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
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • 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
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
• • 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
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • 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
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
  • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
• • 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
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/20—Inorganic coating
  • B32B2255/205—Metallic coating
• • 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
  • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
  • B32B2264/10—Inorganic particles
• • 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
  • B32B2311/00—Metals, their alloys or their compounds
  • B32B2311/12—Copper
• • 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
  • B32B2457/00—Electrical equipment

Definitions

• the present invention relates to a resin film and its manufacturing method, as well as a metallized resin film and a printed wiring board.
• a printed wiring board which has a circuit made of metal conductors on an insulating substrate, is widely used as a component that expresses the functions of electronic devices by mounting various electronic components on the printed wiring board.
• printed wiring boards are required to have narrower pitches of circuit wiring.
• (a) flexible printed wiring boards, (b) rigid-flex boards, (c) multilayer flexible boards, and (d) COFs (chip-on-films), etc. which can be folded and stored compactly inside electronic devices.
• COFs chip-on-films
• Patent Document 1 discloses a method of bonding a thin-film copper foil with a carrier to a polyimide sheet.
• Patent Document 2 discloses a method of forming a metal layer on a polyimide film using a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method.
• Patent Document 3 discloses an example in which a material containing a polyimide resin having a silicone structure and fumed silica is directly plated with copper by electroless plating.
• One embodiment of the present invention has been made in view of the above problems, and an object of the present invention is to provide a novel resin film having excellent solder resistance and adhesion, a method for producing the same, and a metallization obtained from the resin film. It is to provide a resin film and a printed wiring board.
• the layer A containing the polyimide resin and the fumed metal oxide is a heat-resistant resin film having a linear expansion coefficient of 20 ppm / ° C. or less, and at least one surface of the layer B. and the linear expansion coefficient of the polyimide resin is 30 ppm/°C or more and 100 ppm/°C or less.
• the layer A containing a polyimide resin and a fumed metal oxide is a heat-resistant resin film having a linear expansion coefficient of 20 ppm / ° C. or less.
• the layer A formed on one surface and having a linear expansion coefficient of the polyimide resin of 30 ppm/° C. or more and 100 ppm/° C. or less and containing a polyimide resin and a fumed metal oxide is a polyamide precursor of the polyimide resin. It is obtained by mixing an acid solution and a fumed metal oxide and imidating the obtained fumed metal oxide-dispersed polyamic acid solution.
• a material and method that exhibit excellent solder heat resistance and can be used for narrow-pitch circuit formation, specifically, excellent solder heat resistance and strong adhesion to a low-roughness surface It is possible to provide a resin film capable of forming an electroless plated layer showing
• Patent Document 1 irregularities are intentionally formed on the copper foil surface in order to ensure the adhesion between the insulating base material and the copper foil. Therefore, in Patent Document 1, although the thickness of the copper layer is usually thinner than the limit of the copper foil, there is an adverse effect on the circuit shape in the etching process, there is a limit to narrowing the pitch, and there is an adverse effect on the transmission characteristics. be.
• metals such as nickel, chromium, vanadium, titanium, and molybdenum are formed on the substrate surface by physical vapor deposition.
• metals such as nickel, chromium, and titanium cannot be completely removed only by etching with an etchant for copper during circuit formation. There is a problem that an etchant needs to be used and the process is complicated.
• Patent Document 3 discloses a resin film capable of forming an electroless plated layer on a low-roughness surface, there is room for improvement in terms of solder resistance and the like.
• the present invention has been made in view of the above problems, and an object of the present invention is to provide a novel resin film having excellent solder resistance and adhesion, a method for producing the same, and a metallized resin obtained from the resin film. It is to provide films and printed wiring boards.
• One embodiment of the present invention is, for example, a material (resin film) that exhibits excellent solder heat resistance and is compatible with narrow-pitch circuit formation, and a method therefor.
• An object of the present invention is to provide a resin film capable of forming an electroless plated layer exhibiting strong adhesion to a rough surface, and a method for producing the same.
• Another object of one embodiment of the present invention is to provide a metallized resin film and a printed wiring board obtained from the resin film.
• the layer A containing the polyimide resin and the fumed metal oxide is formed on at least one surface of the layer B, which is a heat-resistant resin film having a coefficient of linear expansion of 20 ppm/° C. or less. and the linear expansion coefficient of the polyimide resin is 30 ppm/°C or more and 100 ppm/°C or less.
• the resin film according to one embodiment of the present invention has the advantage of being excellent in solder resistance and adhesiveness due to the above configuration.
• adhesion is evaluated by peel strength (N/cm)
• solder resistance is evaluated by moisture absorption solder heat resistance.
• a layer A (also referred to as layer A) containing a polyimide resin and a fumed metal oxide will be described.
• Layer A of one embodiment of the present invention essentially comprises a polyimide resin and a fumed metal oxide.
• the adhesion between the resin film and the electroless metal plating layer especially the adhesion immediately after forming the electroless metal plating layer without heating, etc., can be greatly improved. It describes below about the way of thinking of the expression mechanism of adhesiveness.
• the electroless metal plating process consists of multiple independent chemical baths. These chemical baths are controlled under prescribed conditions (concentration, temperature, etc.), and the surface of the object to be plated is brought into contact with these chemicals for a prescribed period of time by means of immersion, showering, etc., and the surface undergoes chemical changes, such as causes a physical shape change.
• These chemical solutions contain various components, and their pH varies depending on the type of chemical solution, and some chemical solutions exhibit strong alkalinity and strong acidity.
• both the polyimide resin and the fumed metal oxide essential for one embodiment of the present invention interact with these chemicals, causing changes in chemical structure and physical shape, and electroless metal plating. It is thought that it has an effect on the improvement of adhesion with.
• fumed metal oxides and polyimide resins undergo chemical changes in alkaline environments.
• fumed metal oxides dissolve in alkaline environments to produce ionic metal oxides.
• a polyimide resin produces an ionic amic acid group through an imide ring cleavage reaction in an alkaline environment.
• ionic compounds such as ionic metal oxides and ionic amic acid groups
• react with metal ions in the electroless metal plating bath to A compound derived from the three components of "polyimide resin” can be formed at the interface between the polyimide resin and the metal plating. It is believed that the compound contributes to the adhesion, and as a result, the adhesion between the polyimide resin and the metal plating is enhanced.
• the dissolution rate of polyimide resin and fumed metal oxide in an alkaline environment is thought to be affected by the chemical structure and aggregate structure of polyimide resin, and the chemical structure and specific surface area of fumed metal oxide, respectively.
• Layer A containing the polyimide resin and fumed metal oxide of one embodiment of the present invention is exposed to an alkaline environment, dissolution occurs according to the respective dissolution rates of the polyimide resin and the fumed metal oxide.
• the layer A of one embodiment of the present invention has a structure in which a fumed metal oxide exists in a state of being buried in a polyimide resin phase.
• the surface of the layer A has the same particle size as the fumed metal oxide, depending on the dissolution rate of each of the polyimide resin and the fumed metal oxide in alkaline chemicals.
• the surface area of layer A can be increased as a result of the generation of fine irregularities. It is considered that the increase in the surface area of the layer A also contributes to the improvement in adhesion strength.
• the fumed metal oxide essential to one embodiment of the present invention has a structure in which primary particles are aggregated, and exists in a state of being buried in the polyimide resin phase.
• a part of certain structural units of the fumed metal oxide essential for one embodiment of the present invention is exposed to the surface and/or exists near the surface, and the other part exists in the bulk direction. It is thought that the two are strongly bound together and contribute to the improvement of the adhesion strength. That is, (i) the area of the interface where the compound derived from the three components of "fumed metal oxide" - "metal (e.g.
• a polyimide resin is characterized by containing an imide group in its chemical skeleton. It is believed that the imide group (functional group) in the polyimide resin interacts with the fumed metal oxide and the metal element (for example, copper element) to improve adhesion to the electroless metal plating layer. Therefore, it is essential that the polyimide resin contain an imide group in order to develop adhesion, which is an effect of one embodiment of the present invention.
• the coefficient of linear expansion of the polyimide resin used for layer A affects the adhesion, and specifically shows good adhesion when it is 30 ppm / ° C. or more. has been found independently and has led to an embodiment of the present invention.
• the linear expansion coefficient of the polyimide resin is the linear expansion coefficient in the plane direction when the polyimide resin used for the layer A is made into a film, and the degree of in-plane orientation in the layer A of the polyimide molecular chains is It is a reflection.
• a smaller linear expansion coefficient of the polyimide resin indicates that the polyimide molecular chains are oriented in the plane direction, and conversely, a larger coefficient indicates that the polyimide molecular chains are oriented in the thickness direction as well.
• the linear expansion coefficient of polyimide resin can be controlled by the type of monomer used.
• it is effective to use monomers having a rigid chemical structure and to increase their composition ratio.
• the polyimide molecular chains were oriented in the plane direction when processed (molded) into a film, and the molecular chains accumulated in the thickness direction. A state can be formed.
• the present inventors have independently found that if the coefficient of linear expansion of the polyimide resin of layer A is too small, the adhesion between the resin film and the electroless metal plating layer is reduced.
• the reason for this is not clear, but is presumed as follows.
• a polyimide obtained from a monomer mixture with a rigid chemical structure and a high composition ratio of the monomer is exposed to an alkaline chemical solution, the polyimide molecules near the surface are denatured into polyamic acid due to the cleavage reaction of the imide ring. , a state in which polyamic acid molecules oriented in the plane direction are deposited in the thickness direction is formed.
• the cohesive force between polyamic acid molecular chains is weaker than the cohesive force between polyimide molecular chains. Therefore, when an electroless metal plating layer (film) was formed on the surface of the film obtained by exposing the polyimide to an alkaline chemical solution, and the adhesion was evaluated, layer breakage occurred between polyamic acid molecular chains with weak cohesive force. It is presumed that the adhesion strength between the film and the plating layer (membrane) tends to be low as a result of peeling at the interface. It should be noted that the present invention is by no means limited to such speculation.
• the present inventors have found that the adhesion between the resin film and the electroless metal plating layer is enhanced when the linear expansion coefficient of the polyimide resin of the layer A is large (for example, 30 ppm / ° C. or more). found on its own. The reason for this is not clear, but is presumed as follows.
• the polyimide obtained from a monomer mixture that uses a monomer with a flexible chemical structure and a high composition ratio of the monomer is exposed to an alkaline chemical solution, the polyimide molecules near the surface are modified into polyamic acid due to the cleavage reaction of the imide ring.
