respect to 100 weight part of (a) component, there exists a possibility that the transmittance
- (c) Flame retardant that does not substantially dissolve in organic solvent in the present invention, (c) a flame retardant that does not substantially dissolve in an organic solvent exists as a solid without dissolving in the organic solvent, and has an effect of suppressing the combustion of organic matter, and is a solid compound at room temperature (25 ° C.) It is.
- the said organic solvent means the organic solvent which is one of the other components which comprises the resin composition in this invention.
- substantially insoluble in the organic solvent here means that it does not dissolve in the organic solvent at all, or does not dissolve in the range not impairing the expression of the effect of the present invention.
- the range not impairing the expression of the effect of the present invention means that the weight of the component (c) dissolved in 100 parts by weight of the organic solvent at room temperature (25 ° C.) is less than 0.1 parts by weight. Therefore, the flame retardant which does not substantially dissolve in the organic solvent (c) in the present invention refers to a flame retardant having a dissolution amount of less than 0.1 parts by weight with respect to 100 parts by weight of the organic solvent at room temperature (25 ° C.).
- the organic solvent is not particularly limited, and for example, the organic solvents exemplified above can be used.
- the method of measuring the weight part of the component (c) dissolved in 100 parts by weight of the organic solvent at room temperature (25 ° C.) is not particularly limited, for example, 1 component (c) is added to 100 parts by weight of the organic solvent. After adding parts by weight and stirring at 40 ° C. for 1 hour, the mixture was cooled to room temperature (25 ° C.), left to stand for 24 hours or more, and then filtered under reduced pressure using a PTFE membrane filter having a pore size of 0.45 ⁇ m. There is a method in which the filter is washed three times with the organic solvent used, the filter is dried at 60 ° C. under reduced pressure for 8 hours, and then the weight change of the filter is measured.
- the component (c) in the present invention is at least one selected from the group consisting of a phosphorus compound, a melamine compound and a metal hydroxide, the flame retardancy of the (C) insulating film is improved, and the outgas Generation is reduced, the electrical insulation reliability is excellent, and the warp of the cured film is small, which is preferable.
- the phosphorus compound in the present invention is not particularly limited as long as it does not substantially dissolve in an organic solvent and contains a phosphorus element.
- aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, trisdiphenylphosphinic acid Aluminum, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanyl bismethylethylphosphinate, titanyl bisdiphenylphosphinate, melamine polyphosphate, etc. It can be used alone or in combination of two or more.
- the melamine-based compound in the present invention is not particularly limited as long as it does not substantially dissolve in an organic solvent and contains a melamine structure.
- melamine oligomer condensate, and the like, and these can be used alone or in combination of two or more.
- the metal hydroxide in the present invention is not particularly limited as long as it is a metal compound that does not substantially dissolve in an organic solvent and contains crystal water.
- the content of the component (c) in the present invention is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the total of the components (a) and (b). .
- an insulating film is excellent in a flame retardance and electrical insulation reliability.
- the amount of the component (c) is less than 5 parts by weight, the flame retardancy of the insulating film may be inferior.
- the coating property is deteriorated, the appearance of the coating film may be deteriorated due to foaming or insufficient leveling during coating.
- thermosetting resin in the present invention is a compound having a structure containing at least one thermosetting organic group in the molecule.
- the component (d) in the present invention is not particularly limited as long as it has the above structure.
- thermosetting resins among the above-mentioned thermosetting resins, in particular, the use of a polyfunctional epoxy resin can impart heat resistance to the insulating film, and can provide adhesion to conductors such as metal foil and circuit boards. Since it can provide, it is preferable.
- the polyfunctional epoxy resin is a compound containing at least two epoxy groups in the molecule.
- bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, Biphenyl type epoxy resin, phenoxy type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol methane type epoxy resin, dicyclopentadiene type epoxy resin, amine type epoxy resin, flexible epoxy
- Examples thereof include resins, urethane-modified epoxy resins, rubber-modified epoxy resins, chelate-modified epoxy resins, and heterocyclic-containing epoxy resins.
- bisphenol A type epoxy resin trade names jER828, jER1001, jER1002 manufactured by Japan Epoxy Resin Co., Ltd., trade names Adeka Resin EP-4100E, Adeka Resin EP-4300E manufactured by ADEKA Co., Ltd., Nippon Kayaku Co., Ltd. Brand names RE-310S and RE-410S manufactured by the company, brand names Epicron 840S, Epicron 850S, Epicron 1050, Epicron 7050 manufactured by DIC Corporation, brand names Epototo YD-115, Epototo YD-127, manufactured by Tohto Kasei Co., Ltd. Epototo YD-128.
- Examples of the bisphenol F-type epoxy resin include trade names jER806 and jER807 manufactured by Japan Epoxy Resins Co., Ltd., trade names Adeka Resin EP-4901E, Adeka Resin EP-4930, Adeka Resin EP-4950, manufactured by Nippon Kayaku Co., Ltd. Trade names RE-303S, RE-304S, RE-403S, RE-404S, trade names Epicron 830, Epicron 835 manufactured by DIC Corporation, trade names Epototo YDF-170, Epototo YDF-175S manufactured by Toto Kasei Co., Ltd. Epototo YDF-2001 is mentioned.
- An example of the bisphenol S-type epoxy resin is trade name Epicron EXA-1514 manufactured by DIC Corporation.
- Examples of the hydrogenated bisphenol A type epoxy resin include trade names jERYX8000, jERYX8034 and jERYL7170 manufactured by Japan Epoxy Resin Co., Ltd., trade names Adeka Resin EP-4080E manufactured by ADEKA Corporation, and trade name Epicron EXA-7015 manufactured by DIC Corporation.
- Examples include Epototo YD-3000 and Epototo YD-4000D manufactured by Toto Kasei Co., Ltd.
- Examples of the biphenyl type epoxy resin include trade names jERYX4000, jERYL6121H, jERYL6640, and jERYL6677 manufactured by Japan Epoxy Resin Co., Ltd., and trade names NC-3000 and NC-3000H manufactured by Nippon Kayaku Co., Ltd.
- Examples of the phenoxy type epoxy resin include trade names jER1256, jER4250, and jER4275 manufactured by Japan Epoxy Resin Co., Ltd.
- Examples of the naphthalene-type epoxy resin include DIC Corporation trade name Epicron HP-4032, Epicron HP-4700, Epicron HP-4200, and Nippon Kayaku Co., Ltd. trade name NC-7000L.
