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WO2019135367A1 - Raidisseur - Google Patents

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Publication number
WO2019135367A1
WO2019135367A1 PCT/JP2018/047212 JP2018047212W WO2019135367A1 WO 2019135367 A1 WO2019135367 A1 WO 2019135367A1 JP 2018047212 W JP2018047212 W JP 2018047212W WO 2019135367 A1 WO2019135367 A1 WO 2019135367A1
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WO
WIPO (PCT)
Prior art keywords
polyimide film
coupling agent
silane coupling
film
bis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/047212
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English (en)
Japanese (ja)
Inventor
桂也 ▲徳▼田
全広 山下
奥山　哲雄
渡辺　直樹
俊之 土屋
俊介 市村
美唯妃 林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyobo Co Ltd
Original Assignee
Toyobo Co Ltd
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Filing date
Publication date
Application filed by Toyobo Co Ltd filed Critical Toyobo Co Ltd
Priority to JP2019563968A priority Critical patent/JP7192799B2/ja
Publication of WO2019135367A1 publication Critical patent/WO2019135367A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention adheres a stiffener (supporting plate or reinforcing plate), particularly a plurality of polyimide films, which is used by being adhered to an FPC board in order to maintain the strength of a flexible printed circuit board (hereinafter referred to as "FPC board").
  • the present invention relates to a polyimide film laminate stiffener which is formed by bonding with a coating agent.
  • Typical examples of films provided with a heat-curable adhesive on one side or both sides of a single-layer or multilayer polyimide film include "coverlay films” and "TAB (Tape Automated Bonding) films”.
  • Coverlay films and "TAB (Tape Automated Bonding) films”.
  • TAB Tape Automated Bonding
  • Be The adhesive used for these films is applied on a base film 11 made of a polyimide film and then dried to be an adhesive in a semi-cured state (B-stage), as shown in FIG. 1 (a). It is considered to be layer 12. Then, a separator 13 is usually further laminated on the surface of the adhesive layer 12. This laminate is stored in a form having a semi-cured adhesive layer prior to use.
  • the prepreg obtained by impregnating adhesive varnish with reinforcement substrates, such as a glass cloth, and making it dry is mentioned.
  • the adhesive is also stored in the B-stage state for the prepreg.
  • the base film 11 of the coverlay film or the film for TAB is attached to an object such as the FPC board 14 through the adhesive layer 2 (made of an adhesive or a prepreg).
  • the base film 11 is bonded to an object such as the FPC board 14 by stacking, heating and pressing.
  • an FPC board is also known in which a metal foil 23 such as copper foil and a polyimide film 11 are bonded by an adhesive 22. In bonding these, a metal foil and a polyimide film are used. It is necessary to carry out heat aging after laminating.
  • the thickness of the substrate is usually thin (for example, 12.5 to 100 ⁇ m).
  • a bonding sheet which also includes a portion susceptible to this inconvenience or a portion susceptible to this inconvenience through a thermosetting adhesive (referred to as a bonding sheet). Fixing to a support such as a stiffener is performed. In this case, it is a general bonding condition to heat and press at 150 to 180 ° C. for 15 to 45 minutes under a pressure of 1 to 3 MPa.
  • a single-layer polyimide film is used as a stiffener used to support or reinforce the FPC substrate.
  • a single-layer polyimide film having a thickness of 225 ⁇ m or less is widely and generally commercially available, and this commercially available single-layer polyimide film is used as a stiffener.
  • Typical examples of these single layer polyimide films include Kapton H or V type (manufactured by Toray DuPont Co., Ltd.), Upirex S type (manufactured by Ube Industries, Ltd.), Apical AH or NPI type (Co., Ltd.)
  • the polyimide film marketed by brand names, such as Kaneka make) is mentioned.
  • the single-layer polyimide film has a constant hardness and stiffness (stiffness) depending on each product. However, depending on the application, even with the same thickness, rigidity may be required more than a single layer.
  • the polyimide film is mainly manufactured by the solution film forming by casting, It was difficult to make a thick film in the manufacturing method, or the productivity was extremely inferior.
  • An object of the present invention is to provide a polyimide film laminate stiffener which is superior in heat resistance and rigidity to a single-layer thick polyimide film, and a method for producing the same.
  • the present invention has the following constitution.
  • a stiffener characterized in that the value of elastic modulus at 400 ° C. measured using a cantilever is 0.5 GPa or more and 10 GPa or less.
  • the stiffener is a polyimide film laminate having a structure in which a plurality of polyimide film layers and a silane coupling agent condensation product layer are alternately stacked, and each polyimide film layer has a thickness of 3 ⁇ m to 250 ⁇ m.
  • the thickness of the silane coupling agent condensation product layer is 0.1 nm or more and 300 nm or less.
  • the surface roughness Ra of at least one surface of the surfaces in contact with the silane coupling agent condensation layer is 70 nm or less.
  • the heat resistance required for a flexible printed wiring board is a heat resistance for a short time of about several tens of seconds at about 260 ° C. assuming a soldering temperature, and 150 ° C. used to estimate the component life from the rated temperature. A heat resistance test of about several thousand hours is assumed.