• the polyimide has a small linear expansion coefficient and in-plane molecular orientation as described above. It is presumed that there is no layered separation between polyamic acid molecular chains as in the case of advanced polyimide, and as a result, the adhesion strength to electroless metal plating tends to increase. It should be noted that the present invention is by no means limited to such speculation.
• the polyimide resin used for the layer A tends to be randomly oriented more than the polyimide resin with advanced in-plane molecular orientation from the viewpoint that the cohesive force of the polyimide resin itself is not reduced even if the polyimide resin is exposed to an alkaline chemical solution. It is preferable to use a polyimide resin that has a certain property, that is, a polyimide resin that tends to have isotropic molecular orientation.
• polyimide resin there is a correlation between the degree of in-plane molecular orientation and the coefficient of linear expansion.
• the polyimide resin when the in-plane molecular orientation is highly advanced, and as a result the peel strength between the plane-oriented polymer chains is weakened, the coefficient of linear expansion is less than 30 ppm/°C.
• the polyimide resin used for the layer A has a tendency to be oriented not only in the surface direction but also in the thickness direction, that is, a random orientation tendency, thereby improving the adhesion to the electroless metal plating.
• the linear expansion coefficient of the polyimide resin is preferably 30 ppm/° C.
• the linear expansion coefficient of the polyimide resin of layer A is preferably 100 ppm/° C. or less, more preferably 90 ppm/° C. or less, more preferably 80 ppm/° C. or less, and more preferably 75 ppm/° C. or less. more preferably 70 ppm/°C or less, still more preferably 65 ppm/°C or less, and particularly preferably 60 ppm/°C or less.
• the coefficient of linear expansion of the polyimide resin used for layer A is preferably 30 ppm/°C or more, more preferably greater than 30 ppm/°C. As the linear expansion coefficient of the polyimide resin increases, the polyimide resin tends to exhibit thermoplasticity. Thermoplastic resin softens when it reaches a certain temperature, and there is an advantage that it can be processed by using this fact, for example, it can be thermocompressed with copper foil. From the viewpoint of improving adhesion to electroless metal plating, which is the object of one embodiment of the present invention, thermoplasticity is not an essential requirement.
• the polyimide resin can withstand the temperature of high temperature processes during its processing and the high temperature when parts are mounted.
• the polyimide resin used for the layer A preferably has a high glass transition temperature and a high elastic modulus at high temperatures, and there is no particular problem if the glass transition temperature is too high.
• the glass transition temperature of the polyimide resin which is an index of heat resistance, is preferably as high as possible, for example, preferably 180° C. or higher, more preferably 230° C. or higher.
• the polyimide resin used for the layer A has a certain or more elastic modulus even near the melting point of solder.
• the polyimide resin contained in Layer A preferably has a storage modulus at 300° C. of 0.2 ⁇ 10 8 Pa or more, more preferably 0.5 ⁇ 10 8 Pa or more, and 0 It is more preferably 0.8 ⁇ 10 8 Pa or more, and particularly preferably 1.0 ⁇ 10 8 Pa or more.
• a soluble polyimide that is soluble in an organic solvent As the polyimide resin for the layer A to produce the resin film of one embodiment of the present invention. Specifically, a soluble polyimide is dissolved in an organic solvent, and a fumed metal oxide is further dispersed in the resulting solution to obtain a dispersion. can be dried to obtain the resin film of one embodiment of the present invention.
• the layer A is used to prevent problems such as dissolution of the resin in the process using an organic solvent in the manufacturing process and mounting process of the printed circuit board.
• the polyimide resin used is preferably insoluble.
• the polyimide resin of the layer A and the layer B which is a heat-resistant resin film, are firmly adhered to each other.
• the precursor of the polyimide resin of layer A (or a solution containing the precursor) is brought into contact with layer B, and then the precursor is imidized. is preferred.
• the polyimide resin used for layer A can achieve one embodiment of the present invention whether it is soluble or insoluble, but is preferably insoluble.
• the polyimide resin contained in layer A is preferably a non-soluble polyimide resin.
• the polyimide resin is insoluble means that the polyimide resin does not dissolve in organic solvents generally used for industrial purposes. Specifically, the polyimide resin preferably does not dissolve in an organic solvent at 20° C. to 30° C. in an amount of 10% by weight or more, and more preferably does not dissolve in an amount of 5% by weight or more.
• organic solvents examples include alcohol solvents such as methanol, ethanol and propanol; ketone solvents such as acetone and methyl ethyl ketone; aromatic solvents such as toluene, xylene, cresol and benzene; Ether-based solvents; aprotic polar solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, and acetonitrile, but not limited thereto.
• alcohol solvents such as methanol, ethanol and propanol
• ketone solvents such as acetone and methyl ethyl ketone
• aromatic solvents such as toluene, xylene, cresol and benzene
• Ether-based solvents examples include aprotic polar solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl
• the polyimide resin used for the layer A must have a coefficient of linear expansion of 30 ppm/°C or more and 100 ppm/°C or less. It is preferable to appropriately control the physical properties of the polyimide resin, such as the glass transition temperature, the storage modulus at high temperatures, and the solubility in organic solvents. Selection of raw materials to be used is one means of controlling these physical properties within appropriate ranges. As raw material monomers for polyimide resins, there are monomers with flexible skeletons and monomers with rigid skeletons, and it is possible to realize desired physical properties by appropriately selecting these and adjusting the compounding ratio. Become.
• Diamines having a flexible skeleton include 4,4'-oxydianiline, 3,3'-oxydianiline, 3,4'-oxydianiline, bis ⁇ 4-(4-aminophenoxy)phenyl ⁇ sulfone, 2,2′-bis ⁇ 4-(4-aminophenoxy)phenyl ⁇ propane, bis ⁇ 4-(3-aminophenoxy)phenyl ⁇ sulfone, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3 , 3′-diaminodiphenyl ether, 4,4′-diaminodiphenylthioether, 3,4′-diaminodiphenylthioether, 3,3′-diaminodiphenylthioether, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 3,3'-diaminodipheny
• diamines having a rigid skeleton include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene, 1,2-diaminobenzene, benzidine, 3,3'-dichlorobenzidine, 3, 3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 2,2'-dimethoxybenzidine, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 2,2'- bis(trifluoromethyl)benzidine, 1,5-diaminonaphthalene, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 3,3'-diaminobenzanilide, and the like.
• 1,4-diaminobenzene p-phenylenediamine
• 1,3-diaminobenzene 1,2-diaminobenzene
• 4,4'-oxydianiline, 4,4'-diaminodiphenylpropane, 4,4'-diamino as the diamine having a flexible skeleton from the viewpoint of thermal property control and industrial availability.
• 1,3-bis(4-aminophenoxy)benzene and 2,2′-bis ⁇ 4-(4-aminophenoxy)phenyl ⁇ propane More than one species can be preferably used.
• diamines having a rigid skeleton 1,4-diaminobenzene (p-phenylenediamine), 1, 1, 4-diaminobenzene (p-phenylenediamine), 1, One or more selected from the group consisting of 3-diaminobenzene and 2,2'-dimethylbenzidine can be preferably used.
• 1,4-diaminobenzene p-phenylenediamine
• 2,2'-dimethylbenzidine can be preferably used.
• One of these diamines may be used alone, or two or more of them may be mixed (combined) and used.
• Tetracarboxylic dianhydrides having a flexible skeleton include 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,4'-oxydiphthalic anhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-diphenylsulfone Tetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene) phthalic anhydride, 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride, 2,2-bis( 3,4-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)propane dianhydride, 1,1-bis(2,3-dicarboxyphen
• tetracarboxylic dianhydrides having a rigid skeleton include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 1,2,5,6-naphthalenetetracarboxylic acid. acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, and the like.
• 3,3',4,4'-biphenyltetracarboxylic dianhydride 2 , 3,3′,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride and 4,4′-oxydiphthalic anhydride.
• 3,3',4,4'-biphenyltetracarboxylic dianhydride 2
• 3,3′,4′-biphenyltetracarboxylic dianhydride 3,3′,4,4′-benzophenonetetracarboxylic dianhydride
• 4,4′-oxydiphthalic anhydride 4,4′-oxydiphthalic anhydride.
• One or more of these can be preferably used.
• 3,3′,4,4′-biphenyltetracarboxylic dianhydride is more preferable, and various physical properties desired in a preferred embodiment of the present invention, namely, adhesion to an electroless plated film, It can be effectively used to develop the elastic modulus, the glass transition temperature, the linear expansion coefficient of the polyimide resin, and the like in a well-balanced manner.
• pyromellitic dianhydride is preferably used because it exhibits the effect of hardening the polymer chain with a relatively small amount and is easily available industrially. obtain.
• These tetracarboxylic dianhydrides may be used in combination of two or more.
• the inventors of the present invention have empirically obtained a tendency to show good adhesion by using a combination of acid dianhydrides and diamines that reduce the polarization of the imide ring of the polyimide resin. be. Specifically, at least one of 4,4'-oxydiphthalic dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride as the acid dianhydride, and 2,2'-bis as the diamine. A combination with (trifluoromethyl)benzidine is effective.
• a preferred combination of diamine and acid dianhydride is not particularly limited. 2,2′-bis(trifluoromethyl)benzidine, 4,4′-oxydianiline, 1,3-bis(4-aminophenoxy)benzene and 2,2′-bis ⁇ 4-(4-amino) as diamines phenoxy)phenyl ⁇ propane, and 4,4'-oxydiphthalic dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride as acid dianhydrides. It is preferable to select a combination with at least one of and further combine a fumed metal oxide in an appropriate type and blending amount.
• the adhesion to the electroless metal plating layer of one embodiment of the present invention can be improved, and in particular, the initial state after the formation of the electroless metal plating layer can be greatly improved, which is preferable.
• Polyamic acid which is a precursor of the polyimide of layer A, is obtained by mixing the diamine and acid dianhydride in an organic solvent so as to be substantially equimolar or substantially equimolar and reacting them.
• organic solvent Any organic solvent can be used as long as it can dissolve polyamic acid.
• amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. are preferred, and at least N,N-dimethylformamide and N,N-dimethylacetamide One can be used particularly preferably.
• the solid content concentration of the polyamic acid is not particularly limited, and if it is within the range of 5% by weight to 35% by weight, a polyamic acid having sufficient mechanical strength when made into a polyimide can be obtained.
• the order of addition of the raw materials diamine and acid dianhydride is also not particularly limited. It is possible to control the properties of the resulting polyimide not only by controlling the chemical structures of the raw materials diamine and acid dianhydride, but also by controlling the order of their addition.
• the polyimide structure obtained by combining the two has low durability against desmear liquid, so 1,4-diaminobenzene and pyromellitic acid It is preferable to adjust the order of addition of the dianhydride so as not to form a structure in which the two are directly bonded.