- Examples of the phenol novolac type epoxy resin include trade names jER152 and jER154 manufactured by Japan Epoxy Resin Co., Ltd., trade names EPPN-201-L manufactured by Nippon Kayaku Co., Ltd., trade names Epicron N-740 manufactured by DIC Corporation, and Epicron. N-770, trade name Epototo YDPN-638 manufactured by Toto Kasei Co., Ltd.
- Examples of the cresol novolac type epoxy resin include trade names EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S manufactured by Nippon Kayaku Co., Ltd. and trade names Epicron N-660 and Epicron N-670 manufactured by DIC Corporation. , Epicron N-680 and Epicron N-695.
- Examples of the trisphenol methane type epoxy resin include trade names EPPN-501H, EPPN-501HY and EPPN-502H manufactured by Nippon Kayaku Co., Ltd.
- Examples of the dicyclopentadiene type epoxy resin include trade name XD-1000 manufactured by Nippon Kayaku Co., Ltd., and trade name Epicron HP-7200 manufactured by DIC Corporation.
- Examples of the amine type epoxy resin include trade names jER604 and jER630 manufactured by Japan Epoxy Resin Co., Ltd., trade names Epototo YH-434 and Epototo YH-434L manufactured by Toto Kasei Co., Ltd., trade names TETRAD-X manufactured by Mitsubishi Gas Chemical Co., Ltd. , TERRAD-C.
- Examples of the flexible epoxy resin include trade names jER871, jER872, jERYL7175, jERYL7217 manufactured by Japan Epoxy Resins Co., Ltd., and Epicron EXA-4850 manufactured by DIC Corporation.
- Examples of the urethane-modified epoxy resin include trade names Adeka Resin EPU-6, Adeka Resin EPU-73, and Adeka Resin EPU-78-11 manufactured by ADEKA Corporation.
- Examples of the rubber-modified epoxy resin include Adeka Resin EPR-4023, Adeka Resin EPR-4026, and Adeka Resin EPR-1309 manufactured by ADEKA Corporation.
- Examples of the chelate-modified epoxy resin include trade names Adeka Resin EP-49-10 and Adeka Resin EP-49-20 manufactured by ADEKA Corporation.
- Examples of the heterocyclic ring-containing epoxy resin include trade name TEPIC (triglycidyl isocyanurate) manufactured by Nissan Chemical Co., Ltd.
- a curing agent or a curing accelerator may be used for the purpose of accelerating the curing of the thermosetting resin.
- curing agent used for the resin composition in this invention For example, phenol resins, such as a phenol novolak resin, a cresol novolak resin, a naphthalene type phenol resin, an amino resin, a urea resin, a melamine, a dicyandiamide, etc. are mentioned. These can be used alone or in combination of two or more.
- the curing accelerator used in the resin composition in the present invention is not particularly limited.
- phosphine compounds such as triphenylphosphine; tertiary amines, trimethanolamine, triethanolamine, tetraethanolamine and the like.
- Amine compounds such as 1,8-diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate; imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, Imidazoles such as 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole ; 2-methylimi Imidazolines such as zoline, 2-ethylimidazoline, 2-isopropylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline; 2,4-diamino-6 -[2'-methylimidazolyl- (1
- the (e) photopolymerization initiator in the present invention is a compound that is activated by energy such as UV and initiates / promotes the reaction of the radical polymerizable group-containing resin. Therefore, when the resin composition in the present invention contains a radical polymerizable resin having a radical polymerizable group and (e) a photopolymerization initiator, the resin composition becomes a photosensitive resin composition.
- the radical polymerizable group include an acryloyl group, a methacryloyl group, and a vinyl group.
- the (a) binder polymer may have a radical polymerizable group or a radical polymerizable compound as another component may be contained.
- the insulating film is obtained from a photosensitive resin composition containing (e) a photopolymerization initiator.
- the component (e) in the present invention is not particularly limited, and examples thereof include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 4,4 ′, 4 ′′ -tris (dimethylamino) triphenylmethane, 2, 2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-diimidazole, acetophenone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Ether, benzoin isobutyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, methylanthraquinone, thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 1-hydroxycyclohexyl
- the (e) photopolymerization initiator is preferably blended in an amount of 0.1 to 50 parts by weight with respect to a total of 100 parts by weight of the components (a) and (b). Since the photosensitivity of the photosensitive resin composition in this invention improves by making the mixture ratio of said (e) photoinitiator into said range, it is preferable.
- an organic solvent e.g., a radical polymerizable compound, a filler, an adhesion aid, an antifoaming agent, a leveling agent, a polymerization inhibitor, and (c) an organic solvent substantially.
- Various additives such as a flame retardant other than the flame retardant that does not dissolve can be added.
- the organic solvent is not particularly limited as long as it is an organic polar solvent.
- organic polar solvents such as dimethyl sulfoxide and diethyl sulfoxide
- formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N , N-dimethylacetamide, N, N-diethylacetamide and other acetamide solvents
- N-methyl-2-pyrrolidone N-vinyl-2-pyrrolidone and other pyrrolidone solvents
- hexamethylphosphoramide ⁇ -butyrolactone, etc.
- the organic polar solvent and an aromatic hydrocarbon such as xylene or toluene can be used in combination.
- examples of the organic solvent in the present invention include methyl monoglyme (1,2-dimethoxyethane), methyl diglyme (bis (2-methoxyethyl) ether), methyl triglyme (1,2-bis (2- Methoxyethoxy) ethane), methyltetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyldiglyme (bis (2-ethoxyethyl) ether) ), Symmetric glycol diethers such as butyl diglyme (bis (2-butoxyethyl) ether), methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl D Teracetate, diethylene glycol monoethyl ether
- the above radical polymerizable compound is a compound containing in the molecule a radical polymerizable group that undergoes a polymerization reaction by a radical polymerization initiator.
- the radical polymerizable compound is more preferably a resin having at least one unsaturated double bond as a radical polymerizable group in the molecule.
- the unsaturated double bond is preferably a (meth) acryloyl group or a vinyl group.
- the radical polymerizable compound is preferably used when the component (a) does not contain a (meth) acryloyl group. Moreover, even if (a) component contains the (meth) acryloyl group, you may use it.
- the radical polymerizable compound contains 2 to 50 mol of EO (ethylene oxide) repeating units contained in one molecule of diacrylate or dimethacrylate
- the alkali of the photosensitive resin composition is used. This is preferable because solubility in an aqueous developer typified by an aqueous solution is improved and development time is shortened.
- filler examples include fine inorganic fillers such as silica, mica, talc, barium sulfate, wollastonite, and calcium carbonate.
- antifoaming agent examples include acrylic compounds, vinyl compounds, and butadiene compounds.
- leveling agent examples include acrylic compounds and vinyl compounds.
