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WO2016111130A1 - Composition de mélange polymère, stratifié métallique souple et carte de circuit imprimé souple - Google Patents

Composition de mélange polymère, stratifié métallique souple et carte de circuit imprimé souple Download PDF

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Publication number
WO2016111130A1
WO2016111130A1 PCT/JP2015/085183 JP2015085183W WO2016111130A1 WO 2016111130 A1 WO2016111130 A1 WO 2016111130A1 JP 2015085183 W JP2015085183 W JP 2015085183W WO 2016111130 A1 WO2016111130 A1 WO 2016111130A1
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WIPO (PCT)
Prior art keywords
resin
general formula
film
polymer blend
metal foil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/085183
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English (en)
Japanese (ja)
Inventor
佑 山本
智晴 栗田
翔太 井上
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyobo Co Ltd
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Toyobo Co Ltd
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Filing date
Publication date
Application filed by Toyobo Co Ltd filed Critical Toyobo Co Ltd
Priority to JP2016568309A priority Critical patent/JP6589887B2/ja
Publication of WO2016111130A1 publication Critical patent/WO2016111130A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/14—Polyamide-imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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

Definitions

  • the present invention relates to a polymer blend composition, a film using the same, a flexible metal laminate, and a flexible printed board. More specifically, in addition to dimensional stability (low warpage, dimensional change), a polymer blend composition suitable for use in the fields of electrical and electronic equipment that has both adhesiveness and transparency, a film using the same, and a flexible metal laminate And a flexible printed circuit board.
  • the “flexible metal laminate” is a laminate formed of a metal foil and a film layer (resin layer), and is a laminate useful for manufacturing a flexible printed circuit board, for example.
  • the “flexible printed circuit board” can be manufactured by a conventionally known method such as a subtractive method using a flexible metal laminate, for example, and a conductor circuit may be partially or entirely covered by a coverlay film.
  • FPC flexible circuit boards
  • TAB tape automated bonding
  • COF chip-on-flexible board
  • Polyimide resin is widely used as a resin film for electronic materials because of its excellent insulation reliability in addition to heat resistance and chemical resistance.
  • the polyimide resin is insoluble and infusible, it is necessary to form a film by subjecting the solvent-soluble polyimide precursor to high temperature treatment. As a result, the problem is that the film is colored, the transparency is lowered, and the workability is poor because the procedure is complicated.
  • polyamideimide resin is excellent in solubility and heat-treated at a relatively low temperature to obtain a film having excellent transparency. Therefore, as an alternative material for polyimide resin, an electronic material, particularly a resin film for a flexible metal laminate for COF It is used as
  • a flexible metal laminate for COF when a driver IC is mounted on a substrate, positioning is often performed by irradiating visible light with a wavelength of 400 to 800 nm from the resin film side and performing image recognition processing with a CCD camera or the like.
  • the resin film is often made of a material having a double bond.
  • the wavelength range of 600 to 700 nm is generally regarded as particularly important. For this reason, when the light transmittance of the resin film after etching of the flexible metal laminate is low or when the haze is high, the positional accuracy is lowered, and it becomes impossible to cope with the high density and fine pitch of the wiring pattern.
  • a resin film has a coefficient of linear expansion (CTE) larger than that of metal.
  • CTE coefficient of linear expansion
  • the heat applied when used as an electronic material expands and contracts as a metal laminate, causing a dimensional change.
  • the wires may come into contact with each other and cause a short circuit.
  • the dimensions change it may be difficult to form the fine pattern circuit itself. Therefore, it is desirable that the CTE of the metal foil and the resin film is equally low. From the above, various attempts have been made to satisfy high transparency, high adhesive strength, and low CTE.
  • Patent Document 1 there is a method for producing a metal laminate having a good balance of heat resistance, adhesion, and the like by applying a polyamide imide resin having a high glass transition temperature (Tg) and low CTE onto a copper foil and drying.