• Layer A may contain a resin other than the polyimide resin described above as a resin component. It is preferable that the content ratio of the polyimide resin in the resin component contained in the layer A is large.
• the polyimide resin in 100% by weight of the resin component contained in layer A, is preferably 50% by weight or more, more preferably 60% by weight or more, and more preferably 70% by weight or more. , more preferably 80% by weight or more, still more preferably 90% by weight or more, and most preferably 95% by weight or more. It is most preferable that the polyimide resin is 100% by weight in 100% by weight of the resin component contained in the layer A. In other words, it is most preferable that the layer A contains only the polyimide resin as the resin component.
• Fumed metal oxides used in one embodiment of the present invention are metal oxides based on silica, alumina, titania, or the like.
• the fumed metal oxide used in one embodiment of the present invention is preferably a metal oxide obtained by vapor phase synthesis.
• the resulting fumed metal oxide is characterized in that the structural unit is a structure in which primary particles aggregate.
• the fumed metal oxide has a structural unit of aggregated primary particles (for example, it has an aggregated structure like a cluster of grapes).
• a fumed metal oxide is mixed with a polyimide resin to form Layer A of one embodiment of the present invention.
• layer A has (i) a structural unit of a fumed metal oxide embedded in a polyimide resin with low voids, and (ii) the structural unit is on the surface of layer A. and/or exists from the vicinity of the surface to the bulk direction, and (iii) the structural unit is evenly present and dispersed in the layer A.
• a state is one embodiment of the present invention. We believe that it is effective for developing adhesion, which is the purpose of the morphology.
• spherical or amorphous metal oxide particles in which primary particles exist independently (for example, colloidal metal oxide particles) Silica) is not preferred because it tends to have weaker binding force with the polyimide resin than fumed metal oxides.
• the layer A may further contain spherical or amorphous metal oxide particles in which the primary particles are independently present. It is preferable that the amount of the metal oxide particles in the layer A is as small as possible.
• the amount of the metal oxide particles is preferably less than 10 parts by weight, more preferably 5 parts by weight or less, with respect to 100 parts by weight of the precursor of the polyimide resin, and 1 part by weight. or less, more preferably 0.5 parts by weight or less, and particularly preferably 0.1 parts by weight or less.
• the porosity in the layer A tends to increase when the blending ratio of the fumed metal oxide is increased.
• the porosity in the layer A is not too high, the binding force between the polyimide resin and the fumed metal oxide does not decrease, and the strength of the layer A itself tends to be good, resulting in electroless metal plating.
• the adhesion between the layer A and the layer B tends to be improved. Therefore, in blending the polyimide resin and the fumed metal oxide, it is preferable that the blending ratio of the fumed metal oxide is not too high.
• the porosity tends to decrease as the blending ratio of the fumed metal oxide decreases.
• the porosity in the layer A is not too low, it is preferable because sufficient adhesion to the electroless metal plating is likely to be exhibited. This is because the ratio of fumed metal oxide is not too low, so that the amount of compounds derived from the three components of "fumed metal oxide” - "metal (eg copper)" - “polyimide resin” is sufficient. I think that is the reason. It should be noted that the present invention is not limited to such speculation.
• the compounding ratio of the polyimide resin and the fumed metal oxide within an appropriate range in order to develop good adhesion.
• the primary particle size of the fumed metal oxide is small. It is 5 nm or more and 50 nm or less, more preferably 10 nm or more and 20 nm or less.
• the specific surface area of the fumed metal oxide is also a physical property value that expresses the primary particle size, and the larger the primary particle size, the smaller the specific surface area.
• the specific surface area of the fumed metal oxide is preferably 30 square meters/gram or more and 400 square meters/gram or less, more preferably 100 square meters/gram or more and 250 square meters/gram or less.
• a fumed metal oxide is a structure in which the primary particle diameter aggregates, and the apparent specific gravity can be used as an index representing the state of the structure of the fumed metal oxide.
• a low apparent specific gravity of the fumed metal oxide indicates that the structure of the fumed metal oxide has a bulky structure and large voids.
• a high apparent specific gravity of the fumed metal oxide indicates that the structure of the fumed metal oxide has a less bulky structure and smaller voids.
• a layer A with a small porosity can be produced by filling the voids of the structure in which the primary particle size of the fumed metal oxide aggregates with the polyimide resin component.
• the bonding strength between the polyimide resin and the fumed metal oxide does not decrease, and the strength of the layer A itself tends to be good, and as a result, the adhesion to the electroless metal plating tends to be good, And the adhesion between layer A and layer B also tends to be good. Therefore, in blending the polyimide resin and the fumed metal oxide, it is preferable that the blending ratio of the fumed metal oxide is not too high. Conversely, when the ratio of the fumed metal oxide is not too low, sufficient adhesion to the electroless metal plating tends to be exhibited. In other words, when blending the polyimide resin and the fumed metal oxide, blending the fumed metal oxide in the vicinity of the upper limit of the blending amount is effective for exhibiting good adhesion.
• the upper limit of the amount of fumed metal oxide compounded with respect to a certain amount of polyimide resin for making layer A with a small porosity varies depending on the apparent specific gravity of the fumed metal oxide and the type of surface treatment. That is, the adhesion can be further improved by adjusting the blending amount of the fumed metal oxide with respect to a certain amount of polyimide resin according to the apparent specific gravity of the fumed metal oxide and the type of surface treatment.
• the apparent specific gravity of the fumed metal oxide is preferably 20 grams/liter or more and 250 grams/liter or less, more preferably 20 grams/liter or more and 220 grams/liter or less.
• the apparent specific gravity of the fumed metal oxide is more preferably greater than 50 grams/liter and 250 grams/liter or less, more preferably 60 grams/liter or more and 250 grams/liter or less, and more preferably 70 grams/liter. It is more preferably 70 grams/liter or more and 220 grams/liter or less, more preferably 70 grams/liter or more and 220 grams/liter or less.
• the apparent specific gravity of the fumed metal oxide can be changed by modifying the structure of the fumed metal oxide by mechanically applying stress such as shear to the fumed metal oxide.
• fumed metal oxides Various surface treatments are possible for fumed metal oxides.
• Surface conditions of fumed metal oxides include silanol (untreated), dimethylsilyl, octylsilyl, trimethylsilyl, dimethylsiloxane, dimethylpolysiloxane, aminoalkylsilyl, methacrylsilyl, etc., all of which are industrially available.
• the surface treatment species of the fumed metal oxide and the polarity of the polyimide resin component are close to each other, the upper limit of the compounding amount of the fumed metal oxide tends to be high.
• the surface of the fumed metal oxide is not treated, the wettability with the alkaline chemical solution during the electroless metal plating process is too good, so the amount of the fumed metal oxide dissolved increases, and the surface roughness of the layer A increases. tend to become Therefore, it is preferable that the surface of the fumed metal oxide is subjected to a suitable hydrophobic treatment.
• the apparent specific gravity of the fumed metal oxide can be measured according to ISO787/XI.
• Fumed metal oxides that can be preferably used in one embodiment of the present invention are shown below, but are not limited to these. Fumed metal oxides that meet various property requirements, including apparent specific gravity, are more suitable for use in one embodiment of the present invention. Various grades of fumed metal oxides with different primary particle sizes, specific surface areas, surface treatment types, apparent specific gravities, and metal oxide types are available from Nippon Aerosil Co., Ltd., Asahi Kasei Wacker Silicone Co., Ltd., and Cabot Corporation, and can be preferably used. . The fumed metal oxide produced by Nippon Aerosil Co., Ltd. will be described below in detail.
• Aerosil R972, R972CF, R972V, etc. which are substantially the same except for the apparent specific gravity, can preferably be used, and among these, R972 (50 g/liter), which has a higher apparent specific gravity, can be used more preferably.
• Aerosil R974, R9200, VP RS920, etc. which are equivalent except for their apparent specific gravities, can preferably be used. liter or more and 120 g/liter or less) can be used more preferably.
• Aerosil NX130, RY200S, and R976 are fumed metal oxides manufactured by Nippon Aerosil Co., Ltd., which have a relatively low apparent specific gravity of 70 g/liter or less, which is one of the preferable physical properties of one embodiment of the present invention.
• NAX50, NX90G, NX90S, RX200, RX300, R812, R812S, etc. can be preferably used. Fumed metal oxides manufactured by Nippon Aerosil Co., Ltd.
• Aerosil 200V Aerosil 200V
• AEROIDE TiO2 P90 AEROIDE TiO2 NKT90
• OX50 RY50
• RY51 AEROIDE TiO2 P25, R8200, and RM50.
• RX50, AEROIDE TiO2 T805, R7200, etc. are also preferably usable.
• Aerosil VP RS920 has been sold under the name of "Aerosil E9200" since November 2021.
• "Aerosil” or “AEROSIL” is a registered trademark of Evonik Operations GmbH.
• As the fumed metal oxide a fumed metal oxide synthesized by vapor phase synthesis and having a structure in which primary particle diameters are aggregated can be preferably used.
• fumed silica such as Aerosil R972, 972V, NX130, R9200, VP RS920, R974, R976, R8200 has a good surface shape of layer A formed by dissolution in an alkaline environment. , the surface roughness is also within an appropriate range.
• Layer A containing a polyimide resin and a fumed metal oxide is preferably an imidized product of a mixture of a precursor of the polyimide resin and a fumed metal oxide (for example, a fumed metal oxide-dispersed polyamic acid solution described later). .
• the fumed metal oxide is mixed with a polyamic acid solution that is a precursor of the polyimide resin that constitutes Layer A, (a) the resulting mixture is applied to the heat-resistant film of Layer B, and Layer B is formed.
• the resin film of one embodiment of the present invention is obtained by co-extrusion with the resin precursor solution of layer B or the resin solution of layer B, etc., drying the obtained extrudate, and imidizing the mixture. be able to.
• the amount of the fumed metal oxide compounded is preferably 10 parts by weight or more and 130 parts by weight or less with respect to 100 parts by weight of the polyimide resin precursor of the layer A.
• the preferred number of parts of the fumed metal oxide to be added to the polyimide precursor (polyimide resin) of layer A can be adjusted to some extent by the apparent specific gravity of the fumed metal oxide, but there is also the influence of the surface treatment of the fumed metal oxide. , I can't say for certain.
• the preferred number of parts of the fumed metal oxide to be blended is described.
• the number of parts of the fumed metal oxide (relative to the solid content of the polyimide (precursor) resin) is 100 parts by weight of the precursor of the polyimide resin. 15 parts by weight or more and 80 parts by weight or less, more preferably 20 parts by weight or more and 60 parts by weight or less.