- adhesion assistant also referred to as adhesion-imparting agent
- adhesion-imparting agent examples include silane coupling agents, triazole compounds, tetrazole compounds, and triazine compounds.
- polymerization inhibitor examples include hydroquinone and hydroquinone monomethyl ether.
- the flame retardant other than the flame retardant that does not substantially dissolve in the organic solvent (c) for example, a phosphoric ester compound, a halogen-containing compound, a metal hydroxide, an organic phosphorus compound, a silicone, or the like is used. Can do.
- a flame retardant other than the flame retardant that does not substantially dissolve in the organic solvent (c) it can be used as an additive-type flame retardant or a reactive flame retardant.
- flame retardants it is more preferable to use non-halogen compounds from the viewpoint of environmental pollution, and phosphorus flame retardants are particularly preferable.
- the (C) insulating film uniformly comprises the components (a), (b), and (c), (d), (e), and other components as necessary. Mix to obtain a resin composition. Then, the resin composition is formed on the upper surface of the film with the wiring pattern (D), and then, if necessary, fine openings are formed by exposure / development and heat treatment is performed in the present invention. A flexible printed circuit board can be obtained.
- the method for uniformly mixing the components used in the insulating film (C) is not particularly limited, and may be mixed using a general kneading apparatus such as a three roll or bead mill apparatus.
- the viscosity of the solution of each said component is low, you may mix using a general stirring apparatus.
- the particle diameter of each component in the resin composition after mixing can be measured by a method using a gauge specified in JIS K 5600-2-5.
- a particle size distribution measuring apparatus is used, the average particle diameter of each component in a resin composition after mixing, a particle diameter, and a particle size distribution can be measured.
- an insulating film can be obtained by an arbitrary method.
- a method for obtaining the insulating film for example, (1) the resin composition as it is, (D) a method of coating and curing the film with a wiring pattern, and (2) forming the resin composition on a support. And the method of affixing the film of an uncured state on (D) a film with a wiring pattern, and hardening and forming is mentioned.
- the resin composition is first applied on the film with a wiring pattern (D) and dried to remove the solvent. Remove.
- Application to the film with the wiring pattern can be performed by screen printing, roller coating, curtain coating, spray coating, spin coating using a spinner, or the like.
- the coating film (preferably having a thickness of 5 to 100 ⁇ m) is dried at 120 ° C. or less, preferably 40 to 100 ° C.
- a negative photomask is placed on the dried coating film, and exposure is performed by irradiating active rays such as ultraviolet rays, visible rays, and electron beams.
- active rays such as ultraviolet rays, visible rays, and electron beams.
- the fine opening can be obtained by developing the unexposed portion with a developer using various methods such as shower, paddle, immersion, or ultrasonic wave. Since the time until the pattern is exposed varies depending on the spraying pressure and flow rate of the developing device and the temperature of the etching solution, it is desirable to find the optimum device conditions as appropriate.
- the developer may contain a water-soluble organic solvent such as methanol, ethanol, n-propanol, isopropanol, N-methyl-2-pyrrolidone.
- a water-soluble organic solvent such as methanol, ethanol, n-propanol, isopropanol, N-methyl-2-pyrrolidone.
- alkaline compound that provides the alkaline aqueous solution include hydroxides, carbonates, bicarbonates, and amine compounds of alkali metals, alkaline earth metals, or ammonium ions.
- alkaline compound examples include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, tetramethylammonium hydroxide, Tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylethanolamine, triethanolamine, triisopropanolamine, triisopropylamine, etc.
- other compounds can be used as long as the aqueous solution exhibits basicity.
- the temperature of the developer depends on the composition of the resin composition or the composition of the alkali developer, and is generally 0 ° C. or higher and 80 ° C. or lower, more generally 10 ° C. or higher and 60 ° C. or lower. It is preferable to do.
- the fine openings formed by the development process are rinsed to remove unnecessary residues.
- the rinsing liquid include water and acidic aqueous solutions.
- the thickness of the insulating film is determined in consideration of (D) the thickness of the film with the wiring pattern, etc., but is preferably about 5 to 100 ⁇ m.
- the final heat treatment temperature at this time is preferably 100 ° C. or more and 250 ° C. or less for the purpose of preventing oxidation of the conductor circuit and the like and (D) not lowering the adhesion with the film with the wiring pattern. Is 120 ° C. or higher and 200 ° C. or lower, particularly preferably 130 ° C. or higher and 180 ° C. or lower.
- the heat treatment temperature is higher than 250 ° C., the oxidative deterioration of the conductor circuit or the like proceeds, and (D) the adhesion with the film with the wiring pattern may be lowered.
- the temperature at which the solvent is removed by performing the above heating and / or hot air blowing may be such that the thermosetting resin (d) component contained in the resin composition does not undergo a crosslinking reaction by heating.
- the support to be used is not particularly limited, but various commercially available films such as a polyethylene terephthalate (PET) film, a polyphenylene sulfide film, and a polyimide film can be used.
- PET polyethylene terephthalate
- a PET film is often used because it has a certain degree of heat resistance and is relatively inexpensive.
- the protective film is preferably laminated and laminated on the surface of the resin composition at a temperature of 10 ° C. to 50 ° C.
- a protective film peels at the time of use, it is desirable for the joint surface of a protective film and a resin composition to have appropriate adhesiveness at the time of storage, and to be excellent in peelability.
- a polyethylene film PE film
- a polyethylene vinyl alcohol film EVA film
- the copolymer film of polyethylene and ethylene vinyl alcohol following ( (PE + EVA) copolymer film), “PE film and (PE + EVA) copolymer film laminate”, or “(PE + EVA) copolymer and polyethylene film by simultaneous extrusion” (one side is PE film side) And the other side of the film is a (PE + EVA) copolymer film side).
- thermocompression bonding may be performed by hot pressing, laminating (thermal laminating), hot roll laminating or the like, and is not particularly limited.
- the processing temperature may be equal to or higher than a lower limit temperature (hereinafter, a pressure bonding possible temperature) at which the laminating process is possible.
- the pressure-bondable temperature is preferably in the range of 50 to 150 ° C., more preferably in the range of 60 to 120 ° C., and particularly preferably in the range of 80 ° C. to 120 ° C. If the temperature at which crimping can be performed exceeds 150 ° C., a crosslinking reaction due to heating of the resin composition may occur during the laminating process, and curing of the resin composition may proceed. On the other hand, when the pressure bonding temperature is less than 50 ° C., the fluidity of the resin composition is low, and it becomes difficult to embed the pattern circuit.
- the filmed resin composition is kept in an uncured state. Therefore, when thermocompression treatment such as thermal laminating treatment is performed, it has appropriate fluidity and can be suitably embedded in a conductor circuit of a film with a wiring pattern.