  • Tg glass transition temperature
  • Patent Document 1 since the copper foil with a large surface roughness was used, there existed a problem that the resin film surface after etching a copper foil became rough and visibility deteriorated by irregular reflection of light. Also, the patternability at a narrow pitch is inferior due to the rough surface roughness of the copper foil, and the copper foil with a high surface roughness shows a high value, but the adhesive strength and patternability can be satisfied at the same time. Not.
  • Patent Document 2 a flexible metal laminate having a polyimide insulating layer composed of a plurality of layers on a copper foil by applying a polyimide precursor resin solution to a relatively mirror-finished copper foil having a low surface roughness, followed by drying and curing.
  • this metal laminate has insufficient bare chip mountability and adhesion strength to copper foil with high glossiness and reflectivity, and is further dried and imidized at a high temperature after application of the polyimide precursor resin solution. Therefore, it is inferior in workability.
  • copper foil since it heat-processes at high temperature, copper foil itself recrystallizes and there exists a problem that it is not suitable for the use for which fine pitch patterning property is requested
  • Patent Document 3 discloses a technique for improving adhesive strength by laminating two layers of polyamideimide resin on a relatively mirror-finished copper foil.
  • Patent Document 3 has a problem that the process becomes complicated by laminating two layers, and the productivity is poor. Further, since the thickness increases, there is a problem that it is difficult to reduce the size.
  • an object of the present invention is to provide a polymer blend composition excellent in transparency, adhesiveness, and dimensional stability by blending two kinds of polyamideimide resins as specific components. Furthermore, it is providing the film containing the said polymer blend composition, a flexible metal laminated body, and a flexible printed circuit board.
  • the present invention has the following configuration.
  • a polymer blend composition comprising a polyamideimide resin having two or more components and satisfying the following requirements (1) and (2).
  • a polyamideimide resin (resin ⁇ ) having a composition different from that of the resin ⁇ containing the following general formula (3) as a structural unit is an essential component.
  • R 4 and R 5 may be the same or different and each represents hydrogen, or an alkyl group or alkoxy group having 1 to 4 carbon atoms.
  • Resin ⁇ contains trimellitic anhydride as an acid component, and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride It is preferable that at least one kind selected from the group consisting of the above-mentioned products and o-tolidine as the amine component.
  • the flexible metal laminate preferably has a metal foil Rz of 1.2 ⁇ m or less, a 60 ° gloss of 200 or more, and an adhesive strength between the metal foil and the film of 7.0 N / cm or more.
  • the flexible metal laminate preferably has a light transmittance at a wavelength of 600 nm of 55% or more, a haze of 20% or less, and a linear expansion coefficient in the film portion after the metal foil etching.
  • the amount of film distortion at the glass transition temperature in the TMA method is preferably 200 ⁇ m or less.
  • a flexible printed board containing the flexible metal laminate A flexible printed board containing the flexible metal laminate.
  • the present invention can provide a polymer blend composition excellent in adhesiveness, transparency, and dimensional stability, and a film, a flexible metal laminate, and a flexible printed board containing the polymer blend composition.
  • a material that can be adapted to fine pitch requirements that will be further developed in the future for COF applications and the like can be obtained.
  • the polymer blend composition of the present invention is a composition containing two or more components of polyamideimide resin and satisfying the requirements (1) and (2). Two or more components of the polyamideimide resin are preferably mixed uniformly.
  • the polyamideimide resin can be obtained by uniformly mixing two or more types of polyamideimide resin varnish dissolved in an organic solvent and removing the solvent.
  • Polyamideimide resin ( ⁇ ) having a diphenyl ether skeleton and a phenylene skeleton contributes to transparency and adhesiveness. Further, the polyamideimide resin ( ⁇ ) having a biphenyl skeleton, particularly an o-tolidine skeleton, contributes to dimensional stability (low CTE). In the present invention, a polymer blend composition excellent in transparency, adhesiveness and dimensional stability can be obtained by blending these polyamideimide resins.
  • a polymer blend composition containing two or more components of a resin is compatible with these composition ratios in all practical areas below the thermal decomposition temperature, and incompatible in all areas.
  • incompatible systems and partially compatible systems that are compatible in a certain region.
  • partially miscible systems that induce reactions such as nucleation type and spinodal decomposition type depending on the condition of the phase separation state.
