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WO2009157143A1 - Film de démoulage - Google Patents

Film de démoulage Download PDF

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Publication number
WO2009157143A1
WO2009157143A1 PCT/JP2009/002564 JP2009002564W WO2009157143A1 WO 2009157143 A1 WO2009157143 A1 WO 2009157143A1 JP 2009002564 W JP2009002564 W JP 2009002564W WO 2009157143 A1 WO2009157143 A1 WO 2009157143A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
wiring board
molecular weight
printed wiring
thermal expansion
Prior art date
Application number
PCT/JP2009/002564
Other languages
English (en)
Japanese (ja)
Inventor
小野寺稔
大森一行
浅野誠
Original Assignee
株式会社クラレ
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 株式会社クラレ filed Critical 株式会社クラレ
Publication of WO2009157143A1 publication Critical patent/WO2009157143A1/fr

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • 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
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0141—Liquid crystal polymer [LCP]

Definitions

  • the present invention relates to a release film that is excellent in heat resistance, releasability, and non-contamination, and that can be easily disposed of, and is used during hot press molding of a printed wiring board, and a printed wiring board using the release film. It relates to a manufacturing method.
  • a film made of a thermoplastic liquid crystal polymer that forms an optically anisotropic molten phase.
  • release films are used when hot pressing copper foil.
  • Patent Document 1 discloses a release film that is excellent in heat resistance, release properties, and non-contamination properties and can be easily disposed of.
  • a combination of a metal layer and a thermoplastic film having a specific shear modulus is described as a release film.
  • this thermoplastic film since this thermoplastic film has a specific shear modulus, it is possible to prevent a decrease in cushioning property due to thermal deformation of the thermoplastic film during hot press molding. It is also described that it exhibits excellent followability with respect to irregularities.
  • the TLCP film may be deformed and cannot be used as a printed wiring board.
  • An object of the present invention is to provide a release film that can be applied to a wide variety of TLCP films even when the TLCP film is used as a substrate or coverlay film of a printed wiring board.
  • Another object of the present invention is to provide a release film that can prevent circuit deformation occurring in a printed wiring board to a very high level without adjusting the thermal expansion coefficient of the TLCP film in advance.
  • Yet another object of the present invention is to use such a release film to extremely highly prevent circuit deformation even when a printed wiring board using a TLCP film is hot press molded at a high temperature.
  • Another object of the present invention is to provide a method for manufacturing a printed wiring board.
  • the present inventors studied a release film in view of the existence of a TLCP film that is deformed during hot pressing and cannot be used as a printed wiring board.
  • the TLCP film has a positive coefficient of thermal expansion, so it has traditionally been thought that the thermoplastic film forming the release film must also have a positive coefficient of thermal expansion in order to follow it. It was.
  • the obtained release film not only has excellent release properties and cushioning properties in the thickness direction, but also gives stress derived from thermal expansion to the TLCP film in the temperature range for hot pressing. As a result, it was found that the release film was applicable to a wide variety of TLCP films, and the present invention was completed.
  • the present invention relates to a film made of a thermoplastic liquid crystal polymer that forms an optically anisotropic melt phase.
  • a substrate (ii) a coverlay film, or (iii) a substrate and a coverlay film
  • the release film comprises an ultra-high molecular weight polyolefin film layer and a reinforcing layer superimposed
  • the ultrahigh molecular weight polyolefin film layer has a molecular orientation degree SOR in the longitudinal direction of the film in the range of 0.95 or more and less than 1.05, and the average of the thermal expansion coefficient in the plane direction of the film is a negative value
  • the reinforcing layer is a release film whose average thermal expansion coefficient in the plane direction of the reinforcing layer is a positive value.
  • the ultrahigh molecular weight polyolefin film layer may have an average thermal expansion coefficient (M UP ) of ⁇ 1 ⁇ 10 ⁇ 6 cm / cm / ° C. or less in the planar direction, and the reinforcing layer may have a thermal expansion coefficient in the planar direction.
  • the average coefficient (M RE ) may be in the range of 1 ⁇ 10 ⁇ 6 to 30 ⁇ 10 ⁇ 6 cm / cm / ° C.