- the bonded sample in which the resin composition is laminated on the film with the wiring pattern and the support is further laminated is obtained by the above-described thermocompression treatment.
- a negative photomask is placed on the support of the bonded sample, and exposure is performed by irradiating with active light such as ultraviolet light, visible light, or electron beam.
- active light such as ultraviolet light, visible light, or electron beam.
- the support is peeled off, and a fine opening can be obtained by developing the unexposed portion with a developer using various methods such as shower, paddle, immersion, or ultrasonic wave. Since the time until the pattern is exposed varies depending on the spraying pressure and flow rate of the developing device and the temperature of the etching solution, it is desirable to find the optimum device conditions as appropriate.
- the developer may contain a water-soluble organic solvent such as methanol, ethanol, n-propanol, isopropanol, N-methyl-2-pyrrolidone.
- a water-soluble organic solvent such as methanol, ethanol, n-propanol, isopropanol, N-methyl-2-pyrrolidone.
- alkaline compound that provides the alkaline aqueous solution include hydroxides, carbonates, bicarbonates, and amine compounds of alkali metals, alkaline earth metals, or ammonium ions.
- alkaline compound examples include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, tetramethylammonium hydroxide, Tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylethanolamine, triethanolamine, triisopropanolamine, triisopropylamine, etc.
- other compounds may be used as long as the aqueous solution exhibits basicity.
- the temperature of the developer depends on the composition of the resin composition or the composition of the alkali developer, and is generally 0 ° C. or higher and 80 ° C. or lower, more generally 10 ° C. or higher and 60 ° C. or lower. It is preferable to do.
- the fine openings formed by the above development process are rinsed to remove unnecessary residues.
- the rinsing liquid include water and acidic aqueous solutions.
- the thickness of the insulating film is determined in consideration of (D) the thickness of the film with the wiring pattern, etc., but is preferably about 5 to 100 ⁇ m.
- the final heat treatment temperature at this time is preferably 100 ° C. or more and 250 ° C. or less, and more preferably 120 for the purpose of preventing oxidation of the conductor circuit and the like and (D) not lowering the adhesion to the film with a wiring pattern. It is 130 degreeC or more and 180 degrees C or less especially preferably.
- the heat treatment temperature is higher than 250 ° C., the oxidative deterioration of the conductor circuit or the like proceeds, and (D) the adhesion with the film with the wiring pattern may be lowered.
- the film with a wiring pattern in the present invention is a film having a wiring pattern on one side or both sides of a base film having a thickness of 5 to 100 ⁇ m.
- the method for producing a film with a wiring pattern in the present invention is not particularly limited.
- a flexible metal-clad laminate is produced by forming a conductor layer on a base film, and the conductor layer is produced by pattern etching. Can do.
- the base film in the present invention is not particularly limited as long as it is flexible and has an insulating property.
- An inexpensive polyester film is preferable when the base film does not require heat resistance, and a polyimide film is preferable when heat resistance is required.
- the conductor layer in the present invention is not particularly limited, and examples thereof include copper or copper alloy, stainless steel or alloy thereof, nickel or nickel alloy (including 42 alloy), aluminum or aluminum alloy.
- copper foil such as rolled copper foil and electrolytic copper foil is frequently used, but it can also be preferably used in the present invention.
- the antirust layer, the heat-resistant layer, or the contact bonding layer may be apply
- the method for forming a conductor layer on the base film in the present invention is not particularly limited, and examples thereof include a casting method, a laminating method, and a metalizing method.
- the casting method is a method in which a liquid base film solution is applied on a conductor layer, dried and thermally cured.
- the laminating method is a method of forming a base film and a conductor layer by thermocompression bonding. In the laminating method, a so-called three-layer metal-clad laminate in the case of producing an adhesive between the base film and the conductor layer, and a so-called case of not using an adhesive between the base film and the conductor layer.
- the metallizing method is a method in which a metal thin film is formed on a base film by a vacuum deposition method or a sputtering method, and a conductor layer is formed by wet plating.
- a conductor layer may be formed by wet plating without forming a metal thin film.
- the conductor layer can be formed on one side or both sides of the base film.
- the pattern etching method for the conductor layer in the present invention is not particularly limited, and for example, a photoresist method may be mentioned.
- the photoresist method is a method in which a photoresist layer is formed on a metal-clad laminate, and a wiring pattern is formed by exposure, development, etching of a conductor layer, and peeling of a dry film.
- a negative type or a positive type can be used, and a liquid form, a film form, or the like can be used.
- the method of forming the photoresist layer is not particularly limited. For example, a method of forming a negative dry film type resist on a metal-clad laminate by thermal lamination, or a positive type liquid type resist is applied.
- the method of forming and drying on a metal-clad laminate is mentioned.
- a method using a negative photoresist parts other than the exposed part are removed by development.
- the exposed portion is removed by development.
- a dry film type resist can be easily thickened.
- examples of the negative dry film type photoresist include trade name SPG-152 manufactured by Asahi Kasei Corporation and trade name RY-3215 manufactured by Hitachi Chemical Co., Ltd.
- a known agent for developing and removing the photoresist layer can be appropriately selected and used.
- a sodium carbonate aqueous solution (0.2 to 1.5%, etc.) is sprayed.
- the photoresist layer can be developed and removed.
- known conductor layer etching can be appropriately selected and used.
- potassium ferricyanide aqueous solution, iron chloride aqueous solution, copper chloride aqueous solution, ammonium persulfate aqueous solution, sodium persulfate aqueous solution, hydrogen peroxide solution , Hydrofluoric acid aqueous solutions, and combinations thereof can be used.
- the flexible printed circuit board (FPC) integrated with a reinforcing plate in the present invention has excellent adhesion between the thermosetting adhesive of the reinforcing plate and the insulating film, and has a small warpage. It is particularly suitable as an FPC. Further, it is also used for hinge bending, slide bending, cable, connector, FPC for optical pickup of hard disk, and the like.
- Binder polymer 3> 130.60 g of methyltriglyme ( 1,2-bis (2-methoxyethoxy) ethane) was added as a polymerization solvent to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen introducing tube.
- the resin composition was first mixed by a stirring device equipped with a general stirring blade, and then passed twice through a three-roll mill to obtain a uniform solution.
- a stirring device equipped with a general stirring blade
- the following evaluation was carried out by completely defoaming the foam in the solution with a defoaming device.
- ⁇ 1> to ⁇ 11> in Tables 1 and 2 are as follows.
- Product name, reflectance in wavelength region 800 nm to 2000 nm is 5% or more ⁇ 3> manufactured by BASF Japan Ltd.