  • the uniform polymer blend composition in the present invention refers to a state in which there is no macro phase separation to the extent that scattering by visible light does not occur. When macro phase separation occurs, for example, in the case of a film, a significant decrease in transparency can be confirmed.
  • the requirement (1) includes a polyamide-imide resin (hereinafter also referred to as a resin ⁇ ) containing the general formula (1) and the general formula (2) as structural units as an essential component.
  • a polyamide-imide resin containing the basic structure represented by the general formula (1) and the general formula (2) as a repeating unit.
  • R 1 , R 2 and R 3 may be the same or different, and each represents hydrogen, an alkyl group having 1 to 4 carbon atoms or an alkoxy group. Show.
  • the carbon number is preferably 1 or more and 3 or less, more preferably 2 or less. Particularly preferably, R 1 , R 2 and R 3 are all hydrogen.
  • trimellitic anhydride is essential as the acid component constituting the resin ⁇ .
  • acid components other than trimellitic anhydride include pyromellitic anhydride, phthalic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride, or 3,3 ′, 4,4′- Biphenyltetracarboxylic acid anhydride is mentioned, These can be used alone or in combination of two or more. Of these, pyromellitic acid anhydride and phthalic acid anhydride are preferable.
  • trimellitic acid trimellitic acid, pyromellitic acid, phthalic acid, isophthalic acid, terephthalic acid, biphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfonedicarboxylic acid, 3 as long as the object of the present invention is not impaired.
  • amine component constituting the resin ⁇ 4,4′-diaminodiphenyl ether, p-phenylenediamine, 2,4-diaminotoluene, or diisocyanate corresponding to these, or a mixture of two or more of them should be used. is required.
  • the resin ⁇ having the general formula (1) and the general formula (2) and the resin ⁇ having the general formula (3) are blended to maintain the dimensional stability (low CTE) of the film.
  • transparency can be improved.
  • the reason for the improved adhesiveness is that the ether bond of the general formula (1) provides flexibility, and the anchor is that the polymer blend composition easily enters fine irregularities on the surface even with a relatively mirror-finished metal foil. It is conceivable that it contributes to the improvement of the effect and the affinity with the metal foil. Moreover, it is thought that the characteristic that the ether bond of General formula (1) is hard to carry out heat deterioration contributes to the improvement of transparency.
  • the structural unit of the general formula (1) contained in the resin ⁇ is preferably 55 mol% or more, more preferably 60 mol% or more, further preferably 65 mol% or more, preferably 90 mol% or less, and preferably 85 mol% or less. More preferred is 80 mol% or less.
  • the structural unit of the general formula (2) contained in the resin ⁇ is preferably 10 mol% or more, more preferably 15 mol% or more, further preferably 20 mol% or more, preferably 45 mol% or less, and 40 mol%. The following is more preferable, and 35 mol% or less is more preferable. By setting it as the said range, the improvement effect of adhesiveness and transparency and the curvature prevention effect at the time of making a film can be anticipated.
  • the requirement (2) includes a polyamideimide resin (hereinafter, also referred to as a resin ⁇ ) having a composition different from that of the resin ⁇ including the general formula (3) as a structural unit as an essential component.
  • a polyamideimide resin containing the basic structure represented by the general formula (3) as a repeating unit is preferable.
  • R 4 and R 5 may be the same or different and each represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group.
  • the carbon number is preferably 1 or more and 3 or less, more preferably 2 or less. Particularly preferably, R 4 and R 5 both have 1 carbon.
  • the structural unit of the general formula (3) contained in the resin ⁇ is preferably 60 mol% or more, more preferably 65 mol% or more, and further preferably 70 mol% or more.
  • the upper limit is not particularly limited, and may be 100 mol%. If it is less than 60 mol%, low CTE characteristics are not sufficiently exhibited, and use as an insulating material for electrical and electronic equipment such as flexible printed wiring boards tends to be difficult.
  • Trimellitic anhydride is essential as the acid component constituting the resin ⁇ .
  • Acid components other than trimellitic anhydride include 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, or pyromellitic An acid anhydride is mentioned, These can be used individually or in combination of 2 or more types. Of these, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride are preferable.