• the blending number of the fumed metal oxide (relative to the polyimide (precursor) resin solid content of 100 parts by weight) is 10 parts by weight or more and 130 parts by weight. parts by weight or less, more preferably 15 to 120 parts by weight, and even more preferably 20 to 100 parts by weight.
• the preferred number of parts to be blended varies depending on the apparent specific gravity of the fumed metal oxide, and the higher the apparent specific gravity of the fumed metal oxide, the greater the amount of the fumed metal oxide to be blended, and the more preferable blended amount.
• Tend. By blending the fumed metal oxide in the above range with respect to 100 parts by weight of the precursor of the polyimide resin, it is possible to exhibit a better adhesion strength, especially in the initial state after the electroless plating film is formed. It is possible to make it adhere to. It is also possible to mix (combine) multiple types of fumed metal oxides with different primary particle sizes, specific surface areas, surface treatment types, apparent specific gravities, metal oxide types, and the like.
• a polyimide resin precursor solution for Layer A and a fumed metal oxide are mixed and dispersed to form a fumed metal oxide dispersed polyamic acid solution (hereinafter Layer A dispersion). (sometimes referred to as .) is preferably obtained.
• the layer A can be obtained by imidizing the layer A dispersion.
• layer A is preferably an imidized mixture of a polyimide resin precursor and the fumed metal oxide. This configuration has the advantage that the adhesion between the layer A and the layer B is enhanced.
• the procedure for obtaining the layer A dispersion will be specifically described below, but one embodiment of the present invention is not limited thereto.
• An organic solvent is added to the fumed metal oxide, and the fumed metal oxide is dispersed in the organic solvent to the structural units of the structure in which the primary particles are aggregated.
• Dispersion methods include dispersers, homogenizers, planetary mixers, bead mills, rotation/revolution mixers, rolls, kneaders, high-pressure dispersers, ultrasonic waves, and resolvers. As long as the effect of one embodiment of the present invention can be obtained, the fumed metal oxide does not have to be dispersed to the above structural units in the organic solvent.
• the fumed metal oxide when the fumed metal oxide can be dispersed to the structural unit, the fumed metal oxide does not exist as a lump in the layer A, and in that case, the surface roughness of the layer A is small, which is one of the aspects of the present invention. This is preferable because it is advantageous for the formability of fine wiring, which is the aim of the embodiment. It is also possible to disperse and pulverize the fumed metal oxide under conditions that make the structural unit smaller.
• the organic solvent a solvent used for polyamic acid polymerization can be used, and amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferably used. is not limited to
• the concentration of the finally obtained layer A dispersion is not particularly limited, it is preferable to make the concentration and viscosity suitable for the next process.
• An organic solvent can be appropriately used for adjusting the concentration and viscosity of the layer A dispersion.
• amines for the purpose of imparting adhesion to the layer B, a dehydrating agent for imidizing polyamic acid, a catalyst, etc. may be further added to the layer A dispersion or the like.
• a filler can also be added to the layer A dispersion for the purpose of improving various properties of the film such as slidability, thermal conductivity, electrical conductivity, corona resistance, and loop stiffness.
• Any filler may be used, but preferred examples include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, and mica.
• Thermosetting resins such as epoxy resins and phenoxy resins, and thermoplastic resins such as polyether ketones and polyether ether ketones may also be used as long as the properties of the resulting resin layer as a whole are not impaired.
• a method for adding these resins if they are soluble in a solvent, a method of adding them to the polyamic acid can be mentioned. If the polyimide is also soluble, it may be added to the polyimide solution.
• a layer A dispersion can be obtained by the above procedure.
• Layer A is formed on one side or both sides of layer B, which is a heat-resistant resin film of one embodiment of the present invention.
• the coefficient of linear expansion of layer B is preferably 20 ppm/° C. or less.
• the resin composition of layer B is not particularly limited, a liquid crystal polymer film, a resin film containing reinforcing fibers, a resin film containing an inorganic filler, polyimide, and the like are preferable.
• Layer B is more preferably a film containing polyimide (or made of polyimide) from the viewpoint of heat resistance, flexibility, heat resistance, etc., and contains non-thermoplastic polyimide (or consists of non-thermoplastic polyimide ) film is more preferred.
• the linear expansion coefficient of a polyimide resin film can be controlled by the type of monomer used.
• a monomer having a rigid chemical structure and increase its composition ratio By using a monomer with a rigid chemical structure and increasing its composition ratio, the polyimide molecular chains are oriented in the plane direction when molded (processed) into a film, and the molecular chains are deposited in the thickness direction. can be formed.
• a monomer having a flexible chemical structure and increase its composition ratio in order to increase the linear expansion coefficient of the polyimide resin film.
• the polyimide molecular chains are oriented not only in the plane direction but also in the thickness direction when formed into a film, that is, randomly oriented. tend to show
• the diamine used in the production of the non-thermoplastic polyimide film is not particularly limited, but the linear expansion coefficient of the finally obtained polyimide film is 20 ppm / ° C. or less. need to be Therefore, in the production of a non-thermoplastic polyimide film, it is preferable to use an appropriate combination of a rigid-structured diamine and a flexible-structured diamine according to the structure of the acid dianhydride.
• the acid dianhydride used in the production of the non-thermoplastic polyimide film is not particularly limited, but the linear expansion coefficient of the finally obtained polyimide is 20 ppm / °C or less. Therefore, in the production of the non-thermoplastic polyimide film, it is preferable to use an appropriate combination of a rigid-structure acid dianhydride and a flexible-structure acid dianhydride according to the structure of the diamine.
• Specific acid dianhydrides having a rigid structure that are suitably used for the production of non-thermoplastic polyimide films include 3,3',4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride.
• Acid dianhydrides having a flexible structure which are preferably used for the production of non-thermoplastic polyimide films, are 3,3′,4,4′-benzophenonetetracarboxylic dianhydride and 4,4′-oxydiphthalic dianhydride. etc.
• acid dianhydrides listed when explaining the polyimide resin of Layer A it is also possible to appropriately use the acid dianhydrides listed when explaining the polyimide resin of Layer A.
• Polyamic acid which is a precursor of polyimide, is obtained by mixing the diamine and acid dianhydride in an organic solvent so that they are substantially equimolar or approximately equimolar, and reacting them. Any organic solvent can be used as long as it can dissolve polyamic acid.
• organic solvent amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. are preferred, and at least N,N-dimethylformamide and N,N-dimethylacetamide One can be used particularly preferably.
• the solid content concentration of the polyamic acid is not particularly limited, and if it is within the range of 5% by weight to 35% by weight, a polyamic acid having sufficient mechanical strength when made into a polyimide can be obtained.
• the order of addition of the raw materials diamine and acid dianhydride is also not particularly limited. It is possible to control the properties of the resulting polyimide not only by controlling the chemical structures of the raw materials diamine and acid dianhydride, but also by controlling the order of their addition.
• a filler can also be added to the polyamic acid for the purpose of improving various properties of the film such as slidability, thermal conductivity, electrical conductivity, corona resistance, and loop stiffness.
• Any filler may be used, but preferred examples include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, and mica.
• Thermosetting resins such as epoxy resins and phenoxy resins, and thermoplastic resins such as polyether ketones and polyether ether ketones may also be used as long as the properties of the resulting resin layer as a whole are not impaired.
• a method for adding these resins if they are soluble in a solvent, a method of adding them to the polyamic acid can be mentioned.
• the polyimide is also a soluble polyimide, it may be added to the polyimide solution. If the polyimide is insoluble in a solvent, the polyamic acid is first imidized, and then the polyimide obtained by imidization and the polyimide insoluble in the solvent to be added are combined by melt-kneading. .
• the resulting flexible metal-clad laminate may deteriorate in solder heat resistance and/or heat shrinkage, it is desirable not to use polyimide with meltability in one embodiment of the present invention. Therefore, it is desirable to use a soluble resin for mixing with polyimide.
• a method for obtaining a non-thermoplastic polyimide film preferably used for layer B in one embodiment of the present invention preferably includes the following steps (i) to (iv).
• the methods of subsequent steps are roughly divided into thermal imidization and chemical imidization.
• the thermal imidization method is a method in which a polyamic acid solution as a film forming dope is cast on a support without using a dehydration ring-closing agent or the like, and imidization is proceeded only by heating.
• the chemical imidization method is a method in which at least one of a dehydration ring-closing agent and a catalyst is added to a polyamic acid solution as an imidization accelerator, and a film-forming dope is used to promote imidization. Either method may be used, but the chemical imidization method is superior in productivity.
• an acid anhydride represented by acetic anhydride can be suitably used as the dehydration ring-closing agent.
• Tertiary amines such as aliphatic tertiary amines, aromatic tertiary amines, and heterocyclic tertiary amines can be suitably used as catalysts.
• a glass plate, an aluminum foil, an endless stainless steel belt, a stainless drum, or the like can be suitably used as a support for casting the film-forming dope.
• the heating conditions are set according to the thickness and/or the production rate of the film to be finally obtained, and the film forming dope is either partially imidized or dried, and then the imidized material is peeled off from the support. to obtain a polyamic acid film (hereinafter referred to as a gel film).
• the ends of the gel film are fixed to dry the gel film while avoiding shrinkage during curing, and water, residual solvent, and imidization accelerator are removed from the gel film.
• the amic acid remaining in the gel film is completely imidized to obtain a film containing polyimide.
• the heating conditions may be appropriately set according to the thickness of the finally obtained film and/or the production speed.
• an industrially available polyimide film as the layer B of one embodiment of the present invention.
• Examples of commercially available polyimide films that can be used as layer B include “Apical” (manufactured by Kaneka), “Kapton” (manufactured by DuPont, Toray DuPont), and “Upilex” (manufactured by Ube Industries). be done.
• a resin film according to one embodiment of the present invention may have the following aspects: comprising a layer A and a layer B;
• the layer A contains a polyimide resin and a fumed metal oxide
• the layer B contains a heat-resistant resin film having a coefficient of linear expansion of 20 ppm/° C. or less, or is the heat-resistant resin film
• the layer A is formed on at least one surface of the layer B,
• the resin film, wherein the linear expansion coefficient of the polyimide resin is 30 ppm/°C or more and 100 ppm/°C or less.
• the layer A containing a polyimide resin and a fumed metal oxide is a heat-resistant resin film having a coefficient of linear expansion of 20 ppm/° C. or less.