- Black colorant (organic pigment) product name reflectance in wavelength region 800 nm to 2000 nm is 5% or more ⁇ 4> Product name manufactured by Mitsubishi Chemical Corporation, absorption region in wavelength range of 800 nm to 2000 nm ⁇ 5>
- ⁇ 9> Product name of butadiene type antifoaming agent manufactured by Kyoeisha Chemical Co., Ltd.
- the resin composition is a photosensitive resin composition
- the resin composition is cast and applied on the comb pattern so that the final dry thickness is 20 ⁇ m, dried at 80 ° C. for 20 minutes, and then 300 mJ. / Cm 2 of ultraviolet light with an accumulated exposure dose and exposure, followed by spraying for 90 seconds at a discharge pressure of 1.0 kgf / mm 2 using a 1.0% by weight aqueous solution of sodium carbonate heated to 30 ° C.
- Developed After development, the sample was sufficiently washed with pure water, and then heat-cured in an oven at 150 ° C.
- ⁇ A resistance value of 10 8 or more after 1000 hours from the start of the test and no occurrence of migration, dendrite, etc.
- x An occurrence of migration, dendrite, etc. after 1000 hours from the start of the test.
- the resin composition prepared above is a film with a single-sided wiring pattern (electrolytic copper foil thickness 12 ⁇ m, polyimide film is Kaneka Corporation's Apical 25 NPI, and epoxy adhesive is used to bond the copper foil.
- the film was cast and applied to an area of 100 mm ⁇ 100 mm so that the final dry thickness was 20 ⁇ m, and dried at 80 ° C. for 20 minutes. Subsequently, it was heat-cured for 30 minutes in an oven at 150 ° C. to form an insulating film of the resin composition on the film with a single-sided wiring pattern, and a flexible printed board was produced.
- the film with a single-sided wiring pattern (electrolytic copper foil thickness of 12 ⁇ m, polyimide film is manufactured by Kaneka Corporation, using a Baker type applicator. 25NPI, copper foil is bonded with an epoxy adhesive), cast and applied to an area of 100mm x 100mm so that the final dry thickness is 20 ⁇ m, and dried at 80 ° C for 20 minutes
- exposure was performed by irradiating ultraviolet rays with an accumulated exposure amount of 300 mJ / cm 2 , and then a discharge pressure of 1.0 kgf / mm 2 using a solution of a 1.0 wt% sodium carbonate aqueous solution heated to 30 ° C.
- spray development for 90 seconds. After development, the substrate was thoroughly washed with pure water, and then heat-cured in an oven at 150 ° C. for 30 minutes to form an insulating film of the photosensitive resin composition on the film with a single-sided wiring pattern, thereby producing an FPC.
- thermosetting adhesive (Dupont, trade name: PILARAX LF0100) is temporarily pressure-bonded on a polyimide film (Kaneka Corporation, trade name: Apical 125 NPI), which is a reinforcing plate, with a hot roll laminate at 185 ° C. 1 was produced. Thereafter, the insulating film surface of the FPC produced above and the thermosetting adhesive surface of the laminate 1 were pressure-bonded at 165 ° C./90 min with a hot press to produce a reinforcing plate-integrated FPC evaluation test piece.
- the present invention is a reinforcing plate-integrated flexible printed circuit board constituted in the order of (A) a reinforcing plate, (B) a thermosetting adhesive, (C) an insulating film, and (D) a film with a wiring pattern, (C) The reinforcing plate-integrated flexible printed board, wherein the insulating film contains at least (a) a binder polymer, and (b) a black colorant having a reflective region in the infrared region. Moreover, it is preferable that the (C) insulating film contains a flame retardant that does not substantially dissolve in the organic solvent (c), and (d) is obtained from a resin composition containing a thermosetting resin. It is preferable.