  • trimellitic acid, pyromellitic acid, phthalic acid, isophthalic acid, terephthalic acid, biphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfonedicarboxylic acid, 3,3 ′, 4 are not limited as long as the object of the present invention is impaired.
  • amine component constituting the resin ⁇ o-tolidine, 4,4′-diaminobiphenyl, 2,2′-dimethylbiphenyl-4,4′-diamine, o-dianisidine, or a corresponding diisocyanate alone, Alternatively, a mixture of two or more kinds can be used.
  • 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylmethane, 3,3 ′ may be used as an amine component within the range not impairing the object of the present invention.
  • a particularly preferred combination is a polyamideimide resin mainly composed of repeating units selected from the following monomer components.
  • ⁇ Acid component Trimellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride.
  • ⁇ Amine component o-Tolidine, 2,4-tolylenediamine, or the corresponding diisocyanate.
  • Resin ⁇ and resin ⁇ used in the present invention can be synthesized (polymerized) by an ordinary method.
  • an isocyanate method there are an isocyanate method, an acid chloride method, a low temperature solution polymerization method, a room temperature solution polymerization method, etc., but from the viewpoint of production cost, a particularly preferable production method is an isocyanate method in which a polymer varnish can be obtained by a decarboxylation reaction. .
  • Solvents used for polymerization include amides such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, 1,3-dimethyl-2-imidazolidinone Solvents, sulfur solvents such as dimethyl sulfoxide and sulfolane, ketone solvents such as cyclohexanone and methyl ethyl ketone, nitro solvents such as nitrobenzene and nitroethane, ether solvents such as diglyme and tetrahydrofuran, nitrile solvents such as acetonitrile and propionitrile And ester solvents such as ⁇ -butyllactone and ⁇ -valerolactone can be used alone or as a mixed solvent.
  • amides such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylure
  • the content of the resin ⁇ is preferably 10 to 50% by weight, more preferably 15 to 50% by weight, and still more preferably 20 to 50% by weight based on the total weight of the polymer blend composition. %.
  • the content of the resin ⁇ exceeds 50% by weight, the CTE increases, and it tends to be difficult to use as an insulating material for electric and electronic devices such as flexible printed wiring boards.
  • the content of the resin ⁇ is less than 10% by weight, characteristics inherent to the polymer including the structure represented by the general formula (1), particularly characteristics such as adhesive strength and transparency, tend not to be maintained.
  • the polymer blend composition of the present invention was directly laminated on a metal foil having a 10-point average roughness (Rz) of 1.2 ⁇ m or less and a 60 ° gloss of 200 or more without using an adhesive, and IPC-FC241 ( According to IPC-TM-650, 2.4.9 (A)), the adhesive strength between the metal foil and the polymer blend composition layer (film layer) when a circuit pattern is formed by the subtractive method is 7.0 N / cm. It is preferable to have the above.
  • the molecular weight of the polyamideimide resin ⁇ and the resin ⁇ is a molecular weight corresponding to 0.1 to 2.8 dl / g in N-methyl-2-pyrrolidone (polymer concentration 0.5 g / dl) with a logarithmic viscosity at 30 ° C. And more preferably those having a molecular weight corresponding to 0.3 to 2.5 dl / g. If the logarithmic viscosity is less than 0.1 dl / g, mechanical properties may be insufficient when formed into a molded product such as a film, and if it exceeds 2.8 dl / g, the solution viscosity becomes high. May be difficult.
  • the vertical viscosity at 25 ° C. is in the range of 50 to 1000 dPa ⁇ s. When the viscosity is out of the above range, the coatability may be lowered.
  • the concentration of the polyamideimide resin ⁇ and the resin ⁇ solution can be selected from a wide range, but is generally preferably about 5 to 40% by weight, more preferably about 8 to 30% by weight. preferable. When the concentration is out of the above range, drying efficiency is deteriorated, and it is feared that formation of a smooth surface becomes difficult and a necessary amount of heat increases.