  • equipment used in the field such as internal combustion engines, external combustion engines, nuclear energy facilities, aerospace applications, crustal drilling equipment, and metal industry are required to have long-term heat resistance at higher temperatures, and such Similarly, high heat resistance life is required for electronic devices used for sensing and electric / electronic control.
  • the stiffeners according to the invention relate to stiffeners which, as in these applications, exhibit adequate reinforcing properties, in particular also in the high temperature range, preferably in the temperature range of the order of 400.degree.
  • Such a stiffener is preferably used for partial reinforcement of a flexible printed wiring board used in a high temperature region, for example, semi-rigidization of a part mounting portion or reinforcement of a connector insertion and removal portion.
  • stiffeners are used as stiffeners (reinforcing plates) for flexible printed wiring boards
  • many of the examples of stiffeners intended for use in high-temperature areas above 400 ° C. are inorganic.
  • the use of glass, ceramics, metals etc is common.
  • a plurality of thin polyimide films are laminated so as to have the same thickness as a single polyimide film in a range exceeding 50 ⁇ m, preferably 76 ⁇ m, bending rigidity becomes higher and stiffness is increased.
  • the stiffener which can be used even in a high temperature range by a flexible, elastic polymer material is most effective.
  • FIG. 1 is a schematic cross-sectional view of a PI film (a) provided with an adhesive layer on one side and an FPC board (b) to which the PI film is bonded.
  • FIG. 2 is a cross-sectional schematic diagram of the FPC board which bonded copper foil and PI film together.
  • FIG. 3 is a schematic cross-sectional view of a stiffener in which two thin PI films are laminated.
  • FIG. 4 is a schematic view of a stiffener in which a plurality of polyimide films according to the present invention are laminated.
  • FIG. 5 is a schematic block diagram showing an example of an apparatus used for a silane coupling agent treatment method through a gas phase to a film in the present invention.
  • FIG. 6 is a schematic view showing an example of a jig used for measuring an elastic modulus by a cantilever in the present invention.
  • the stiffener in the present invention is a reinforcing material on which a resin is laminated, and the shape is not particularly limited.
  • the shape of the upper surface may be square, rectangle, circle or the like.
  • the number of stacked layers may be any number as long as it is two or more.
  • the silane coupling agent in the present invention refers to a compound having elemental silicon in the molecule, physically and chemically interposing between polyimide films, and having an effect of enhancing the adhesion between the two.
  • silane coupling agent examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, vinyltrichlorosilane, Vinyltrimethoxysilane, vinyltrimethoxys
  • silane coupling agent which can be used in the present invention, n-propyltrimethoxysilane, butyltrichlorosilane, 2-cyanoethyltriethoxysilane, cyclohexyltrichlorosilane, decyltrichlorosilane, diacetoxydimethylsilane, di-dimethylsilane, di-cyclopentadisilane, di- Ethoxydimethylsilane, dimethoxydimethylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, dodecyltrichlorosilane, dodecyltrimethoxysilane, ethyltrichlorosilane, hexyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, n-octyl
  • alkoxysilanes such as tetramethoxysilane, tetraethoxysilane and the like may be appropriately added to the silane coupling agent.
  • mixing and heating operations are added to the silane coupling agent, with or without the addition of other alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, etc., as appropriate, and the reaction is slightly delayed. You may go ahead and use it.
  • the silane coupling agent preferably used in the present invention is preferably a silane coupling agent having a chemical structure having one silicon atom per molecule of the coupling agent.
  • particularly preferred silane coupling agents include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2 -(Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysi
  • a phosphorus-based coupling agent a titanate-based coupling agent, etc. may be used in combination.
  • the silane coupling agent treatment refers to a treatment for forming a thin film layer comprising a silane coupling agent or a condensate of a silane coupling agent on the surface of an object.
  • a silane coupling agent is used as a solution such as alcohol and applied to an object or applied to the object by dipping or the like in a silane coupling agent solution, and then dried and heated to form a silane. By condensing the coupling agent at the same time as being chemically reactively bound to the object surface.
  • a coating method of a silane coupling agent As a coating method of a silane coupling agent, a spin coat method, a spray coat method, a capillary coat method, a dip method, etc. are common.
  • the silane coupling agent treatment is carried out on one side or both sides of the polyimide film as needed.
  • the silane coupling agent coating step can be performed via a gas phase.
  • a gas phase a method of exposing a polyimide film to a vaporized silane coupling agent.
  • Vaporization refers to a vapor of a silane coupling agent, that is, a state in which a substantially gaseous silane coupling agent or a particulate silane coupling agent is present.
  • the exposure to this refers to bringing the polyimide film into contact with the atmosphere containing the vaporized silane coupling agent. Since the silane coupling agent has a certain vapor pressure, a certain amount of silane coupling agent in a gaseous state is present even in a normal temperature atmosphere.
  • the vaporized silane coupling agent may be atomized due to the relationship of the dew point and may be present in the form of fine particles in a gas. Such a state can also be used in the present invention. Also, the operation of increasing the vapor density can be performed by the operation of temperature and pressure.