- the (C) insulating film is more preferably obtained from a photosensitive resin composition containing (e) a photopolymerization initiator.
- the reinforcing plate-integrated flexible printed circuit board according to the present invention can be used for circuit boards of various electronic devices.
Abstract
Description
図1に、本発明の補強板一体型フレキシブルプリント基板の構成図を示すが、本発明は、これに限定されるものではない。先ず、配線パターン(2)及びベースフィルム(1)からなる(D)配線パターン付きフィルム(3)の上表面の上及び下表面の上に、(C)絶縁膜(4)を形成し、フレキシブルプリント基板(5)を得る。続いて、(A)補強板(6)を(B)熱硬化性接着剤(7)を介して、フィルム(3)の上表面の上に形成された(C)絶縁膜(4)の上に形成し、本発明の補強板一体型フレキシブルプリント基板を得ることができる。
本発明における(A)補強板は、フレキシブルプリント基板を補強する目的で用いることができる材料であればよく、特に限定されない。しかし、フレキシブルプリント基板の用途により、上記(A)補強板の材料を使い分ける場合がある。上記(A)補強板として、例えば、厚手の補強板材料、薄型の補強板材料がある。厚手の補強板材料としては、例えば、紙フェノール、ガラスエポキシ板、薄型の補強板材料としては、例えば、ポリイミドフィルム、ポリエステルフィルムなどがあり、その他、薄型の補強板材料としては、金属板(銅板、アルミ板)などがある。また、補強板にポリイミドフィルムを用いることにより、耐熱性、柔軟性に優れた補強板一体型フレキシブルプリント基板を得ることができる。ポリイミドフィルムとしては、適宜選択することができるが、上記ポリイミドフィルムの厚さが75μm~225μmであることが好ましく、例えば、株式会社カネカ製 商品名アピカル125NPI(厚さ125μm)が挙げられる。上記ポリイミドフィルムの厚さが、75μmよりも小さい場合、(D)配線パターン付きフィルムを支持するために必要な強度が得られないおそれがある。一方、上記ポリイミドフィルムの厚さが、225μmよりも大きい場合、補強板一体型フレキシブルプリント基板全体としての厚さが大きくなり過ぎ、小型化、軽量化の傾向に反するおそれがある。
本発明における(B)熱硬化性接着剤は、一般的な熱硬化性接着剤であればよく、適宜選択することができる。上記(B)熱硬化性接着剤としては、例えば、エポキシ系、アクリル系又はアクリル/エポキシ系の熱硬化性接着剤が挙げられる。上記エポキシ系の熱硬化性接着剤としては、例えば、ソニーケミカル&インフォメーションデバイス株式会社製の商品名D3410、D3411等が挙げられる。また、上記アクリル系の熱硬化性接着剤としては、例えば、デュポン社製の商品名パイララックスLF0100、パイララックスFR0100等が挙げられる。また、上記アクリル/エポキシ系熱硬化性接着剤としては、例えば、ソニーケミカル&インフォメーションデバイス株式会社製の商品名D3450、D3451等が挙げられる。
本発明における(C)絶縁膜は、絶縁性を有し、かつ厚さが5~100μmの膜であって、樹脂組成物を硬化させることにより得られるものである。
本発明における(a)バインダーポリマーは、有機溶媒に対して可溶性であり、重量平均分子量が、ポリエチレングリコール換算で1,000以上、1,000,000以下のポリマーである。
使用装置:東ソーHLC-8220GPC相当品
カラム :東ソー TSK gel Super AWM-H(6.0mmI.D.×15cm)×2本
ガードカラム:東ソー TSK guard column Super AW-H
溶離液:30mM LiBr+20mM H3PO4 in DMF
流速:0.6mL/min
カラム温度:40℃
検出条件:RI:ポラリティ(+)、レスポンス(0.5sec)
試料濃度:約5mg/mL
標準品:PEG(ポリエチレングリコール)。
で示されるジオール化合物と、下記一般式(2)
で示されるジイソシアネート化合物を反応させることにより、下記一般式(3)
で示されるウレタン結合を含有する繰り返し単位を分子内に含んでいる構造として得られる。
で示される水酸基及び少なくとも1つの(メタ)アクリロイル基を含有する化合物及び/又は下記一般式(5)
で示されるイソシアネート基、及び少なくとも1つの(メタ)アクリロイル基を含有する化合物を反応させることにより得られる。
で示される2つの水酸基及び1つのカルボキシル基を含有する化合物を反応させることにより得られる。
で示されるテトラカルボン酸二無水物を反応させることにより得られる。
で示されるテトラカルボン酸二無水物とジアミノ化合物を反応させることにより得られる。
本発明における(b)赤外線領域において反射領域を有する黒色着色剤は、黒色染料、黒色顔料などの他の物質を黒色に着色する効果を有する物質であり、かつ赤外線領域である波長領域800nm~2000nmにおける反射率が5%以上である物質であればよい。本発明における(b)赤外線領域において反射領域を有する黒色着色剤の反射率の測定方法としては、特に限定はされないが、例えば下記方法によって測定する事が出来る。(b)赤外線領域において反射領域を有する黒色着色剤の反射率は、セルに測定検体を導入し、日本分光光度計U-4100によって測定することができる。
本発明における(c)有機溶媒に実質的に溶解しない難燃剤は、有機溶媒中に溶解せずに固体として存在し、有機物の燃焼を抑制する効果を有する、室温(25℃)で固体の化合物である。ここで、上記有機溶媒は、本発明における樹脂組成物を構成する、他成分の1つである有機溶媒を意味する。
本発明における(d)熱硬化性樹脂は、分子内に少なくとも1つの熱硬化性の有機基を含有している構造の化合物である。