  • the ultrahigh molecular weight polyolefin constituting the ultrahigh molecular weight polyolefin film layer usually has a viscosity average molecular weight of 1 million or more in many cases.
  • the release film the average of the average of the planar direction of the thermal expansion coefficient of the ultra-high molecular weight polyolefin film layer (M UP), the average of the planar direction of the thermal expansion coefficient of the reinforcing layer (M RE) (M T)
  • M UP ultra-high molecular weight polyolefin film layer
  • M RE reinforcing layer
  • M T it may be a negative value.
  • each layer can be appropriately set.
  • the thickness (A) of the ultrahigh molecular weight polyolefin film layer may be about 30 to 200 ⁇ m
  • the thickness (B) of the reinforcing layer is Further, the ratio (B) / (A) of the thickness (B) of the reinforcing layer to the thickness (A) of the ultra-high molecular weight polyolefin film layer may be 60 / 40-10. It may be about / 90.
  • the present invention further provides a film comprising a thermoplastic liquid crystal polymer that forms an optically anisotropic melt phase, wherein (i) a substrate, (ii) a coverlay film, or (iii) a substrate and a coverlay film.
  • a method for manufacturing a printed wiring board by hot press molding A method for producing a printed wiring board in which the release film according to any one of claims 1 to 7 is disposed in such a manner that the reinforcing layer is in contact with the press hot plate at the time of hot press molding is also included.
  • the hot press molding temperature may be selected from a range (for example, about 250 to 320 ° C.) that is at least 15 ° C. lower than the melting point of the thermoplastic liquid crystal polymer and lower than 15 ° C. above the melting point.
  • the present invention also includes a printed wiring board manufactured by such a manufacturing method.
  • the present invention also includes a printed wiring board, a cover lay film, or a film made of a thermoplastic liquid crystal polymer that forms an optically anisotropic molten phase for forming both a substrate and a cover lay film; Placed above and below the wiring board or the coverlay film so as to sandwich the printed wiring board or the coverlay film, in combination with a reinforcing layer whose average thermal expansion coefficient in the plane direction of the reinforcing layer is a positive value An ultra-high molecular weight polyolefin film for constituting a release film;
  • the invention relates to a material for laminating that is sandwiched between press hot plates and is subjected to hot press molding.
  • the ultrahigh molecular weight polyolefin film layer has a molecular orientation in the longitudinal direction of the film.
  • the degree SOR is in the range of 0.95 or more and less than 1.05, and the average thermal expansion coefficient in the plane direction of the film is a negative value.
  • the average of the thermal expansion coefficients in the plane direction means the thermal expansion coefficient in the machine axis direction (hereinafter abbreviated as MD direction) in the plane direction of the film and the like and the direction orthogonal to the machine axis direction (hereinafter referred to as “the direction of the machine axis”). , which is abbreviated as TD direction) and means an average value obtained by dividing the sum of the thermal expansion coefficients by 2.
  • a release film is formed by combining an ultra-high molecular weight polyolefin film layer having a negative coefficient of thermal expansion and a reinforcing layer having a positive coefficient of thermal expansion. Therefore, for a wide variety of TLCP films, Even if applied, deformation due to hot press molding of the printed wiring board can be reduced.
  • the circuit deformation that occurs in the printed wiring board can be extremely advanced without adjusting the thermal expansion coefficient of the TLCP film in advance. Can be prevented.
  • the release film of the present invention comprises a TLCP film (that is, a film made of a thermoplastic liquid crystal polymer that forms an optically anisotropic melt phase), (i) a substrate, (ii) a coverlay film, or (iii) ) Used in hot press molding in the manufacturing process of printed wiring boards used as both a base material and a coverlay film.
  • the release film is a laminate of an ultrahigh molecular weight polyolefin film and at least one reinforcing layer. Prepare in the state.
  • the molecular orientation degree SOR in the longitudinal direction of the film is in the range of 0.95 or more and less than 1.05, and the average thermal expansion coefficient in the plane direction of the film is a negative value.
  • the molecular orientation degree SOR in the longitudinal direction of the ultra high molecular weight polyolefin film is in the range of 0.95 or more and less than 1.05, the orientation state of the molecules can be kept isotropic, During subsequent cooling, it is possible to prevent the printed wiring board from being unevenly distorted or deformed due to the anisotropy of the film.