  • the boiling point of the silane coupling agent varies depending on the chemical structure, but is approximately in the range of 100 to 250.degree. However, heating at 200 ° C. or higher is not preferable because it may cause a side reaction on the organic group side of the silane coupling agent.
  • the environment under which the silane coupling agent is heated may be under pressure, under normal pressure or under reduced pressure, but when promoting vaporization of the silane coupling agent, it is preferably under normal pressure or under reduced pressure. Since many silane coupling agents are flammable liquids, it is preferable to carry out the vaporization operation in an enclosed container, preferably after replacing the container with an inert gas. However, from the viewpoint of improving the production efficiency and reducing the cost of production equipment, it is desirable to apply a silane coupling agent in an environment not using vacuum.
  • the silane coupling agent deposition method not using vacuum according to the present invention does not use vacuum only at the time of deposition, but usually sets the polyimide film in the atmosphere and then substitutes the carrier gas for the silane coupling agent.
  • the time for which the polyimide film is exposed to the silane coupling agent is not particularly limited, but is within 60 minutes, preferably within 20 minutes, and more preferably within 10 minutes.
  • the exposure time is a process design value determined by the relationship between the concentration of the silane coupling agent and the required silane coupling agent application amount. Although the lower limit of the exposure time is not particularly limited, it is better to provide a time of about 10 seconds or more, preferably about 30 seconds or more, in order to reduce industrially generated unevenness of coating amount.
  • the polyimide film temperature during exposure of the polyimide film to the silane coupling agent is controlled to an appropriate temperature between -50.degree. C. and 200.degree. C. depending on the type of silane coupling agent and the thickness of the silane coupling agent layer required. Is preferred.
  • the polyimide film exposed to the silane coupling agent is preferably heated to 70 ° C. to 200 ° C., more preferably 75 ° C. to 150 ° C. after the exposure. By this heating, hydroxyl groups on the surface of the polyimide film react with the alkoxy group or silazane group of the silane coupling agent, and the silane coupling agent treatment is completed.
  • the time required for heating is 10 seconds or more and about 10 minutes or less.
  • the temperature is too high or the time is too long, deterioration of the coupling agent may occur. If the length is too short, the processing effect can not be obtained. In the case where the substrate temperature during exposure to the silane coupling agent is already 80 ° C. or higher, the subsequent heating can be omitted.
  • the surface of the polyimide film coated with the silane coupling agent it is preferable to hold the surface of the polyimide film coated with the silane coupling agent downward and expose it to the silane coupling agent vapor.
  • the coated surface of the polyimide film necessarily faces upward during and before application, so that floating foreign matter and the like in the working environment may be deposited on the surface of the inorganic substrate I can not deny it.
  • the polyimide film can be held downward. It is possible to significantly reduce the adhesion of foreign matter in the environment.
  • a gas containing a vaporized silane coupling agent when introducing a gas containing a vaporized silane coupling agent into a room where the polymer substrate is exposed, separating and introducing the gas into two or more once, colliding the two or more gases in the room It is also effective to generate turbulent flow by homogenization to make the silane coupling agent distribution uniform.
  • a method of vaporizing the silane coupling agent there may be a method of introducing a gas into the silane coupling agent liquid to generate air bubbles, in addition to evaporation by heating. This is called bubbling hereafter. For bubbling, simply put the piping through which the gas passes into the silane coupling agent solution, attach a porous body to the end of the piping so that many fine bubbles come out, superimpose ultrasonic waves, and evaporate It is also effective to prompt
  • the vaporized silane coupling agent may be charged.
  • the dew point is low.
  • the dew point is 15 ° C. or less, more desirably 10 ° C. or less, and further desirably 5 ° C. or less.
  • the number of silicon-containing foreign particles having a long diameter of 10 ⁇ m or more present in the silane coupling agent layer of the silane coupling agent layer-laminated polyimide film is 2000 pieces / m 2 or less, preferably 1000 pieces / m 2 or less, and more preferably 500 pieces / m 2 or less Is a preferred form of the invention. Further, the number of silicon-containing foreign matter can be achieved by combining the above operations.
  • the application amount of the silane coupling agent depends on the thickness of the silane coupling agent condensate layer.
  • the thickness of the silane coupling agent condensate layer of the present invention is preferably 0.1 nm or more and 300 nm or less, and more preferably 0.5 nm or more and 200 nm or less.
  • the upper limit of the thickness is preferably less than 200 nm, preferably 150 nm or less, more preferably 100 nm or less for practical use, more preferably 70 nm or less, and still more preferably 50 nm or less.
  • the coupling agent is not in the form of a uniform coating film but in the form of clusters, which is not preferable.
  • the film thickness of the silane coupling agent condensation product layer is obtained by polishing a cross section in the direction perpendicular to the film surface of the polyimide film laminate, forming an ultrathin section with a microtome, taking a cross-sectional photograph with a transmission electron microscope It calculated back from the magnification.
  • the upper limit of the thickness of the polyimide film is not particularly limited, but is preferably 250 ⁇ m or less, more preferably 150 ⁇ m or less, and still more preferably 90 ⁇ m or less in view of the demand for a flexible electronic device.