• the layer A formed on the surface, the linear expansion coefficient of the polyimide resin is 30 ppm / ° C. or more and 100 ppm / ° C. or less
• the layer A containing the polyimide resin and the fumed metal oxide is a precursor of the polyimide resin. and the fumed metal oxide, and imidizing the resulting fumed metal oxide-dispersed polyamic acid solution.
• a method for producing a resin film according to an embodiment of the present invention may be in the following aspects: A method for producing a resin film, Step 1 of mixing a polyamic acid solution of a polyimide resin precursor and a fumed metal oxide; and a step 2 of imidizing the fumed metal oxide-dispersed polyamic acid solution obtained in step 1,
• the resin film is including the layer A and the layer B;
• the layer A contains the polyimide resin and the fumed metal oxide,
• the layer B contains a heat-resistant resin film having a coefficient of linear expansion of 20 ppm/° C.
• the layer A is formed on at least one surface of the layer B,
• the method for producing a resin film, wherein the linear expansion coefficient of the polyimide resin is 30 ppm/°C or more and 100 ppm/°C or less.
• the fumed metal oxide-dispersed polyamic acid solution obtained in Step 1 and Step 1 is the same as the embodiment described in the section ⁇ Fumed metal oxide-dispersed polyamic acid solution>, so the description is incorporated herein. Description is omitted.
• the preferred embodiment described in the section ⁇ Fumed metal oxide-dispersed polyamic acid solution> is also a preferred embodiment for Step 1 and the fumed metal oxide-dispersed polyamic acid solution obtained in Step 1.
• the resin film of one embodiment of the present invention includes layer A and layer B. Moreover, the resin film of one embodiment of the present invention is composed of a layer A and a layer B. As shown in FIG. Layer B in one embodiment of the present invention must be a heat-resistant resin film having a coefficient of linear expansion of 20 ppm/° C. or less.
• the layer B that is, the heat-resistant resin film, a liquid crystal polymer film, a resin film containing reinforcing fibers, a resin film containing an inorganic filler, an industrially available polyimide film, and the above steps (i) to (iv) and non-thermoplastic polyimide films produced through
• the layer A dispersion obtained in step 1 is applied (applied) to the surface of these heat-resistant resin films (layer B), and the layer A dispersion is dried and imidized to form one embodiment of the present invention.
• Obtaining a resin film is preferably feasible.
• a co-extrusion die having a plurality of flow paths may be used to obtain a resin film of one embodiment of the present invention having multiple layers.
• the layer A dispersion is applied to the surface of the gel film in the step (iii), and both the gel film and the layer A are simultaneously dried and imidized to obtain the resin film of one embodiment of the present invention. Also good.
• the heating conditions may also affect various film properties and/or adhesion to the electroless metal plating layer. Therefore, it is preferable to set an appropriate heating temperature and heating time.
• the layer A dispersion and/or the final thickness of the layer A it is also preferable to set appropriate heating conditions according to the chemical structure, concentration, and solvent type of the polyamic acid contained in the layer A dispersion and/or the final thickness of the layer A, and generally suitable heating conditions are set.
• step 2 There are roughly two methods for imidization in step 2: thermal imidization and chemical imidization.
• thermal imidization method which is a method of promoting imidization only by heating without using a dehydrating ring-closing agent or the like.
• Layer A has the function of adhering the electroless metal plating layer. It is assumed that the layer A is laminated with a copper foil to produce a copper-clad laminate. In this case, it is preferable that the adhesive layer has a thickness enough to bite into the surface unevenness of the roughened surface of the copper foil. In order to obtain a metal layer, even if the thickness of the layer A is relatively thin, the original function of adhesion with the electroless metal plating layer can be exhibited. From the viewpoint of industrially stably forming the layer A, the layer A preferably has a thickness of 0.1 microns or more and 30 microns or less, more preferably 1 micron or more and 10 microns or less.
• the linear expansion coefficient of the resin film of one embodiment of the present invention when used for a printed wiring board, it is preferable to design the linear expansion coefficient appropriately so that the temperature of the composite with the conductor layer including the electroless metal plating layer It is possible to control warping due to environmental changes.
• the linear expansion coefficient of the resin film of one embodiment of the present invention can be controlled. be.
• An electroless metal plating layer can be formed on the surface of the layer A of the resin film of one embodiment of the present invention.
• a metallized resin film can be obtained.
• a metallized resin film in which an electroless metal plating layer is formed on the surface of layer A is also an embodiment of the present invention.
• An electroless metal plating layer (film) obtained by electroless metal plating can be thinner than a general copper foil.
• the thickness of the electroless metal plating layer is preferably 0.01 microns to 10.00 microns, more preferably 0.10 microns to 2.00 microns, still more preferably 0.20 microns to 1.00 microns. be.
• Electroless metal plating of one embodiment of the present invention is preferably applicable to reduction-type electroless plating using a chemical reaction.
• Metal species for electroless metal plating include copper, nickel, gold, silver, and the like, all of which are applicable to one embodiment of the present invention. Of these, electroless copper plating and electroless nickel plating are preferred. Among them, electroless copper plating is widely used as a process for making the insulating resin surface of through-holes and via walls of printed wiring boards conductive. Yes, and most preferably available. In other words, the electroless metal plating of one embodiment of the present invention is preferably electroless copper plating.
• the electroless copper plating process which is widely used for printed wiring boards, can use the chemical processes of plating chemical manufacturers.
• desmear treatment is generally performed before electroless copper plating.
• Desmear treatment is originally performed for the purpose of removing smears generated on the surface of copper generated in the through-hole forming process and the laser via forming process.
• Desmear treatment also chemically changes the surface of the resin film of one embodiment of the present invention, and can be preferably used.
• the desmear process and the electroless copper plating process are each performed by sequentially treating the object to be plated with a plurality of chemical solutions.
• the desmear process consists of a chemical solution responsible for swelling, a chemical solution responsible for etching, and a chemical solution responsible for reduction.
• the electroless copper plating process includes a series of chemical solutions for cleaning and conditioner, chemical solutions for soft etching, chemical solutions for pre-dip, chemical solutions for catalyst application, chemical solutions for activation, and chemical solutions for electroless copper plating. It is composed of each chemical solution that plays each role.
• chemical solutions manufactured by Atotech, Adcopper IW manufactured by Okuno Chemical Industry Co., Ltd., Surcup PEA manufactured by Uemura Kogyo Co., Ltd., chemical solutions manufactured by Rohm and Haas Electronic Materials Co., Ltd., chemical solutions manufactured by Meltex Co., Ltd., and various chemical solutions and processes. can be applied, and can be combined as appropriate.
• electroless copper platings sometimes contain a small amount of nickel component, but these electroless metal platings (electroless copper platings) can be used as long as they do not impair the effects of one embodiment of the present invention.
• the layer A When the layer A is electrolessly plated, the layer A may be electrolessly plated directly, or the layer A is pretreated by alkali treatment, desmear treatment, or the like. After that, electroless plating may be applied to the layer A after the pretreatment.
• alkaline aqueous solutions for alkali treatment include sodium hydroxide aqueous solutions and potassium hydroxide aqueous solutions.
• the resin film and the electroless metal plating are sufficiently The aim is to develop good adhesion. If the adhesion is low, problems such as the circuit peeling off from the resin film substrate may occur in the subsequent circuit forming process.
• the metallized resin film is heated at a temperature of 150 ° C. or higher, for example, to improve the adhesion. Improvements may be made.
• the fact that the resin film according to one embodiment of the present invention has excellent adhesion means that at least the metallized resin film obtained by forming an electroless metal plating layer on the surface of the layer A of the resin film is
• the electroless metal plating layer in the metallized resin film is excellent in peel strength (for example, exhibits a peel strength of 3 N/cm or more) without subjecting the metallized resin film to heat treatment at 150 ° C. or higher. Intend.
• a metallized resin film obtained by forming an electroless metal plating layer on the surface of layer A of a resin film, and the metallized resin film is subjected to heat treatment at 150° C. or higher.
• the peel strength of the electroless metal-plated layer in the metallized resin film without the coating is sometimes referred to as "initial peel strength".
• a metallized resin film obtained by forming an electroless metal plating layer on the surface of the layer A of the resin film is subjected to heat treatment at 150° C. or higher. It is preferable that the electroless metal plating layer in the metallized resin film exhibits a peel strength of 3 N/cm or more, more preferably 5 N/cm or more.
• in the metallized resin film, after forming the electroless metal plating layer, without performing heat treatment at 150 ° C. or higher it is 3 N / cm or more, more preferably 5 N / cm or more. It is preferable to exhibit peel strength.
• the base material (resin film) is made conductive by electroless metal plating, even if good adhesion strength is exhibited if there is no circuit pattern on the back surface of the base material (resin film), When there is a circuit pattern on the back surface, sufficient adhesion strength may not be exhibited.
• the metallized resin film is not heated to a high temperature, good adhesion can be obtained regardless of the presence or absence of a circuit pattern on the back surface, and the heat resistance when used as a printed wiring board. It also has sex.
• the resin film according to one embodiment of the present invention is not essential, but for the metallized resin film obtained by forming electroless metal plating layers on both sides of the layer A of the resin film, the metallized resin It is preferable that the electroless metal plating layer in the metallized resin film has excellent peel strength (for example, exhibits a peel strength of 3 N/cm or more) without subjecting the film to heat treatment at 150° C. or higher.
• a metallized resin film obtained by forming electroless metal plating layers on both sides of layer A of a resin film is subjected to heat treatment at 150° C. or higher.
• the electroless metal plating layer in the metallized resin film exhibits a peel strength of 3 N/cm or more, more preferably 5 N/cm or more.
• the heat treatment at 150° C. or higher is not performed, and the thickness of the metallized resin film is 3 N/cm or more, more preferably 5 N/cm or more. It is preferable to express the above peel strength.
• the metallized resin film obtained by forming an electroless metal plating layer on the surface of the layer A of the resin film is not actively heated and dried at room temperature. However, sufficient adhesion can be obtained. If the metallized resin film obtained after forming the electroless metal plating layer is wet with a cleaning liquid such as water, problems may occur in the next process, such as the dry film resist lamination process. Therefore, the heat drying treatment for the purpose of drying can be preferably carried out on the metallized resin film obtained by the treatment for forming the electroless metal plating layer.
• the heating temperature in the heat drying treatment is preferably 150° C. or lower, more preferably less than 150° C., and still more preferably 100° C. or lower.
• the heating time in the heat drying treatment is preferably 30 minutes or less, more preferably 10 minutes or less.
• a metallized resin film (heat treatment at 150 ° C. or higher) obtained by performing only the formation treatment of the electroless metal plating layer on the resin film It is preferable that the metallized resin film that has not been subjected to the above) has sufficient adhesion.