  • a preferred solvent for the polyamideimide resin solution N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, sulfolane, dimethylsulfone, and the like are used as dilution solvents after polymerization because of coating properties and the like.
  • Oxides, ⁇ -butyrolactone, cyclohexanone, cyclopentanone and the like are preferable, and N, N-dimethylacetamide and N-methyl-2-pyrrolidone are particularly preferable.
  • Some of these can be replaced with hydrocarbon organic solvents such as toluene and xylene, ether organic solvents such as diglyme, triglyme and tetrahydrofuran, and ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone.
  • these solvents can also be applied as solvents during polymerization, the polymerization solution can be applied as it is, so that a resin solution having excellent processability can be easily obtained.
  • the polymer blend composition of the present invention may be added to the above-described polymer blend composition for the purpose of improving various properties of the flexible metal laminate or flexible printed circuit board, such as mechanical properties, electrical properties, slipperiness, and flame retardancy.
  • Other resins, organic compounds, and inorganic compounds may be mixed or reacted to be used in combination.
  • lubricant silicon, talc, silicone, etc.
  • adhesion promoter flame retardant (phosphorus, triazine, aluminum hydroxide, etc.), stabilizer (antioxidant, UV absorber, polymerization inhibitor, etc.), plating activity Agents, organic and inorganic fillers (talc, titanium oxide, silica, fluorine polymer fine particles, pigments, dyes, calcium carbide, etc.), silicone compounds, fluorine compounds, isocyanate compounds, blocked isocyanate compounds, acrylic resins, urethanes Resin, polyester resin, polyamide resin, epoxy resin, phenolic resin and organic compounds, or these curing agents, silicon oxide, titanium oxide, calcium carbonate, iron oxide and other inorganic compounds do not hinder the purpose of this invention Can be used together in a range.
  • a catalyst for polyimide formation such as aliphatic tertiary amine, aromatic tertiary amine, heterocyclic tertiary amine, aliphatic acid anhydride, aromatic acid anhydride, hydroxy compound, etc. It may be added.
  • triethylamine, triethylenediamine, dimethylaniline, pyridine, picoline, isoquinoline, imidazole, undecene, hydroxyacetophenone and the like are preferable, and pyridine compound, imidazole compound and undecene compound are particularly preferable.
  • benzimidazole, triazole, 4 -Pyridinemethanol, 2-hydroxypyridine and diazabicyclo [5.4.0] undecene-7 are preferred, and 2-hydroxypyridine and diazabicyclo [5.4.0] undecene-7 are more preferred.
  • the film of the present invention is a film containing a polymer blend composition, and can be produced using the polymer blend composition solution (varnish). Applying the polymer blend composition solution (varnish) on a support such as a metal foil, endless belt, drum, carrier film, etc., drying the coating, and optionally heat-treating the film after peeling off the support. It is formed by.
  • a conventionally known method can be applied, for example, roll coater, knife coater, doctor, blade coater, gravure coater, die coater, reverse coater. It can apply
  • the drying conditions after casting the polymer blend composition solution are not particularly limited, but in general, the polymer blend composition solution was initially dried at a temperature 70 to 130 ° C. lower than the boiling point (Tb (° C.)) of the solvent used in the polymer blend composition solution. Thereafter, secondary drying (heat treatment) is preferably performed at a temperature near or above the boiling point of the solvent.
  • Tb boiling point
  • warping may occur in the flexible metal laminate on which the film is laminated, and warping of the flexible printed circuit board obtained by processing the circuit may be increased.
  • the drying temperature is lower than (Tb-130) ° C.
  • the initial drying temperature varies depending on the type of solvent, but is generally about 60 to 150 ° C., preferably about 80 to 120 ° C.
  • the time required for the initial drying is generally an effective time for the solvent remaining rate in the coating film to be about 5 to 40% by weight under the above temperature conditions, but generally about 1 to 30 minutes, Especially about 2 to 15 minutes.
  • the secondary drying may be performed at a temperature near or above the boiling point of the solvent, but is generally 150 to 500 ° C., preferably 200 to 400 ° C.
  • the time required for the secondary drying is generally an effective time for the solvent remaining amount in the coating film to be 1% by weight or less under the above-mentioned temperature conditions. is there.