  • the area of the polyimide film of the present invention is preferably a large area from the viewpoint of production efficiency and cost of a laminate and a flexible electronic device. It is preferably 1000 cm 2 or more, more preferably 1500 cm 2 or more, and still more preferably 2000 cm 2 or more.
  • polyimide film aromatic polyimide, alicyclic polyimide, polyamide imide, polyether imide and the like can be used. More preferably, it refers to a polymer containing 50% or more of a polyimide skeleton.
  • a polyimide film is prepared by applying a solution of a polyamide acid (polyimide precursor) obtained by reacting diamines and tetracarboxylic acids in a solvent on a support for producing a polyimide film, and drying the green film ("precursor film Or a “polyamic acid film”), further on a support for producing a polyimide film, or in the state of being peeled off from the support, the green film is heat-treated at high temperature to carry out a dehydration ring closure reaction.
  • a polyamide acid polyimide precursor
  • diamine which comprises a polyamic acid there is no restriction
  • combination, aliphatic diamines, alicyclic diamines etc. can be used.
  • aromatic diamines are preferable, and among aromatic diamines, aromatic diamines having a benzoxazole structure are more preferable.
  • aromatic diamines having a benzoxazole structure are used, it is possible to develop high heat resistance, high elastic modulus, low heat shrinkage, and low linear expansion coefficient.
  • the diamines may be used alone or in combination of two or more.
  • the aromatic diamines having a benzoxazole structure are not particularly limited.
  • aromatic diamines other than the aromatic diamines having the benzoxazole structure described above include, for example, 2,2′-dimethyl-4,4′-diaminobiphenyl, 1,4-bis [2- (4-aminophenyl) ) -2-Propyl] benzene (bisaniline), 1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene, 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl, 4,4 '-Bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl Sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl Nyl
  • aliphatic diamines examples include 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane and the like.
  • alicyclic diamines examples include 1,4-diaminocyclohexane, 4,4′-methylenebis (2,6-dimethylcyclohexylamine) and the like.
  • the total amount of diamines (aliphatic diamines and alicyclic diamines) other than aromatic diamines is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less of all diamines It is.
  • the aromatic diamines are preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more of all diamines.
  • tetracarboxylic acids constituting the polyamic acid examples include aromatic tetracarboxylic acids (including their acid anhydrides), aliphatic tetracarboxylic acids (including their acid anhydrides) and alicyclic tetracarboxylic acids which are usually used for polyimide synthesis. Acids (including their acid anhydrides) can be used. Among them, aromatic tetracarboxylic acid anhydrides and alicyclic tetracarboxylic acid anhydrides are preferable, and from the viewpoint of heat resistance, aromatic tetracarboxylic acid anhydrides are more preferable, and from the viewpoint of light transmittance, alicyclic Family tetracarboxylic acids are more preferred.
  • the number of anhydride structures in the molecule may be one or two, but preferably those having two anhydride structures (dianhydrides) Good.
  • the tetracarboxylic acids may be used alone or in combination of two or more.
  • Alicyclic tetracarboxylic acids include, for example, cycloaliphatic tetra-carboxylic acids such as cyclobutane tetracarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic acid, 3,3 ', 4,4'-bicyclohexyl tetracarboxylic acid, etc. Carboxylic acids and their acid anhydrides can be mentioned.
  • dianhydrides having two anhydride structures eg, cyclobutanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 3,3 ′, 4,4 '-Bicyclohexyltetracarboxylic acid dianhydride etc.
  • the alicyclic tetracarboxylic acids may be used alone or in combination of two or more. When importance is attached to transparency of the alicyclic tetracarboxylic acids, for example, 80% by mass or more of all tetracarboxylic acids is preferable, more preferably 90% by mass or more, and still more preferably 95% by mass or more.
  • aromatic tetracarboxylic acids are not particularly limited, but are preferably pyromellitic acid residues (that is, those having a structure derived from pyromellitic acid), and more preferably the acid anhydride.
  • aromatic tetracarboxylic acids for example, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 3 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl sulfone tetracarboxylic dianhydride, 2,2-bis [4- (3,4-di) Carboxy phenoxy) phenyl] propanoic acid anhydride etc.
  • aromatic tetracarboxylic acids for example, 80% by mass or more of all tetracarboxylic acids is preferable, more preferably 90% by mass or more, and still more preferably 95% by mass or more.
  • the polyimide film of the present invention preferably has a glass transition temperature of 250 ° C. or more, preferably 300 ° C. or more, more preferably 350 ° C. or more, or no glass transition point in a region of 500 ° C. or less.
  • the glass transition temperature in the present invention is determined by differential thermal analysis (DSC).
  • the linear expansion coefficient (CTE) of the polyimide film of the present invention is preferably -5 ppm / K to +20 ppm / K, more preferably -5 ppm / K to +15 ppm / K, and still more preferably 1 ppm / K to +10 ppm It is / K.
  • CTE linear expansion coefficient
  • the linear expansion coefficient of the polyimide film in the present invention in question uses an average value between 30 and 200 ° C.
  • the temperature range of interest changes, considering the process at high temperature, When examining the range of 30 ° C to 400 ° C, it may be in the range of 100 ° C to 400 ° C.
  • the working temperature range is -50 ° C to 150 It may be possible to emphasize the range of ° C.