• the peel strength (initial peel strength) of the metallized resin film is preferably 3 N/cm or more, more preferably 5 N/cm or more, still more preferably 6 N/cm or more, and even more preferably 7 N/cm or more.
• a printed wiring board using the resin film according to one embodiment of the present invention or the metallized resin film according to one embodiment of the present invention is also one embodiment of the present invention.
• a method for manufacturing a printed wiring board using the resin film of one embodiment of the present invention will be described below.
• the resin film of one embodiment of the present invention is an electroless copper plating film (electroless copper plating layer) firmly adhered to the surface of the low-roughness layer A by electroless metal plating, especially using a general-purpose electroless copper plating chemical. ) can be a formed metallized resin film.
• narrow-pitch circuits can be formed regardless of the subtractive method or the additive method, and without using complicated methods such as button plating. is.
• a conductor layer and a circuit having a narrow pitch and a good circuit shape, excellent transmission characteristics, and a thin thickness can be obtained.
• Obtainable That is, by using the resin film or metallized film according to one embodiment of the present invention, it is possible to manufacture a printed wiring board having high flexibility. Substrates, chip-on-film substrates, etc. can be manufactured.
• various printed wiring boards described above can be obtained by performing the following methods (1) to (3) on the resin film of one embodiment of the present invention:; 1) First, a through-hole is formed, and then an electroless metal-plated layer forming process is performed to simultaneously form an electroless metal-plated layer (film) on the wall surface of the through-hole and the surface of the resin film; Further, (3) multilayering treatment, protective film forming treatment, surface treatment, etc. are performed by known methods. In order to form a narrow-pitch circuit, it is preferable that the surface roughness of the resin film of one embodiment of the present invention is small.
• the surface roughness Ra of the resin film (layer A) exposed by removing the electroless metal plating layer (film) by etching is preferably 200 nm or less, and preferably 150 nm. It is more preferably 100 nm or less, and more preferably 100 nm or less.
• the surface roughness is the number of parts of the fumed metal oxide added to the polyimide precursor, the type of fumed metal oxide (apparent specific gravity, surface treatment, etc.), the chemical structure of the polyimide resin of layer A, the desmear condition, and the electroless metal plating layer. can be adjusted by changing the conditions of the forming process of .
• a printed wiring board obtained according to one embodiment of the present invention can transmit electrical signals in the GHz band by using the resin film or metallized resin film according to one embodiment of the present invention.
• transmitting an electrical signal in the GHz band means having, in order, a 12-micron-thick signal line/a 25-micron-thick resin film according to an embodiment of the present invention/a 12-micron-thick ground layer, and the characteristic impedance is
• the insertion loss S21 parameter of a microstrip line transmission line processed to be 50 ⁇ is measured using a network analyzer E5071C (Keysight Technologies) and a GSG250 probe
• the transmission loss at 10 GHz is less than 7 dB/100 mm
• It means that the transmission loss at 20 GHz is less than 11 dB/100 mm and the transmission loss at 30 GHz is less than 14 dB/100 mm.
• the signal line with a thickness of 12 microns is intended to be a wiring composed of a conductor layer with a total thickness of 12 microns, which is composed of an electroless metal plating layer and an electrolytic copper plating layer.
• the 12-micron-thick ground layer is intended to be a ground layer composed of a conductor layer with a total thickness of 12 microns, which is composed of an electroless metal-plated layer and an electrolytic copper-plated layer.
• a film (laminate) having, in order, a 12-micron-thick signal line/a 25-micron-thick resin film according to an embodiment of the present invention and (ii) a 12-micron-thick signal line/a 25-micron-thick
• the resin film according to one embodiment of the present invention/film (laminate) having a 12-micron-thick ground layer in order can also be said to be the metallized resin film according to one embodiment of the present invention.
• a layer A containing a polyimide resin and a fumed metal oxide is formed on at least one surface of a layer B, which is a heat-resistant resin film having a coefficient of linear expansion of 20 ppm/° C. or less, A resin film, wherein the linear expansion coefficient of the polyimide resin is 30 ppm/°C or more and 100 ppm/°C or less.
• the metallized resin film exhibits a peel strength of 5 N/cm or more without heat treatment at 150° C. or more after forming the electroless metal plating layer [9] The metallized resin film according to any one of [11].
• a layer A containing a polyimide resin and a fumed metal oxide is formed on at least one surface of a layer B, which is a heat-resistant resin film having a coefficient of linear expansion of 20 ppm/° C. or less, and the linear expansion of the polyimide resin
• the layer A having an expansion coefficient of 30 ppm/° C. or more and 100 ppm/° C. or less and containing the polyimide resin and the fumed metal oxide comprises a polyamic acid solution of the precursor of the polyimide resin and the fumed metal oxide.
• the fumed metal oxide-dispersed polyamic acid solution is applied to the layer B made of the heat-resistant resin film, and the fumed metal oxide-dispersed polyamic acid solution is dried and imidized [ 15].
• the coefficient of linear expansion was measured using TMA120C manufactured by Seiko Electronics Corporation. The sample size was 3 mm wide and 10 mm long. After raising the temperature of the sample from 10 ° C. to 400 ° C. at 10 ° C./min with a load of 3 g, the temperature of the sample was cooled to 10 ° C., and the temperature of the sample was further increased at 10 ° C./min. was heated, and the average value was calculated from the coefficient of thermal expansion from 100° C. to 200° C. during the second temperature rise.
• ⁇ Solubility> The solubility in the following organic solvents was evaluated for the monolayer film obtained in the section ⁇ Preparation of monolayer film of polyimide resin for layer A>. If there was an organic solvent that dissolved at a concentration of 10% by weight or more in any one of them, it was soluble and evaluated as ⁇ (bad), and if it did not dissolve at 10% by weight or more, it was insoluble and evaluated as ⁇ (good). .
• the temperature of the organic solvent was 25°C.
• Organic solvent species methanol, methyl ethyl ketone, toluene, tetrahydrofuran, N,N-dimethylformamide ⁇ Preparation of double-sided copper-clad laminate for evaluation>
• the resin films obtained in Examples and Comparative Examples were subjected to desmear treatment, electroless copper plating and electrolytic copper plating in sequence under the conditions shown in Tables 1 to 3 (Atotech) to obtain double-sided laminates for evaluation. rice field.
• the electrolytic copper plating thickness was 12 microns.
• a sample for peel strength measurement without copper on the back surface and a sample for peel strength measurement with copper on the back surface were prepared from the metallized resin films (double-sided copper-clad laminates) produced from the resin films obtained in Examples and Comparative Examples. made. Initial peel strength, peel strength after high-temperature heat treatment, and heat-resistant peel strength were measured for each sample for peel strength measurement.
• the copper layer on one side of the double-sided copper-clad laminate was entirely removed by etching, and the copper layer on the remaining side was etched with a masking tape to form a copper pattern of 5 mm width.
• the initial peel strength, the peel strength after high-temperature heat treatment, and the heat-resistant peel strength were measured according to the following procedure.
• Heat-resistant peel strength - no copper on the back side After pattern etching, water droplets on the double-sided copper-clad laminate were wiped off, the masking tape was removed, and drying was performed at 50°C for 10 minutes. Then, the double-sided copper-clad laminate was subjected to a heat resistance test environment of 150° C. for 168 hours, and then the peel strength was measured. It was carried out for evaluation of heat resistance.
• Form 2 - with back copper A copper pattern with a width of 5 mm was formed on the copper layer on one side of the double-sided copper-clad laminate by etching using a masking tape, and a pattern for evaluation with a copper layer on the entire back surface was formed.
• the initial peel strength, the peel strength after high-temperature heat treatment, and the heat-resistant peel strength were measured according to the following procedure.
• Heat-resistant peel strength-with copper on the back side After pattern etching, water droplets on the double-sided copper-clad laminate were wiped off, the masking tape was removed, and drying was performed at 50°C for 10 minutes. Then, the double-sided copper-clad laminate was subjected to a heat resistance test environment of 150° C. for 168 hours, and then the peel strength was measured. It was carried out for evaluation of heat resistance.
• peel strength measurement The six types of peel strength measurements were performed on one double-sided copper-clad laminate. The peel strength was measured by peeling at a crosshead speed of 50 mm/min and a peeling angle of 180°, and measuring the load.
• ⁇ Surface roughness Ra> The copper layers of the double-sided copper-clad laminates for evaluation obtained in Examples and Comparative Examples were dissolved and removed by etching.
• the surface roughness (Ra) of the exposed resin film was measured according to JIS C 0601-2001 using a scanning probe microscope (SPM, Dimension Icon manufactured by Bruker AXS).
• BPDA solution (1) A solution of 0.51 g of BPDA dissolved in 9.7 g of DMF (hereinafter sometimes referred to as BPDA solution (1)) was separately prepared.
• the BPDA solution (1) was gradually added to the reaction solution while paying attention to the viscosity, and the reaction solution in the flask was stirred. When the viscosity of the reaction solution reached 1000 poise, addition of the BPDA solution (1) and stirring of the reaction solution were stopped. Through such operations, a polyamic acid solution, which is a polyimide precursor, was obtained.
• a solution was separately prepared by dissolving 0.55 g of BPDA in 10.5 g of DMF (hereinafter sometimes referred to as BPDA solution (2)).
• BPDA solution (2) was gradually added to the reaction solution while paying attention to the viscosity, and the reaction solution in the flask was stirred. When the viscosity of the reaction solution reached 1000 poise, addition of the BPDA solution (2) and stirring of the reaction solution were stopped. Through such operations, a polyamic acid solution, which is a polyimide precursor, was obtained.
• a solution was separately prepared by dissolving 0.53 g of BPDA in 10.1 g of DMF (hereinafter sometimes referred to as BPDA solution (3)).
• the BPDA solution (3) was gradually added to the reaction solution while paying attention to the viscosity, and the reaction solution in the flask was stirred. When the viscosity of the reaction solution reached 1000 poise, addition of the BPDA solution (3) and stirring of the reaction solution were stopped. Through such operations, a polyamic acid solution, which is a polyimide precursor, was obtained.
• the BPDA solution (4) was gradually added to the reaction solution while paying attention to the viscosity, and the reaction solution in the flask was stirred. When the viscosity of the reaction solution reached 1000 poise, addition of the BPDA solution (4) and stirring of the reaction solution were stopped. Through such operations, a polyamic acid solution, which is a polyimide precursor, was obtained.
• the BPDA solution (5) was gradually added to the reaction solution while paying attention to the viscosity, and the reaction solution in the flask was stirred. When the viscosity of the reaction solution reached 1000 poise, addition of the BPDA solution (5) and stirring of the reaction solution were stopped. Through such operations, a polyamic acid solution, which is a polyimide precursor, was obtained.