本発明における(e)光重合開始剤は、UVなどのエネルギーによって活性化し、ラジカル重合性基含有樹脂の反応を開始・促進させる化合物である。したがって、本発明における樹脂組成物が、ラジカル重合性基を有したラジカル重合性樹脂と(e)光重合開始剤とを含有する場合、上記樹脂組成物は感光性樹脂組成物となる。ここで、ラジカル重合性基としては、アクリロイル基、メタクリロイル基またはビニル基が挙げられる。本発明におけるラジカル重合性樹脂としては、ラジカル重合性基を(a)バインダーポリマーが兼ね備えている場合もあるし、その他成分であるラジカル重合性化合物が含まれている場合もある。本発明における補強板一体型フレキシブルプリント基板は、(C)絶縁膜が(e)光重合開始剤を含有している感光性樹脂組成物から得られることが好ましい。本発明における(e)成分としては、特に限定されないが、例えば、ミヒラーズケトン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、4,4’,4’’-トリス(ジメチルアミノ)トリフェニルメタン、2,2’-ビス(2-クロロフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ジイミダゾール、アセトフェノン、ベンゾイン、2-メチルベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエ-テル、2-t-ブチルアントラキノン、1,2-ベンゾ-9,10-アントラキノン、メチルアントラキノン、チオキサントン、2,4-ジエチルチオキサントン、2-イソプロピルチオキサントン、1-ヒドロキシシクロヘキシルフェニルケトン、ジアセチルベンジル、ベンジルジメチルケタール、ベンジルジエチルケタール、2-(2’-フリルエチリデン)-4,6-ビス(トリクロロメチル)-S-トリアジン、2-[2’-(5’’-メチルフリル)エチリデン]-4,6-ビス(トリクロロメチル)-S-トリアジン、2-(p-メトキシフェニル)-4,6-ビス(トリクロロメチル)-S-トリアジン、2,6-ジ(p-アジドベンザル)-4-メチルシクロヘキサノン、4,4’-ジアジドカルコン、ジ(テトラアルキルアンモニウム)-4,4’-ジアジドスチルベン-2,2’-ジスルフォネート、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノプロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタン-1、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド、ビス(2,6-ジメトキシベンゾイル)-2,4,4-トリメチル-ペンチルフォスフィンオキサイド、2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-ケトン、ビス(n-5,2,4-シクロペンタジエン-1-イル)-ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)-フェニル)チタニウム、1,2-オクタンジオン,1-[4-(フェニルチオ)-2-(O-ベンゾイルオキシム)]、ヨード二ウム,(4-メチルフェニル)[4-(2-メチルプロピル)フェニル]-ヘキサフルオロフォスフェート(1-)、エチル-4-ジメチルアミノベンゾエート、2-エチルヘキシル-4-ジメチルアミノベンゾエート、エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-1-(O-アセチルオキシオム)などが挙げられる。上記(e)光重合開始剤は適宜選択することが望ましく、1種以上を混合させて用いることが望ましい。
本発明における樹脂組成物には、さらに必要に応じて、有機溶媒、ラジカル重合性化合物、充填剤、接着助剤、消泡剤、レベリング剤、重合禁止剤、(c)有機溶媒に実質的に溶解しない難燃剤以外の難燃剤等の各種添加剤を加えることができる。
本発明における(C)絶縁膜は、上記各成分(a)成分、(b)成分、必要に応じて以下(c)成分、(d)成分、(e)成分、及びその他の成分を均一に混合し、樹脂組成物を得る。その後、上記樹脂組成物を(D)配線パターン付きフィルムの上表面の上に形成し、その後、必要に応じて露光・現像により微細開口部を形成し、加熱処理を行うことにより、本発明におけるフレキシブルプリント基板を得られることができる。上記(C)絶縁膜に用いる各成分を均一に混合する方法としては、特に限定されるものではないが、例えば3本ロール、ビーズミル装置等の一般的な混練装置を用いて混合すればよい。また、上記各成分の溶液の粘度が低い場合には、一般的な攪拌装置を用いて混合してもよい。上記の混合する装置の中でも、特に3本ロールを用いて粉砕・分散させて混同した場合、(c)成分が均一な大きさになるため好ましい。混合後の樹脂組成物中の各成分の粒子径は、JIS K 5600-2-5で規定されたゲージを用いる方法で測定することができる。また粒度分布測定装置を使用すれば、混合後の樹脂組成物中の各成分の平均粒子径、粒子径、粒度分布を測定することができる。
本発明における配線パターン付きフィルムは、厚さ5~100μmのベースフィルムの片面又は両面に配線パターンを有するフィルムである。本発明における配線パターン付きフィルムの作製方法は、特に限定されないが、例えば、ベースフィルムに導体層を形成することにより、フレキシブル金属張積層板を作製し、導体層をパターンエッチングする事によって作製することができる。
<(a)バインダーポリマー1>
攪拌機、温度計、滴下漏斗、冷却管及び窒素導入管を備えた反応容器に、重合用溶媒としてメチルトリグライム(=1,2-ビス(2-メトキシエトキシ)エタン)100.0gを仕込み、窒素気流下で攪拌しながら80℃まで昇温した。これに、室温(25℃)で予め混合しておいた、メタクリル酸12.0g(0.14モル)、メタクリル酸ベンジル28.0g(0.16モル)、メタクリル酸ブチル60.0g(0.42モル)、ラジカル重合開始剤としてのアゾビスイソブチロニトリル0.5gを、80℃に保温した状態で3時間かけて滴下漏斗から滴下した。滴下終了後、反応溶液を攪拌しながら90℃まで昇温し、反応溶液の温度を90℃に保ちながら更に2時間にわたって攪拌を行い反応させた。上記反応を行うことでポリ(メタ)アクリル系樹脂溶液(a-1)を得た。得られた樹脂溶液の固形分濃度は50%、重量平均分子量は48,000、固形分の酸価は78mgKOH/gであった。尚、固形分濃度、重量平均分子量、酸価は下記の方法で測定した。
JIS K 5601-1-2に従って測定を行った。尚、乾燥条件は170℃×1時間の条件を選択した。
下記条件で測定を行った。
使用装置:東ソー HLC-8220GPC相当品
カラム :東ソー TSK gel Super AWM-H(6.0mmI.D.×15cm)×2本
ガードカラム:東ソー TSK guard column Super AW-H
溶離液:30mM LiBr+20mM H3PO4 in DMF
流速:0.6mL/min
カラム温度:40℃
検出条件:RI:ポラリティ(+)、レスポンス(0.5sec)
試料濃度:約5mg/mL
標準品:PEG(ポリエチレングリコール)。
JIS K 5601-2-1に従って測定を行った。
<(a)バインダーポリマー2>
攪拌機、温度計、滴下漏斗、冷却管及び窒素導入管を備えた反応容器に、重合用溶媒としてメチルトリグライム(=1,2-ビス(2-メトキシエトキシ)エタン)30.00gを仕込み、これに、ノルボルネンジイソシアネート10.31g(0.050モル)を添加して、窒素気流下で攪拌しながら80℃に加温して溶解させた。この溶液に、ポリカーボネートジオール50.00g(0.025モル)(旭化成株式会社製、製品名PCDL T5652、重量平均分子量2000)及び2-ヒドロキシエチルメタクリレート6.51g(0.050モル)をメチルトリグライム30.00gに溶解した溶液を1時間かけて滴下漏斗から滴下した。滴下終了後、この溶液を5時間80℃で加熱攪拌を行い反応させた。上記反応を行うことで分子内にウレタン結合を有するウレタン系樹脂溶液(a-2)を得た。得られた樹脂溶液の固形分濃度は53%、重量平均分子量は5,200であった。尚、固形分濃度、重量平均分子量は合成例1と同様の方法で測定した。
<(a)バインダーポリマー3>
攪拌機、温度計、滴下漏斗、冷却管及び窒素導入管を備えた反応容器に、重合用溶媒としてメチルトリグライム(=1,2-ビス(2-メトキシエトキシ)エタン)130.60gを添加して、これに、3,3’,4,4’-オキシジフタル酸二無水物31.02g(0.100モル)、ビス[4-(3-アミノフェノキシ)フェニル]スルホン34.45g(0.080モル)、ポリ(テトラメチレン/3-メチルテトラメチレンエーテル)グリコールビス(4-アミノベンゾエート)24.76g(0.020モル)を添加して、窒素気流下で30分間攪拌してポリアミド酸溶液を得た。次いで、この溶液を190℃に加温して2時間にわたって反応させた。上記反応を行うことでポリイミド系樹脂溶液(a-3)を得た。得られた樹脂溶液の固形分濃度は49%、重量平均分子量は36,000であった。尚、固形分濃度、重量平均分子量は合成例1と同様の方法で測定した。