  • the breaking strength of the polyimide film in the present invention is 60 MPa or more, preferably 120 MP or more, and more preferably 240 MPa or more. Although the upper limit of the breaking strength is not limited, it is practically less than about 1000 MPa. In addition, the breaking strength of the said polyimide film refers to the average value of the length direction of a polyimide film, and the width direction here.
  • the thickness unevenness of the polyimide film in the present invention is preferably 20% or less, more preferably 12% or less, still more preferably 7% or less, and particularly preferably 4% or less. When the thickness unevenness exceeds 20%, application to narrow portions tends to be difficult.
  • the polyimide film in the present invention is preferably obtained in the form of being wound up as a long polyimide film having a width of 300 mm or more and a length of 10 m or more at the time of its production.
  • Rolled polyimide wound around a winding core More preferred are in the form of a film.
  • a lubricant in the polyimide film, in order to ensure the handling property and the productivity, it is preferable to add and contain a lubricant (particles) in the film to impart fine irregularities to the surface of the polyimide film to secure the slip property.
  • the lubricant (particles) is preferably a fine particle made of an inorganic substance, such as metal, metal oxide, metal nitride, metal carbonate, metal salt, phosphate, carbonate, talc, mica, clay, etc. Particles of clay mineral, etc. can be used.
  • metal oxides such as silicon oxide, calcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium pyrophosphate, hydroxyapatite, calcium carbonate, glass fillers, phosphates, and carbonates can be used.
  • the lubricant may be only one kind or two or more kinds.
  • the volume average particle diameter of the lubricant (particles) is usually 0.001 to 10 ⁇ m, preferably 0.03 to 2.5 ⁇ m, more preferably 0.05 to 0.7 ⁇ m, still more preferably 0.05 to It is 0.3 ⁇ m.
  • the volume average particle size is based on the measurement value obtained by the light scattering method. If the particle size is smaller than the lower limit, industrial production of the polyimide film becomes difficult, and if the upper limit is exceeded, the surface irregularities become too large, and the bonding strength becomes weak, which may cause practical problems.
  • the addition amount of the lubricant is 0.02 to 50% by mass, preferably 0.04 to 3% by mass, more preferably 0.08 to 1.2, as the addition amount with respect to the polymer component in the polyimide film. It is mass%. If the addition amount of the lubricant is too small, the effect of the lubricant addition is difficult to expect, and there is a case where the slip property is not secured so much that the production of the polyimide film may be disturbed. Even if the slip property is secured, problems such as a decrease in smoothness, a decrease in breaking strength and a breaking elongation of the polyimide film, and an increase in CTE may be caused.
  • a lubricant When a lubricant (particles) is added to or contained in the polyimide film, it may be a single layer polyimide film in which the lubricant is uniformly dispersed, but for example, one surface is made of a polyimide film containing lubricant.
  • the lubricant concentration gradient type polyimide film may be formed of a polyimide film having a small amount of lubricant content even if the other surface does not contain lubricant or has a lubricant content. In such a lubricant concentration gradient type film, fine asperities can be imparted to the surface of one layer (film), and the layer (film) can ensure slipperiness, resulting in good handling and productivity. Can be secured.
  • the lubricant concentration-graded polyimide film is first filmed using, for example, a polyimide film material not containing a lubricant, and placed on the way of the process to at least one side of the film It can be obtained by applying a resin layer containing a lubricant.
  • film formation is carried out using a polyimide film raw material containing a lubricant, and a polyimide film raw material not containing a lubricant is applied to obtain a film during the process or after film formation is completed. It can.
  • a polyimide film obtained by using a solution film forming method such as a polyimide film
  • a solution film forming method such as a polyimide film
  • a polyamic acid solution precursor solution of polyimide
  • a lubricant preferably having an average particle diameter of 0.05 to 2
  • Content of 0.02 to 50% by mass preferably 0.04 to 3% by mass, more preferably 0.08 to 1.2% by mass
  • the polyamide acid solution and containing no lubricant or having a small content preferably less than 0.02% by mass, more preferably less than 0.01% by mass based on the solid content of the polymer in the polyamic acid solution
  • the lubricant concentration gradient type method (lamination) method of the lubricant concentration gradient type polyimide film is not particularly limited as long as there is no problem in the adhesion between the two layers, and adhesion is made without using an adhesive layer or the like. I hope there is.
  • a polyimide film for example, i) after producing one polyimide film, continuously applying the other polyamic acid solution on the polyimide film for imidization, ii) casting one polyamic acid solution After preparing a polyamic acid film, the other polyamic acid solution is continuously coated on this polyamic acid film and then imidized, iii) coextrusion method, iv) lubricant is not contained or its content is On the film formed by the polyamic-acid solution which is a small amount, the method of apply
  • the ratio of the thickness of each layer in the lubricant concentration gradient type polyimide film is not particularly limited, but the polymer layer containing a large amount of lubricant (a) layer, does not contain a lubricant, or the content thereof is small
  • the polymer layer is the (b) layer
  • the (a) layer / (b) layer preferably has a thickness of 0.05 to 0.95.