  • the SOR is more preferably in the range of 0.98 to 1.03.
  • the average (M UP ) of the thermal expansion coefficient in the plane direction of the ultrahigh molecular weight polyolefin film needs to be a negative value. It is preferably ⁇ 1 ⁇ 10 ⁇ 6 cm / cm / ° C. or less, more preferably about ⁇ 500 ⁇ 10 ⁇ 6 to ⁇ 10 ⁇ 10 ⁇ 6 cm / cm / ° C., and further preferably ⁇ 400. It may be about ⁇ 10 ⁇ 6 to ⁇ 30 ⁇ 10 ⁇ 6 cm / cm / ° C.
  • the thermal expansion coefficient of the printed wiring board is a positive value (for example, about 18 ⁇ 10 ⁇ 6 cm / cm / ° C.)
  • the thermal expansion coefficient of the ultra-high-molecular-weight polyolefin film constituting the release film is set to a negative value, and the force that deforms to the heat shrink side due to the stress in the plane direction is exerted, so that the heat of the entire laminate that works during hot pressing is applied. Expansion can be reduced.
  • the thickness of the ultra-high molecular weight polyolefin film is preferably in the range of about 30 to 200 ⁇ m, more preferably in the range of about 30 to 180 ⁇ m.
  • the thermal contraction force due to the negative thermal expansion coefficient of the film increases, and the printed wiring board may be distorted in the contraction direction.
  • the film is too thin, it will be close to the thickness of the circuit provided on the printed wiring board, and the cushioning property that the release film should have and the fluidity will be insufficient. Adhesion may be reduced.
  • the method for producing the ultrahigh molecular weight polyolefin film is not particularly limited as long as it has a predetermined SOR and thermal expansion coefficient, and may be produced by various methods.
  • such an ultra high molecular weight polyolefin film can be obtained by inflation molding an ultra high molecular weight polyolefin having a predetermined intrinsic viscosity.
  • the intrinsic viscosity is less than 5 dl / g, mechanical strength such as tensile strength and impact strength is not sufficient.
  • the melt viscosity is low, twisting due to co-rotation of the melt of the ultra-high molecular weight polyolefin and the mandrel in the screw die and uneven thickness due to bending of the mandrel are likely to occur, and it is difficult to obtain a uniform film, resulting in poor moldability.
  • the upper limit of the intrinsic viscosity [ ⁇ ] is not particularly limited, but those exceeding 25 dl / g tend to be inferior in extrusion moldability because the melt viscosity is too high.
  • the viscosity average molecular weight of the ultra-high molecular weight polyolefin may be, for example, 1 million or more, preferably about 2 million to 7 million, and more preferably about 3 million to 6 million.
  • the measuring method of the intrinsic viscosity used for calculation of a viscosity average molecular weight can be measured based on JISK7367-3: 1999.
  • the shear modulus at the press molding temperature of the ultrahigh molecular weight polyolefin can be selected from a wide range of 5 ⁇ 10 4 to 1 ⁇ 10 7 Pa, preferably about 1 ⁇ 10 5 to 5 ⁇ 10 6 Pa. More preferably, it is about 1 ⁇ 10 5 to 5 ⁇ 10 5 Pa (for example, 1 ⁇ 10 5 or more and less than 5 ⁇ 10 5 Pa), particularly preferably about 1 ⁇ 10 5 to 3 ⁇ 10 5 Pa. May be.
  • the shear modulus is obtained by dynamic viscoelasticity measurement and can be measured with a viscoelastic rheometer.
  • ultra high molecular weight polyolefin examples include ultra high molecular weight polyethylene and ultra high molecular weight polypropylene. Among these, ultra high molecular weight polyethylene is preferably used.
  • the ultrahigh molecular weight polyethylene contains ethylene as a repeating unit, and may further contain other copolymerization components in addition to ethylene.
  • copolymer components include ⁇ -olefins having 2 to 20 carbon atoms such as propylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene; methyl acrylate, ethyl acrylate, ⁇ , ⁇ -unsaturated carboxylic acid esters such as butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate; acrylonitrile, methacrylate Examples include ronitrile, acrolein, methacrolein, ethyl vinyl ether, styrene, vinyl acetate and the like.