<樹脂組成物の調製>
合成例で得られた(a)バインダーポリマー、(b)赤外線領域において反射領域を有する黒色着色剤、(c)有機溶媒に実質的に溶解しない難燃剤、(d)熱硬化性樹脂、(e)光重合開始剤、及びその他成分を添加して樹脂組成物を作製した。それぞれの構成原料の樹脂固形分での配合量及び原料の種類を表1及び表2に記載する。なお、表中の有機溶媒である1,2-ビス(2-メトキシエトキシ)エタンは上記合成した樹脂溶液に含まれる溶剤も含めた全溶剤量である。樹脂組成物ははじめに一般的な攪拌翼を備えた攪拌装置にて混合し、その後、3本ロールミルに2回通して均一な溶液とした。グラインドメーターにて粒子径を測定したところ、いずれも10μm以下であった。混合溶液を脱泡装置で溶液中の泡を完全に脱泡して下記評価を実施した。
<1>アサヒ化成工業株式会社製 黒色着色剤(金属複合酸化物)の製品名、波長領域800nm~2000nmにおける反射率が5%以上
<2>アサヒ化成工業株式会社製 黒色着色剤(金属複合酸化物)の製品名、波長領域800nm~2000nmにおける反射率が5%以上
<3>BASFジャパン株式会社製 黒色着色剤(有機顔料)の製品名、波長領域800nm~2000nmにおける反射率が5%以上
<4>三菱化学株式会社製 製品名、波長領域800nm~2000nmにおいて吸収領域がある
<5>クラリアントジャパン株式会社製 ホスフィン酸塩の製品名、1,2-ビス(2-メトキシエトキシ)エタン100重量部に対する溶解性0.01重量部未満
<6>BASFジャパン株式会社製 メラミンシアヌレートの製品名、1,2-ビス(2-メトキシエトキシ)エタン100重量部に対する溶解性0.01重量部未満
<7>ナバルテック社製 ベーマイト型水酸化アルミニウムの製品名、1,2-ビス(2-メトキシエトキシ)エタン100重量部に対する溶解性0.01重量部未満
<8>日産化学株式会社製 多官能エポキシ樹脂(トリグリシジルイソシアヌレート)の製品名
<9>共栄社化学株式会社製 ブタジエン系消泡剤の製品名
<10>BASFジャパン株式会社製 オキシムエステル系光重合開始剤の製品名
<11>日立化成工業株式会社製 EO変性ビスフェノールAジメタクリレートの製品名。
(i)電気絶縁信頼性
フレキシブル銅貼り積層版(電解銅箔の厚さ12μm、ポリイミドフィルムは株式会社カネカ製アピカル25NPI、ポリイミド系接着剤で銅箔を接着している)上にライン幅/スペース幅=100μm/100μmの櫛形パターンを作製し、10容量%の硫酸水溶液中に1分間浸漬した後、純水で洗浄し銅箔の表面処理を行った。その後、上記櫛形パターン上に最終乾燥厚さが20μmになるように樹脂組成物を流延・塗布し、80℃で20分間乾燥した。その後、150℃のオーブン中で30分間加熱硬化させて絶縁膜とし試験片を得た。尚、樹脂組成物が感光性樹脂組成物の場合は、上記櫛形パターン上に最終乾燥厚さが20μmになるように樹脂組成物を流延・塗布し、80℃で20分乾燥した後、300mJ/cm2の積算露光量の紫外線を照射して露光、次いで、1.0重量%の炭酸ナトリウム水溶液を30℃に加熱した溶液を用いて、1.0kgf/mm2の吐出圧で90秒間スプレー現像を行った。現像後、純水で十分洗浄した後、150℃のオーブン中で30分間加熱硬化させて絶縁膜とし試験片を得た。85℃、85%RHの環境試験機中で試験片の両端子部分に100Vの直流電流を印加し、絶縁抵抗値の変化やマイグレーションの発生などを観察した。観察した結果を下記「○」又は「×」で示す。
○:試験開始から1000時間経過後に、10の8乗以上の抵抗値を示し、マイグレーション、デンドライトなどの発生が無いもの
×:試験開始から1000時間経過後に、マイグレーション、デンドライトなどの発生があるもの。
上記樹脂組成物を、ベーカー式アプリケーターを用いて、25μmのポリイミドフィルム(株式会社カネカ製:商品名25NPI)に最終乾燥厚さが20μmになるように100mm×100mmの面積に流延・塗布し、80℃で20分間乾燥した。その後、150℃のオーブン中で30分間加熱硬化させて絶縁膜とし試験片を得た。尚、樹脂組成物が感光性樹脂組成物の場合は、上記櫛形パターン上に最終乾燥厚さが20μmになるように樹脂組成物を流延・塗布し、80℃で20分間乾燥した後、300mJ/cm2の積算露光量の紫外線を照射して露光、次いで、1.0重量%の炭酸ナトリウム水溶液を30℃に加熱した溶液を用いて、1.0kgf/mm2の吐出圧で90秒間スプレー現像を行った。現像後、純水で十分洗浄した後、150℃のオーブン中で30分間加熱硬化させて絶縁膜とし試験片を得た。1mm角のマス目を有する方眼紙の上に上記試験片を置き、目視にて試験片の上からマス目を確認する方法で隠蔽性の評価を行った。評価結果を下記「○」又は「×」で示す。
○:マス目が見えないもの
×:マス目が見えるもの。
上記で調整した樹脂組成物を、ベーカー式アプリケーターを用いて、片面配線パターン付きフィルム(電解銅箔の厚さ12μm、ポリイミドフィルムは株式会社カネカ製アピカル25NPI、エポキシ系接着剤で銅箔を接着している)の銅箔面上に、最終乾燥厚さが20μmになるように100mm×100mmの面積に流延・塗布し、80℃で20分間乾燥した。次いで、150℃のオーブン中で30分間加熱硬化させて樹脂組成物の絶縁膜を片面配線パターン付きフィルム上に形成し、フレキシブルプリント基板を作製した。
得られた補強板一体型フレキシブルプリント基板について、以下の項目につき評価を行った。評価結果を表3及び表4に記載する。
上記<補強板一体型フレキシブルプリント基板評価試験片の作製>で得られた試験片を用いて、JIS K5400に従って碁盤目テープ法で評価した。評価結果を下記「○」、「△」又は「×」で示す。
○:碁盤目テープ法で剥がれの無いもの
△:升目の95%以上が残存しているもの
×:升目の残存量が80%未満のもの。
上記<補強板一体型フレキシブルプリント基板評価試験片の作製>で得られた試験片を用いて、260℃:ピークトップ260℃×20secのリフロー条件でリフロー処理した後の試験片の外観を観察する。観察結果を下記「○」又は「×」で示す。
○:試験前後で外観に変化の無いもの
×:試験後、試験片の何れかの積層界面で膨れが発生するもの。
2 配線パターン
3 配線パターン付きフィルム
4 絶縁膜
5 フレキシブルプリント基板
6 補強板
7 熱硬化性接着剤
Claims (4)
- (A)補強板、(B)熱硬化性接着剤、(C)絶縁膜、(D)配線パターン付きフィルムの順で構成された補強板一体型フレキシブルプリント基板であって、該(C)絶縁膜が少なくとも(a)バインダーポリマー、及び(b)赤外線領域において反射領域を有する黒色着色剤を含有していることを特徴とする補強板一体型フレキシブルプリント基板。
- 上記(C)絶縁膜が、(c)有機溶媒に実質的に溶解しない難燃剤を含有していることを特徴とする請求項1に記載の補強板一体型フレキシブルプリント基板。
- 上記(C)絶縁膜が、(d)熱硬化性樹脂を含有している樹脂組成物から得られることを特徴とする請求項1または2に記載の補強板一体型フレキシブルプリント基板。
- 上記(C)絶縁膜が(e)光重合開始剤を含有している感光性樹脂組成物から得られることを特徴とする請求項1~3のいずれか1項に記載の補強板一体型フレキシブルプリント基板。
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US20150189740A1 (en) | 2015-07-02 |
US10292262B2 (en) | 2019-05-14 |
JP6360792B2 (ja) | 2018-07-18 |
TWI586230B (zh) | 2017-06-01 |
JPWO2014014043A1 (ja) | 2016-07-07 |
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