  • initial drying and secondary drying may be performed under an inert gas atmosphere or under reduced pressure.
  • the inert gas include nitrogen, carbon dioxide, helium, and argon, but it is preferable to use easily available nitrogen.
  • the reaction is preferably performed under a pressure of about 10 ⁇ 5 to 10 3 Pa, preferably about 10 ⁇ 1 to 200 Pa.
  • both the initial drying and heat treatment methods are not particularly limited, but can be performed by a conventionally known method such as a roll support method or a floating method. Moreover, continuous heat treatment in a heating furnace such as a tenter type is also possible.
  • the film containing the polymer blend composition of the present invention thus obtained can obtain a tough film with mechanical properties, that is, high strength and high elongation, without impairing the low CTE property of the resin ⁇ .
  • the thickness of the film can be selected from a wide range, it is generally about 5 to 100 ⁇ m, preferably about 10 to 50 ⁇ m, after drying. When the thickness is less than 5 ⁇ m, the mechanical properties such as film strength and handling properties are inferior. On the other hand, when the thickness exceeds 100 ⁇ m, the properties such as flexibility and workability (drying property, coating property) are deteriorated. There are things to do.
  • surface treatment may be performed as necessary.
  • surface treatment such as hydrolysis, corona discharge, low temperature plasma, physical roughening, and easy adhesion coating treatment can be performed.
  • the flexible metal laminate of the present invention is preferably a two-layer metal laminate in which the film and the metal foil are directly laminated without using an adhesive.
  • Examples of the production method include a laminating method and a casting method, and are not particularly limited. However, it is preferable to produce by a casting method that can be produced at low cost and processability.
  • the thickness of the metal foil is not particularly limited, but a metal foil of 1 to 50 ⁇ m, preferably 3 to 35 ⁇ m, more preferably 3 to 18 ⁇ m can be suitably used.
  • a metal foil of 1 to 50 ⁇ m, preferably 3 to 35 ⁇ m, more preferably 3 to 18 ⁇ m can be suitably used.
  • the thickness of the metal foil is less than 1 ⁇ m, the yield at the time of conveyance is lowered, and when it is thicker than 50 ⁇ m, the winding as a long object is poor and the winding property is deteriorated, and the yield may be lowered.
  • a metal foil having a 10-point average roughness Rz of 1.2 ⁇ m or less, preferably 1.0 ⁇ m or less, more preferably 0.8 ⁇ m or less can be suitably used. If Rz exceeds 1.2 ⁇ m, the unevenness of the copper foil is transferred to the resin film, the transparency of the resin film after etching is lowered, and sufficient positioning accuracy may not be ensured.
  • the glossiness of the metal foil is 200 or more, preferably 300 or more, more preferably 400 or more.
  • the glossiness is measured according to JIS-Z8741-1997, and irradiated at an incident angle of 60 °, and the reflected light at 60 ° is measured.
  • the flexible metal laminate of the present invention is preferably formed by directly applying a solution of the polymer blend composition to a metal foil, drying the coating film, and optionally heat-treating it.
  • a metal foil copper foil, aluminum foil, steel foil, nickel foil, etc. can be used, composite metal foil that combines these, zinc, chromium, nickel, cobalt, molybdenum compounds, or alloys thereof, Metal foils treated with other metals can also be used.
  • a more preferable metal foil is a copper foil, but a commercially available electrolytic foil or a rolled foil can be used as it is if the above-mentioned characteristics are satisfied.
  • the amount of strain is the amount of change in the film caused by the release of internal stress when the flexible metal laminate is exposed to a temperature higher than the glass transition temperature, and the amount of strain is preferably 200 ⁇ m or less. If it exceeds 200 ⁇ m, the amount of change is large, the dimensional change of the flexible metal laminate is large, and the positional accuracy during mounting may be insufficient.
  • the flexible metal laminate of the present invention thus obtained has high mechanical properties of the insulating resin layer, that is, high strength, high strength, without impairing the high transparency, high adhesive strength of the resin ⁇ , and the low CTE of the resin ⁇ . It is possible to obtain a flexible metal laminate in which an elongation and tough film is laminated.