  • the smoothness of the (b) layer tends to be lost, while when it is less than 0.05, the improvement effect of the surface characteristics is insufficient and the slipperiness is lost. There is something I can do.
  • ⁇ Surface activation treatment of polyimide film> It is preferable to perform surface activation treatment on the polyimide film used in the present invention.
  • the surface activation treatment in the present invention is a dry or wet surface treatment.
  • dry processing of the present invention processing of irradiating the surface with active energy rays such as ultraviolet rays, electron beams, X-rays, corona treatment, vacuum plasma treatment, atmospheric pressure plasma treatment, flame treatment, itro treatment, etc. can be used. .
  • As a wet process the process which makes the film surface contact with an acid thru
  • the surface activation treatment preferably used in the present invention is plasma treatment, and is a combination of plasma treatment and wet acid treatment.
  • the plasma treatment is not particularly limited, and includes RF plasma treatment in vacuum, microwave plasma treatment, microwave ECR plasma treatment, atmospheric pressure plasma treatment, corona treatment, etc., gas treatment including fluorine, ion treatment Also included are ion implantation using a source, processing using a PBII method, flame processing exposed to thermal plasma, and intro processing. Among these, RF plasma treatment in vacuum, microwave plasma treatment and atmospheric pressure plasma treatment are preferable.
  • Suitable conditions for plasma treatment include oxygen plasma, plasma containing fluorine such as CF.sub.4, C.sub.2 F.sub.6, or a plasma known to have a high etching effect, or physical such as Ne, Ar, Kr, Xe, or plasma. It is desirable to use plasma treatment, which has a high effect of physically applying energy to the polymer surface. Further, it is also preferable to add a plasma such as CO 2 , CO, H 2 , N 2 , NH 4 , CH 4 and the like, and a mixed gas of these, and further water vapor.
  • a plasma such as CO 2 , CO, H 2 , N 2 , NH 4 , CH 4 and the like, and a mixed gas of these, and further water vapor.
  • OH, N 2 , N, CO, CO 2 , H, H 2 , H 2 , O 2 , NH, NH 2 , NH 3 , COOH, NO, NO 2 , He, Ne, Ar, Kr, Xe, CH At least one selected from the group consisting of 2 O, Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 , C 3 H 7 Si (OCH 3 ) 3 , C 3 H 7 Si (OC 2 H 5 ) 3 and the like It is necessary to create a plasma that contains one or more components as a gas or as a decomposition product in the plasma.
  • the plasma When aiming at processing in a short time, it is desirable that the plasma has a high energy density, a high kinetic energy of ions in the plasma, and a high density of active species, but the surface smoothness is required. There is a limit to increasing the density.
  • oxygen plasma is used, surface oxidation proceeds, which is good in terms of OH group formation, but it is easy to form a surface that is poor in adhesion to the film itself, and the surface roughness (roughness) increases. Adhesion also worsens.
  • the plasma using Ar gas purely physical collision effects occur on the surface, and in this case, the surface roughness also increases. Considering these things comprehensively, microwave plasma processing, microwave ECR plasma processing, plasma irradiation by an ion source that can easily implant ions of high energy, PBII method, etc. are also desirable.
  • Such surface activation treatment cleans the polymer surface and generates more active functional groups.
  • the generated functional group is linked to the coupling agent layer by hydrogen bonding or a chemical reaction, and it becomes possible to firmly bond the polyimide film layer and the coupling agent layer.
  • the effect of etching the polyimide film surface can also be obtained.
  • the protrusions by the lubricant may inhibit the adhesion between the film and the inorganic substrate. In this case, it is possible to remove the lubricant particles in the vicinity of the film surface if the polyimide film surface is thinly etched by plasma treatment to expose a part of the lubricant particles and the treatment with hydrofluoric acid is performed.
  • the surface activation treatment may be applied to only one side of the polyimide film or to both sides.
  • plasma treatment may be performed only on the side not in contact with the electrode of the polyimide film by placing the polyimide film in contact with the electrode on one side by plasma treatment with the parallel plate type electrode it can.
  • the polyimide film is placed in a state of being electrically floated in the space between the two electrodes, plasma processing can be performed on both sides.
  • single-sided processing becomes possible by performing a plasma processing in the state which stuck the protective film on the single side
  • a protective film a PET film with an adhesive, an olefin film, etc. can be used.
  • the surface roughness Ra of the polyimide film in the present invention is desirably 70 nm or less, more desirably 30 nm or less, and further desirably 1.5 nm or less.
  • Ra is larger than 70 nm, when a plurality of polyimide films are pasted together via a silane coupling agent layer, it causes uneven coating of the silane coupling agent and peeling unevenness due to it.
  • a polyimide film is laminated via a silane coupling agent layer to obtain a polyimide film laminate in which the polyimide film layer and the silane coupling agent condensate are alternately laminated.
  • Lamination of the polyimide film is performed by overlapping and pressing the polyimide film so that the surface subjected to the silane coupling agent treatment is disposed between the polyimide film layers.
  • the combination of pressurization and heating is effective.
  • the pressure treatment may be performed while heating, for example, a press, a laminate, a roll laminate, or the like in an atmospheric pressure atmosphere or in vacuum.