• the BPDA solution (6) was gradually added to the reaction solution while paying attention to the viscosity, and the reaction solution in the flask was stirred. When the viscosity of the reaction solution reached 1000 poise, addition of the BPDA solution (6) and stirring of the reaction solution were stopped. Through such operations, a polyamic acid solution, which is a polyimide precursor, was obtained.
• a solution was separately prepared by dissolving 0.54 g of BPDA in 10.3 g of DMF (hereinafter sometimes referred to as BPDA solution (7)).
• the BPDA solution (7) was gradually added to the reaction solution while paying attention to the viscosity, and the reaction solution in the flask was stirred. When the viscosity of the reaction solution reached 1000 poise, addition of the BPDA solution (7) and stirring of the reaction solution were stopped. Through such operations, a polyamic acid solution, which is a polyimide precursor, was obtained.
• a solution was prepared separately by dissolving 0.68 g of ODPA in 12.9 g of DMF (hereinafter sometimes referred to as ODPA solution (1)).
• the ODPA solution (1) was gradually added to the reaction solution while paying attention to the viscosity, and the reaction solution in the flask was stirred. When the viscosity of the reaction solution reached 1000 poise, addition of the ODPA solution (1) and stirring of the reaction solution were stopped. Through such operations, a polyamic acid solution, which is a polyimide precursor, was obtained.
• the ODPA solution (2) was gradually added to the reaction solution while paying attention to the viscosity, and the reaction solution in the flask was stirred. When the viscosity of the reaction solution reached 1000 poise, addition of the ODPA solution (2) and stirring of the reaction solution were stopped. Through such operations, a polyamic acid solution, which is a polyimide precursor, was obtained.
• a solution was prepared separately by dissolving 0.54 g of BPDA in 10.2 g of DMF (hereinafter sometimes referred to as BPDA solution (8)).
• BPDA solution (8) was gradually added to the reaction solution while paying attention to the viscosity, and the reaction solution in the flask was stirred. When the viscosity of the reaction solution reached 1000 poise, addition of the BPDA solution (8) and stirring of the reaction solution were stopped. Through such operations, a polyamic acid solution, which is a polyimide precursor, was obtained.
• the BPDA solution (9) was gradually added to the reaction solution while paying attention to the viscosity, and the reaction solution in the flask was stirred. When the viscosity of the reaction solution reached 1000 poise, addition of the BPDA solution (9) and stirring of the reaction solution were stopped. Through such operations, a polyamic acid solution, which is a polyimide precursor, was obtained.
• a solution was prepared separately by dissolving 0.62 g of BTDA in 11.9 g of DMF (hereinafter sometimes referred to as BTDA solution (1)).
• the BTDA solution (1) was gradually added to the reaction solution while paying attention to the viscosity, and the reaction solution in the flask was stirred. When the viscosity of the reaction solution reached 1000 poise, addition of the BTDA solution (1) and stirring of the reaction solution were stopped. Through such operations, a polyamic acid solution, which is a polyimide precursor, was obtained.
• the BTDA solution (2) was gradually added to the reaction solution while paying attention to the viscosity, and the reaction solution in the flask was stirred. When the viscosity of the reaction solution reached 1000 poise, addition of the BTDA solution (2) and stirring of the reaction solution were stopped. Through such operations, a polyamic acid solution, which is a polyimide precursor, was obtained.
• the ODPA solution (3) was gradually added to the reaction solution while paying attention to the viscosity, and the reaction solution in the flask was stirred. When the viscosity of the reaction solution reached 1000 poise, addition of the ODPA solution (3) and stirring of the reaction solution were stopped. Through such operations, a polyamic acid solution, which is a polyimide precursor, was obtained.
• the ODPA solution (4) was gradually added to the reaction solution while paying attention to the viscosity, and the reaction solution in the flask was stirred. When the viscosity of the reaction solution reached 1000 poise, addition of the ODPA solution (4) and stirring of the reaction solution were stopped. Through such operations, a polyamic acid solution, which is a polyimide precursor, was obtained.
• the PMDA solution was gradually added to the reaction solution while paying attention to the viscosity, and the reaction solution in the flask was stirred. When the viscosity of the reaction solution reached 1000 poise, addition of the PMDA solution and stirring of the reaction solution were stopped. Through such operations, a polyamic acid solution, which is a polyimide precursor, was obtained.
• a solution was separately prepared by dissolving 0.58 g of BPADA in 11.0 g of DMF (hereinafter sometimes referred to as BPADA solution).
• BPADA solution was gradually added to the reaction solution while paying attention to the viscosity, and the reaction solution in the flask was stirred. Addition of the BPADA solution and stirring of the reaction solution were stopped when the viscosity of the reaction solution reached 1000 poise. Through such operations, a polyamic acid solution, which is a polyimide precursor, was obtained.
• the chemical structural formula of KF-8010 manufactured by Shin-Etsu Chemical Co., Ltd. is shown in general formula (1).
• Preparation Example 2 Dispersion of fumed metal oxide for layer A
• a fumed metal oxide dispersion was obtained in the same manner as in Preparation Example 1, except that Aerosil R9200 manufactured by Nippon Aerosil Co., Ltd. was changed to Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.
• Preparation Example 3 Dispersion of fumed metal oxide for layer A
• a fumed metal oxide dispersion was obtained in the same manner as in Preparation Example 1 except that Aerosil R9200 manufactured by Nippon Aerosil Co., Ltd. in Preparation Example 1 was changed to Aerosil NX130 manufactured by Nippon Aerosil Co., Ltd.
• Formulation Example 4 Fumed metal oxide dispersion for layer A
• a fumed metal oxide dispersion was obtained in the same manner as in Preparation Example 1, except that Aerosil R9200 manufactured by Nippon Aerosil Co., Ltd. was changed to Aerosil VP RS920 manufactured by Nippon Aerosil Co., Ltd.
• the concentration of the fumed metal oxide in the fumed metal oxide dispersions obtained in Preparation Examples 1 to 4 was 20% by weight/weight.
• Example 1 40 g of the polyamic acid solution obtained in Synthesis Example 1 and 17 g of the dispersion of Preparation Example 1 were mixed, and the resulting mixture was further mixed with 40 g of DMF and 2 g of lutidine to obtain a Layer A dispersion.
• the Layer A dispersion was applied to one side of a non-thermoplastic polyimide film (Apical FP, thickness 17 microns, manufactured by Kaneka Corporation) so that the final thickness of Layer A on one side was 4 microns, and heated at 120°C for 2 minutes. Then, the layer A dispersion was applied and dried on the remaining surface in the same manner.
• a non-thermoplastic polyimide film Apical FP, thickness 17 microns, manufactured by Kaneka Corporation
• the non-thermoplastic polyimide film coated with the Layer A dispersion is heated at 450° C. for 12 seconds to imidize the polyamic acid of Layer A, Layer A (comprising polyimide resin and fumed metal oxide)/ A resin film having a structure in which the non-thermoplastic polyimide film/layer A was laminated in this order was obtained.
• a non-thermoplastic polyimide film (Apical FP) corresponds to layer B. That is, in Example 1, the layer B is made of a polyimide resin, specifically made of only a non-thermoplastic polyimide film. Also, the coefficient of linear expansion of the apical FP was 12 ppm/°C.
• the resin film was subjected to desmear treatment, electroless copper plating, and electrolytic copper plating under the conditions shown in Table 1 to obtain a double-sided copper-clad laminate, and the peel strength, moisture absorption solder heat resistance, and surface roughness Ra were evaluated.
• the compositions and results are shown in Tables 4-7.
• Example 2 A resin film and a double-sided copper-clad laminate were obtained in the same manner as in Example 1 except that the dispersion of Preparation Example 1 used in Example 1 was changed to the dispersion of Preparation Example 2, and the same evaluation was performed. rice field. The compositions and results are shown in Tables 4-7.
• Example 3 A resin film and a double-sided copper-clad laminate were obtained in the same manner as in Example 1 except that the dispersion of Preparation Example 1 used in Example 1 was changed to the dispersion of Preparation Example 3, and the same evaluation was performed. rice field. The compositions and results are shown in Tables 4-7.
• Example 4 A resin film and a double-sided copper-clad laminate were obtained in the same manner as in Example 1 except that the dispersion of Preparation Example 1 used in Example 1 was changed to the dispersion of Preparation Example 4, and the same evaluation was performed. rice field. The compositions and results are shown in Tables 4-7.
• Example 1 A mixed solution was obtained by mixing 40 g of the polyamic acid solution obtained in Synthesis Example 1 with 40 g of DMF and 2 g of lutidine.
• a resin film and a double-sided copper-clad laminate were obtained in the same manner as in Example 1, except that the layer A dispersion used in Example 1 was changed to the above mixture, and evaluated in the same manner.
• the initial peel strength did not show a sufficient value both with and without the backing copper.
• the peel strength after high-temperature heat treatment showed good adhesion with no backing copper, but did not show a sufficient value with backing copper, and the results of adhesion differed depending on the presence or absence of backing copper.
• the compositions and results are shown in Tables 4-7.
• Example 5 A resin film and a double-sided copper-clad laminate were obtained by performing the same operation as in Example 2 except that the amount of the dispersion liquid of Preparation Example 2 used in Example 2 was changed to 3.4 g, and the same evaluation was performed. .
• the compositions and results are shown in Tables 4-7.
• Example 6 A resin film and a double-sided copper-clad laminate were obtained by performing the same operation as in Example 2 except that the amount of the dispersion liquid of Preparation Example 2 used in Example 2 was changed to 6.8 g, and the same evaluation was performed. .
• the compositions and results are shown in Tables 4-7.
• Example 7 A resin film and a double-sided copper-clad laminate were obtained by performing the same operation as in Example 2 except that the amount of the dispersion liquid of Preparation Example 2 used in Example 2 was changed to 10.2 g, and the same evaluation was performed. .
• the compositions and results are shown in Tables 4-7.
• Example 8 A resin film and a double-sided copper-clad laminate were obtained in the same manner as in Example 2 except that the amount of the dispersion liquid of Preparation Example 2 used in Example 2 was changed to 34 g, and the same evaluation was performed. The compositions and results are shown in Tables 4-7.
• Example 9 A resin film and a double-sided copper-clad laminate were obtained by performing the same operation as in Example 3 except that the amount of the dispersion liquid of Preparation Example 3 used in Example 3 was changed to 3.4 g, and the same evaluation was performed. .
• the compositions and results are shown in Tables 4-7.