  • the adhesive strength between the metal foil and the film in the flexible metal laminate is preferably 7.0 N / cm or more, more preferably 7.5 N / cm or more, and still more preferably 8.0 N / cm or more. If it is less than 7.0 N / cm, the wiring may be peeled off from the substrate due to repeated shrinkage and expansion due to heat generated when used as an electronic component, making it difficult to cope with fine pitch. is there. Therefore, the higher the adhesive strength, the better, but 10.0 N / cm or more is sufficient.
  • the light transmittance is a characteristic related to the positioning accuracy when the driver is mounted, and the parallel light transmittance at 600 nm is defined as the light transmittance.
  • the light transmittance in the film portion after etching the metal foil of the flexible metal laminate is preferably 60% or more, more preferably 65% or more, and still more preferably 70% or more. If it is less than 60%, the positioning accuracy at the time of mounting described above may be lowered, and it may be difficult to cope with fine pitch.
  • haze is also a characteristic related to positioning accuracy, similar to light transmittance.
  • Haze is an index of turbidity, and the higher the haze, the lower the transparency of the object and the lower the transmittance.
  • the haze in the film portion after etching the metal foil of the flexible metal laminate is preferably 20% or less, more preferably 15% or less, and still more preferably 13% or less.
  • the coefficient of linear expansion (CTE) in the film portion after etching the metal foil of the flexible metal laminate is preferably 10 to 25 ppm / K, more preferably 12 to 25 ppm / K, and still more preferably 15 to 25 ppm / K. .
  • the flexible metal laminate of the present invention is excellent in transparency by specifying the surface characteristics of the copper foil. Furthermore, it is excellent in adhesive force by blending two kinds of polyamideimide resins whose resin composition is specified, and is excellent in dimensional stability and workability by specifying the blend ratio. Therefore, as an electronic material, it can be suitably used not only for FPC, flat cable, and TAB applications but also for COF film carrier tapes that have high needs for miniaturization and high performance and fine wiring pitches.
  • V1 represents the solution viscosity measured with an Ubbelohde type viscosity tube
  • V2 represents the solvent viscosity measured with an Ubbelohde type viscosity tube
  • V1 and V2 represent a polymer solution and a solvent (N-methyl-2-pyrrolidone).
  • V3 is the polymer concentration (g / dl).
  • ⁇ Glass transition temperature and strain> TMA Thermo-mechanical analyzer / manufactured by Seiko Instruments Inc.
  • the glass transition temperature was defined as the intersection of the base line before the endothermic peak and the tangent toward the endothermic peak in the endothermic curve at elevated temperature.
  • the amount of strain was calculated from the inflection point of the baseline and the change length of the endothermic peak point.
  • the sample used the film part after etching the metal foil of the flexible metal laminated body obtained by the experiment example.
  • Load 5g Sample size: 4 (width) x 20 (length) mm
  • Temperature increase rate 10 ° C / min
  • Atmosphere Nitrogen
  • the glossiness of the metal foil was in accordance with the specular glossiness measuring method described in JIS Z8741-1997, and the intensity of light reflected at a reflection angle of 60 ° was measured by irradiating a light source at an incident angle of 60 °.
  • the incident angle here is 0 ° in the direction perpendicular to the light irradiation surface. Measurement was performed using a VG200 gloss meter manufactured by Nippon Denshoku Co., Ltd. The measurement measured the resin application surface of metal foil.
  • a circuit pattern was prepared by a subtractive method in accordance with IPC-FC241 (IPC-TM-650, 2.4.9 (A)) from the flexible metal foil laminate sample obtained in the experimental example, and the metal foil and film (polymer The adhesive strength with the blend composition layer) was measured.
  • the measuring instrument was measured using a spectrophotometer V650 manufactured by JASCO Corporation. In order to measure the parallel light transmittance, an integrating sphere unit that receives diffused light was not used, and measurement was performed in a standard state. The measurement range was 300 to 800 nm, and the value at 600 nm was read.
  • the measuring instrument was NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd., and the measurement was performed according to JIS-K7136.