  • the method of pressure-heating in the state put in the flexible bag is also applicable. From the viewpoint of improvement in productivity and reduction in processing cost brought about by high productivity, press or roll lamination under an air atmosphere is preferable, and in particular, a method of using a roll (roll laminate etc.) is preferable.
  • the pressure in the pressure treatment is preferably 1 MPa to 20 MPa, and more preferably 3 MPa to 10 MPa. If the pressure is too high, the support may be broken, and if the pressure is too low, parts that do not adhere may be formed, resulting in insufficient adhesion.
  • a temperature in the case of a pressure treatment it carries out in the range which does not exceed the heat-resistant temperature of the polyimide film to be used. In the case of a non-thermoplastic polyimide film, treatment at 10 ° C. to 400 ° C., more preferably 150 ° C. to 350 ° C. is preferred.
  • the pressure treatment can also be carried out in the atmospheric pressure atmosphere as described above, but in order to obtain stable adhesive strength over the entire surface, it is preferable to carry out under vacuum. At this time, a degree of vacuum by a normal oil rotary pump is sufficient, and about 10 Torr or less is sufficient.
  • a degree of vacuum by a normal oil rotary pump is sufficient, and about 10 Torr or less is sufficient.
  • an apparatus which can be used for the pressure heating process for example, “11FD” manufactured by Imoto Seisakusho Co., Ltd. can be used to press in vacuum, and a roll type film laminator in vacuum or vacuum is used.
  • MVLP manufactured by Meiki Seisakusho
  • the pressurization process can be performed separately in the pressurization process and the heating process.
  • the polyimide film and the inorganic substrate are pressurized (preferably about 0.2 to 50 MPa) at a relatively low temperature (for example, a temperature of less than 120 ° C., more preferably 95 ° C. or less) to secure adhesion between them.
  • a relatively low temperature for example, a temperature of less than 120 ° C., more preferably 95 ° C. or less
  • low pressure preferably less than 0.2 MPa, more preferably 0.1 MPa or less
  • relatively high temperature at normal pressure eg, 120 ° C.
  • the adhesion strength between polyimide film layers of the polyimide film laminate in the present invention is 0.1 N / cm or more and 20 N / cm or less, preferably 0.1 N / cm or more and 18 N / cm or less in the 90 degree peeling method. More preferably, they are 0.15 N / cm or more and 15 N / cm or less.
  • the thickness was measured using a micrometer such as polyimide film (manufactured by FINE LUG, Millitron 1245D).
  • Elastic modulus of polyimide film room temperature and 400 ° C
  • What cut out the polyimide film or polyimide film laminated body of a measuring object in strip shape of length 150 mm x width 20 mm was made into the test piece.
  • the position of 100 mm from the free end of the test piece was fixed with a metal jig and the elastic modulus was determined by measuring the amount of deflection from the side.
  • FIG. 6 shows a schematic view of a metal jig used for measurement. The following equation was used to calculate the elastic modulus.
  • a value of 30 minutes after placing the sample in the electric furnace was taken as the amount of deflection at 400 ° C., using a program electric furnace MMF-2W with a window by As One.
  • the adhesive strength between the polyimide film layers of the polyimide film laminate was determined according to the 90 degree peeling method of JIS K 6854-1. Device name; Shimadzu Corporation autograph AG-IS Measurement temperature: Room temperature peeling speed: 50 mm / min Atmosphere: Atmospheric measurement sample width: 1 cm The sample was cut to a depth corresponding to 120% of the thickness of the outermost polyimide film on the surface of a square polyimide film laminate having a side of 100 mm, and was measured by peeling the outermost polyimide film from the end of the laminate. . The adhesive strength was measured after heat treatment at 200 ° C. for one hour.
  • the film thickness of the silane coupling agent condensate layer is a cross section in the direction perpendicular to the film surface of the polyimide film laminate, after which a microtome is made into an ultra-thin section by a transmission electron microscope A cross-sectional photograph was taken, and the measured value was calculated back from the magnification.
  • the polyamic acid solution V1 obtained above was used as a final film thickness (imide) on a smooth surface (non-slipper surface) of a long polyester film (“A-4100” manufactured by Toyobo Co., Ltd.) having a width of 1050 mm using a slit die.
  • the coating was applied so that the film thickness after conversion was 38 .mu.m, dried at 105.degree. C. for 20 minutes, and peeled from the polyester film to obtain a self-supporting polyamic acid film having a width of 920 mm.
  • heat treatment is carried out by a pin tenter for the first stage 150 ° C.
  • the polyamic acid solution V1 obtained above was used as a final film thickness (imide) on a smooth surface (non-slipper surface) of a long polyester film (“A-4100” manufactured by Toyobo Co., Ltd.) having a width of 1050 mm using a slit die.
  • the film was applied so as to give a film thickness of 114 ⁇ m, dried at 105 ° C. for 20 minutes, and peeled from the polyester film to obtain a self-supporting polyamic acid film having a width of 920 mm.
  • heat treatment is carried out by a pin tenter for the first stage 150 ° C.