• Example 10 A resin film and a double-sided copper-clad laminate were obtained in the same manner as in Example 3 except that the amount of the dispersion liquid of Preparation Example 3 used in Example 3 was changed to 6.8 g, and the same evaluation was performed. .
• the compositions and results are shown in Tables 4-7.
• Example 11 A resin film and a double-sided copper-clad laminate were obtained by performing the same operation as in Example 3 except that the amount of the dispersion liquid of Preparation Example 3 used in Example 3 was changed to 10.2 g, and the same evaluation was performed. .
• the compositions and results are shown in Tables 4-7.
• Example 12 A resin film and a double-sided copper-clad laminate were obtained in the same manner as in Example 3 except that the amount of the dispersion liquid of Preparation Example 3 used in Example 3 was changed to 34 g, and the same evaluation was performed.
• the compositions and results are shown in Tables 4-7.
• Example 13 A resin film and a double-sided copper-clad laminate were obtained in the same manner as in Example 1 except that the amount of the dispersion liquid of Preparation Example 1 used in Example 1 was changed to 6.8 g, and the same evaluation was performed. .
• the compositions and results are shown in Tables 4-7.
• Example 14 A resin film and a double-sided copper-clad laminate were obtained in the same manner as in Example 1 except that the amount of the dispersion of Preparation Example 1 used in Example 1 was changed to 10.2 g, and the same evaluation was performed. .
• the compositions and results are shown in Tables 4-7.
• Example 15 A resin film and a double-sided copper-clad laminate were obtained in the same manner as in Example 1 except that the amount of the dispersion liquid of Preparation Example 1 used in Example 1 was changed to 34 g, and the same evaluation was performed. The compositions and results are shown in Tables 4-7.
• Example 16 A resin film and a double-sided copper-clad laminate were obtained in the same manner as in Example 1 except that the amount of the dispersion liquid of Preparation Example 1 used in Example 1 was changed to 51 g, and the same evaluation was performed. The compositions and results are shown in Tables 4-7.
• Example 17 A resin film and a double-sided copper-clad laminate were obtained by the same operation as in Example 4 except that the amount of the dispersion liquid of Preparation Example 4 used in Example 4 was changed to 6.8 g, and the same evaluation was performed. .
• the compositions and results are shown in Tables 4-7.
• Example 18 A resin film and a double-sided copper-clad laminate were obtained in the same manner as in Example 4 except that the amount of the dispersion liquid of Preparation Example 4 used in Example 4 was changed to 10.2 g, and the same evaluation was performed. .
• the compositions and results are shown in Tables 4-7.
• Example 19 A resin film and a double-sided copper-clad laminate were obtained in the same manner as in Example 4 except that the amount of the dispersion liquid of Preparation Example 4 used in Example 4 was changed to 34 g, and the same evaluation was performed. The compositions and results are shown in Tables 4-7.
• Example 20 A resin film and a double-sided copper-clad laminate were obtained in the same manner as in Example 4 except that the amount of the dispersion of Preparation Example 4 used in Example 4 was changed to 51 g, and the same evaluation was performed. The compositions and results are shown in Tables 4-7.
• Example 21 Of the processing conditions listed in Table 1 for producing the double-sided copper-clad laminate of Example 1, the conditions for the drying process after electroless copper plating were changed to only wiping off water droplets, and the drying process after copper sulfate plating was changed.
• a double-sided copper-clad laminate was obtained by performing the same operation as in Example 1, except that only water droplets were wiped off, and the same evaluation was performed.
• the compositions and results are shown in Tables 4-7.
• six types of peel strength showed good values as in Example 1. That is, the metal plating layer adhered well to the resin film without heating after the electroless metal plating layer forming treatment.
• Example 22 The same operation as in Example 1 was performed except that the polyamic acid solution of Synthesis Example 1 used in Example 1 was changed to the polyamic acid solution of Synthesis Example 2 to obtain a resin film and a double-sided copper-clad laminate, and the same evaluation was performed. did The compositions and results are shown in Tables 4-7.
• Example 23 The same operation as in Example 1 was performed except that the polyamic acid solution of Synthesis Example 1 used in Example 1 was changed to the polyamic acid solution of Synthesis Example 3 to obtain a resin film and a double-sided copper-clad laminate, and the same evaluation was performed. did The compositions and results are shown in Tables 4-7.
• Example 24 The same operation as in Example 1 was performed except that the polyamic acid solution of Synthesis Example 1 used in Example 1 was changed to the polyamic acid solution of Synthesis Example 4 to obtain a resin film and a double-sided copper-clad laminate, and the same evaluation was performed. did The compositions and results are shown in Tables 4-7.
• Example 25 The same operation as in Example 1 was performed except that the polyamic acid solution of Synthesis Example 1 used in Example 1 was changed to the polyamic acid solution of Synthesis Example 5 to obtain a resin film and a double-sided copper-clad laminate, and the same evaluation was performed. did The compositions and results are shown in Tables 4-7.
• Example 26 The same operation as in Example 1 was performed except that the polyamic acid solution of Synthesis Example 1 used in Example 1 was changed to the polyamic acid solution of Synthesis Example 6 to obtain a resin film and a double-sided copper-clad laminate, and the same evaluation was performed. did The compositions and results are shown in Tables 4-7.
• Example 27 The same operation as in Example 1 was performed except that the polyamic acid solution of Synthesis Example 1 used in Example 1 was changed to the polyamic acid solution of Synthesis Example 7 to obtain a resin film and a double-sided copper-clad laminate, and the same evaluation was performed. did The compositions and results are shown in Tables 4-7.
• Example 28 The same operation as in Example 1 was performed except that the polyamic acid solution of Synthesis Example 1 used in Example 1 was changed to the polyamic acid solution of Synthesis Example 8 to obtain a resin film and a double-sided copper-clad laminate, and the same evaluation was performed. did The compositions and results are shown in Tables 4-7.
• Example 29 The same operation as in Example 1 was performed except that the polyamic acid solution of Synthesis Example 1 used in Example 1 was changed to the polyamic acid solution of Synthesis Example 9 to obtain a resin film and a double-sided copper-clad laminate, and the same evaluation was performed. did The compositions and results are shown in Tables 4-7.
• Example 30 The same operation as in Example 1 was performed except that the polyamic acid solution of Synthesis Example 1 used in Example 1 was changed to the polyamic acid solution of Synthesis Example 10 to obtain a resin film and a double-sided copper-clad laminate, and the same evaluation was performed. did The compositions and results are shown in Tables 4-7.
• Example 31 The same operation as in Example 1 was performed except that the polyamic acid solution of Synthesis Example 1 used in Example 1 was changed to the polyamic acid solution of Synthesis Example 11 to obtain a resin film and a double-sided copper-clad laminate, and the same evaluation was performed. did The moisture absorption solder heat resistance evaluation was ⁇ .
• the compositions and results are shown in Tables 4-7.
• Example 32 The same operation as in Example 1 was performed except that the polyamic acid solution of Synthesis Example 1 used in Example 1 was changed to the polyamic acid solution of Synthesis Example 12 to obtain a resin film and a double-sided copper-clad laminate, and the same evaluation was performed. did The moisture absorption solder heat resistance evaluation was ⁇ .
• the compositions and results are shown in Tables 4-7.
• Example 2 The same operation as in Example 1 was performed except that the polyamic acid solution of Synthesis Example 1 used in Example 1 was changed to the polyamic acid solution of Synthesis Example 13 to obtain a resin film and a double-sided copper-clad laminate, and the same evaluation was performed. did The moisture absorption solder heat resistance evaluation was x. The compositions and results are shown in Tables 4-7.
• Example 33 The same operation as in Example 1 was performed except that the polyamic acid solution of Synthesis Example 1 used in Example 1 was changed to the polyamic acid solution of Synthesis Example 14 to obtain a resin film and a double-sided copper-clad laminate, and the same evaluation was performed. did The moisture absorption solder heat resistance evaluation was ⁇ .
• the compositions and results are shown in Tables 4-7.
• Example 34 The same operation as in Example 1 was performed except that the polyamic acid solution of Synthesis Example 1 used in Example 1 was changed to the polyamic acid solution of Synthesis Example 15 to obtain a resin film and a double-sided copper-clad laminate, and the same evaluation was performed. did The moisture absorption solder heat resistance evaluation was ⁇ .
• the compositions and results are shown in Tables 4-7.
• Example 3 The same operation as in Example 1 was performed except that the polyamic acid solution of Synthesis Example 1 used in Example 1 was changed to the polyamic acid solution of Synthesis Example 16 to obtain a resin film and a double-sided copper-clad laminate, and the same evaluation was performed. did In addition, the moisture absorption solder heat resistance evaluation was x. The compositions and results are shown in Tables 4-7.
• Example 4 The same operation as in Example 1 was performed except that the polyamic acid solution of Synthesis Example 1 used in Example 1 was changed to the polyamic acid solution of Synthesis Example 17 to obtain a resin film and a double-sided copper-clad laminate, and the same evaluation was performed.
• the polyimide resin of Layer A contains a silicone skeleton, and volatilization of the siloxane component from the main chain skeleton may cause contact failure in electronic devices and process contamination.
• the layer A had a large coefficient of linear expansion, and the evaluation of moisture absorption solder heat resistance was x. It has poor dimensional stability, is soluble in organic solvents, and has poor resistance to organic solvents in the process of manufacturing printed wiring boards.
• Tables 4-7 The compositions and results are shown in Tables 4-7.
• a dispersion of fumed metal oxide was obtained.
• 40 g of the polyimide solution and 17 g of the fumed metal oxide dispersion were mixed to obtain a fumed metal oxide-dispersed polyimide solution (hereinafter also referred to as layer A solution).
• the layer A solution was applied to one side of a non-thermoplastic polyimide film (Apical FP, thickness 17 microns, manufactured by Kaneka Corporation) so that the final thickness of layer A on one side was 4 microns, and heated at 60°C for 5 minutes.
• the layer A solution was dried at 150° C. for 5 minutes, and then the remaining surface was coated with the layer A solution and dried in the same manner. By this operation, a resin film having a structure of layer A/non-thermoplastic polyimide film/layer A was obtained. After that, the same operation as in Example 1 was performed to obtain a double-sided copper-clad laminate, and the same evaluation was performed.
• the polyimide resin of Layer A contains a silicone skeleton, and volatilization of the siloxane component from the main chain skeleton may cause contact failure in electronic devices and process contamination.
• the moisture absorption solder heat resistance evaluation was x.
• Layer A has a large coefficient of linear expansion, poor dimensional stability, is soluble in organic solvents, and has poor resistance to organic solvents in the printed wiring board manufacturing process. The compositions and results are shown in Tables 4-7.

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