  • the scattered light transmittance divided by the total light transmittance was expressed as a percentage.
  • Example 7 As shown in Tables 1 and 2, a metal laminate was obtained under the same conditions as in Experimental Example 1 except that the resin composition of the resin ⁇ was changed. By changing the composition of the resin ⁇ , the properties of the metal laminate were greatly deteriorated. From this, it can be seen that the composition of the resin ⁇ is important in the present invention.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'objectif de la présente invention est de proposer une composition de mélange polymère dotée d'excellentes propriétés d'adhésivité, de transparence et de stabilité dimensionnelle. La présente invention concerne en particulier un matériau capable de répondre aux demandes de pas plus fin, qui deviendront plus contraignantes à l'avenir dans le domaine des puces sur substrat souple « chip on flex » et d'autres applications. La composition de mélange polymère est caractérisée en ce qu'elle comprend deux ou plusieurs résines polyamide-imide et qu'elle satisfait aux exigences (1) et (2) ci-après. (1) Comprendre, en tant que composant essentiel, une résine de polyamide-imide (résine alpha) comprenant la formule générale (1) et la formule générale (2) en tant que motifs constitutifs, le rapport molaire de la formule générale (1) à la formule générale (2) dans la résine alpha, [formule générale (1) / formule générale (2)], allant de 55/45 à 90/10. (2) Comprendre, en tant que composant essentiel, une résine de polyamide-imide (résine bêta) qui comprend la formule générale (3) en tant que motif constitutif et qui diffère dans sa composition de la résine alpha.
PCT/JP2015/085183 2015-01-09 2015-12-16 Composition de mélange polymère, stratifié métallique souple et carte de circuit imprimé souple Ceased WO2016111130A1 (fr)

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WO2017099172A1 (fr) * 2015-12-09 2017-06-15 東レ株式会社 Résine, bouillie, et stratifié mettant en œuvre ceux-ci ainsi que procédé de fabrication de celui-ci
US11261303B2 (en) * 2016-07-21 2022-03-01 Mitsubishi Gas Chemical Company, Inc. Polyimide resin film and method for producing polyimide resin film

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
CN111533909B (zh) * 2020-06-08 2023-04-25 武汉柔显科技股份有限公司 一种聚酰胺酰亚胺、聚酰胺酰亚胺薄膜及显示装置

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JPH06103822A (ja) * 1992-09-18 1994-04-15 Sumitomo Electric Ind Ltd 絶縁電線
JPH06196025A (ja) * 1992-12-22 1994-07-15 Sumitomo Electric Ind Ltd 絶縁電線
JP2009141337A (ja) * 2007-11-12 2009-06-25 Toyobo Co Ltd 金属積層体
WO2011152178A1 (fr) * 2010-05-31 2011-12-08 東洋紡績株式会社 Stratifié souple recouvert de métal

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
JPH06103822A (ja) * 1992-09-18 1994-04-15 Sumitomo Electric Ind Ltd 絶縁電線
JPH06196025A (ja) * 1992-12-22 1994-07-15 Sumitomo Electric Ind Ltd 絶縁電線
JP2009141337A (ja) * 2007-11-12 2009-06-25 Toyobo Co Ltd 金属積層体
WO2011152178A1 (fr) * 2010-05-31 2011-12-08 東洋紡績株式会社 Stratifié souple recouvert de métal

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017099172A1 (fr) * 2015-12-09 2017-06-15 東レ株式会社 Résine, bouillie, et stratifié mettant en œuvre ceux-ci ainsi que procédé de fabrication de celui-ci
JPWO2017099172A1 (ja) * 2015-12-09 2018-11-01 東レ株式会社 樹脂、スラリーおよびそれらを用いた積層体とその製造方法
JP7135272B2 (ja) 2015-12-09 2022-09-13 東レ株式会社 樹脂、スラリーおよびそれらを用いた積層体とその製造方法
US11261303B2 (en) * 2016-07-21 2022-03-01 Mitsubishi Gas Chemical Company, Inc. Polyimide resin film and method for producing polyimide resin film

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