  • F3 Upirex 25S (Ube Industries, Ltd. polyimide film, 25 ⁇ m thick)
  • F4 Kapton 100H (Toray Dupont Co., Ltd. polyimide film, 25 ⁇ m thick)
  • F5 Upirex 75S (Ube Industries, Ltd. polyimide film, 75 ⁇ m thick)
  • F6 Kapton 200H (Toray Dupont Co., Ltd. polyimide film, 25 ⁇ m thick)
  • the vacuum plasma process was performed to the polyimide film as a pre-process which performs a silane coupling agent process to a polyimide film.
  • a device for sheet glass is used, a metal mask is stacked on the surface of the glass treated with a silane coupling agent, and the inside of the vacuum chamber is evacuated to 1 ⁇ 10 ⁇ 3 Pa or less.
  • Argon gas was introduced into the vacuum chamber, and the surface of the glass plate was plasma-treated with argon gas for 20 seconds under conditions of a discharge power of 100 W and a frequency of 15 kHz.
  • ⁇ Silane coupling agent treatment example 1> Using a coater, a polyimide film was coated with a silane coupling agent SC1 ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd .: 3-glycidoxypropyl methoxysilane) under the following conditions. Using a wire bar that moves a 280 mm wide polyimide film at 10 m / s and adjusts the distance to the film to 20 ⁇ m, 0.5 wt% of the silane coupling agent isopropanol solution from the film upstream side of the wire bar Were obtained to obtain a silane coupling agent coated polyimide film roll.
  • a silane coupling agent SC1 (KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd .: 3-glycidoxypropyl methoxysilane)
  • silane coupling agent treatment example 2 The silane coupling agent was apply
  • a polyimide film having a width of 220 mm was passed through a 750 mm ⁇ 20 mm ⁇ 10 mm chamber having a 20 mm ⁇ 250 mm slit at a speed of 240 mm / min.
  • the stiffener of the present invention is higher in rigidity than a single layer film of the same thickness, and is excellent in heat resistance. Therefore, the stiffener is not limited to the use for reinforcing an FPC board, and can be used in high temperature processes. In addition, by using the technique of the present invention, it is possible to make thick sheets and plates by repeating lamination. By machining these, engineering plastic use becomes possible.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention aborde le problème de la réalisation d'un raidisseur comprenant un stratifié de film de polyimide présentant une résistance à la chaleur et une rigidité supérieures à celle d'un film de polyimide d'un corps d'une seule couche d'épaisseur, et de fournir un procédé de production de celui-ci. La solution selon l'invention porte sur l'activation de la surface du film de polyimide, puis à sa soumission à un traitement par agent de couplage au silane. Ensuite, les films de polyimide traités par agent de couplage au silane obtenus sont empilés les uns sur les autres, et mis sous pression et chauffés pour obtenir un stratifié de film de polyimide. Le stratifié de film de polyimide obtenu a une structure en coupe transversale comprenant des couches de film de polyimide et des couches de condensat d'agent de couplage au silane alternées. Ce stratifié de film de polyimide a un module d'élasticité élevé égal ou supérieur à 0,5 GPa, même à 400 °C.
PCT/JP2018/047212 2018-01-05 2018-12-21 Raidisseur Ceased WO2019135367A1 (fr)

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WO2021040004A1 (fr) * 2019-08-30 2021-03-04 株式会社カネカ Film de polyimide, son procédé de production et composition de résine de polyimide
JP2021145045A (ja) * 2020-03-12 2021-09-24 東洋紡株式会社 品位が良く、耐折り曲げ性に優れたスティフナー
JP2021147439A (ja) * 2020-03-17 2021-09-27 東洋紡株式会社 ポリイミドフィルム積層体の製造方法
JP2021163785A (ja) * 2020-03-30 2021-10-11 三井化学東セロ株式会社 電子装置の製造方法
CN114830842A (zh) * 2019-12-13 2022-07-29 卡纳图有限公司 成形膜及其制造方法

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WO2021040004A1 (fr) * 2019-08-30 2021-03-04 株式会社カネカ Film de polyimide, son procédé de production et composition de résine de polyimide
JPWO2021040004A1 (fr) * 2019-08-30 2021-03-04
CN114830842A (zh) * 2019-12-13 2022-07-29 卡纳图有限公司 成形膜及其制造方法
CN114830842B (zh) * 2019-12-13 2024-05-24 卡纳图有限公司 成形膜及其制造方法
JP2021145045A (ja) * 2020-03-12 2021-09-24 東洋紡株式会社 品位が良く、耐折り曲げ性に優れたスティフナー
JP7651824B2 (ja) 2020-03-12 2025-03-27 東洋紡株式会社 品位が良く、耐折り曲げ性に優れたスティフナー
JP2021147439A (ja) * 2020-03-17 2021-09-27 東洋紡株式会社 ポリイミドフィルム積層体の製造方法
JP7452135B2 (ja) 2020-03-17 2024-03-19 東洋紡株式会社 ポリイミドフィルム積層体の製造方法
JP2021163785A (ja) * 2020-03-30 2021-10-11 三井化学東セロ株式会社 電子装置の製造方法
JP7374039B2 (ja) 2020-03-30 2023-11-06 三井化学東セロ株式会社 電子装置の製造方法

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