  • copolymerization components can be used alone or in combination of two or more. Of these copolymer components, ⁇ -olefins are preferred.
  • the ultra high molecular weight polyethylene preferably contains 99.5 mol% or more, preferably 99.8 mol% or more of the repeating units.
  • the ultrahigh molecular weight polyolefin may be blended with an inorganic filler, fiber, nucleating agent, mold release agent, antioxidant (anti-aging agent), heat stabilizer and the like. These may be used alone or in combination of two or more.
  • the inorganic filler is not particularly limited, and examples thereof include layered double hydrates such as calcium carbonate, titanium oxide, mica, talc, barium sulfate, alumina, silicon oxide, and hydrotalcite.
  • the fiber is not particularly limited, and examples thereof include glass fiber, carbon fiber, boron fiber, silicon carbide fiber, inorganic fiber such as alumina fiber; organic fiber such as aramid fiber.
  • the antioxidant is not particularly limited.
  • the heat stabilizer is not particularly limited, and examples thereof include tris (2,4-di-t-butylphenyl) phosphite, trilauryl phosphite, 2-t-butyl- ⁇ - (3-t-butyl-4 -Hydroxyphenyl) -p-cumenylbis (p-nonylphenyl) phosphite, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythryl tetrakis (3-laurylthiopro) Pionate) and ditridecyl 3,3'-thiodipropionate.
  • ultra-high molecular weight polyolefin inflation molding can be performed by a known or conventional method to obtain an ultra-high molecular weight polyolefin film having a predetermined SOR and thermal expansion coefficient used in the present invention. As long as the obtained film exhibits a predetermined SOR and thermal expansion coefficient, three-dimensional crosslinking may be introduced. The degree of polymerization of the polymer is increased during polymerization, or post-treatment such as electron beam crosslinking after polymerization. May be performed. Furthermore, the ultrahigh molecular weight polyolefin film may be used in a single layer, but may have a multilayer structure, and a film made of different materials may be multilayered as necessary.
  • the reinforcing layer needs to have a positive average thermal expansion coefficient in the plane direction of the reinforcing layer, for example, within a range of 1 ⁇ 10 ⁇ 6 to 30 ⁇ 10 ⁇ 6 cm / cm / ° C. Is preferred. If the thermal expansion coefficient is a negative value, the degree of thermal shrinkage increases due to the sum of the negative thermal expansion coefficient of the ultrahigh molecular weight polyolefin film and the printed wiring board is distorted in the shrinking direction. On the other hand, if the thermal expansion coefficient is too high, the printed wiring board may be distorted in the expansion direction.
  • the reinforcing layer preferably has heat resistance.
  • a cover lay film made of a liquid crystal polymer is bonded to a printed wiring board by heat melting, a high lamination temperature is required and is usually 260 ° C. or higher. Therefore, as a material suitable for the reinforcing plate, a metal foil with little oxidation deterioration, such as an aluminum foil or a stainless steel foil, is used.
  • a polyimide film which is a thermosetting resin is suitable. These materials may be used alone or in combination of two or more.
  • the reinforcing layer may be used as a single layer, but may have a multilayer structure, and a film made of different materials may be multilayered as necessary.
  • the thickness of the reinforcing layer is preferably in the range of about 10 to 100 ⁇ m, and more preferably in the range of about 20 to 50 ⁇ m. If the reinforcing layer is too thick, the contribution of the positive thermal expansion coefficient in the plane direction will increase, offsetting the negative thermal expansion coefficient contribution of the ultra-high molecular weight polyolefin film, and distorting the printed wiring board. End up. On the other hand, if the reinforcing layer is too thin, the contribution of the negative thermal expansion coefficient of the ultra-high molecular weight polyolefin film increases, and the printed wiring board is distorted.
  • the ultrahigh molecular weight polyolefin film and the reinforcing layer are laminated in a laminated state.
  • the superposition may be integrated as well as simple superposition.
  • the ultrahigh molecular weight polyolefin film and the reinforcing layer are usually composed of one sheet each, but a plurality of layers may be used.
  • the average (M UP ) of the thermal expansion coefficient in the planar direction of the ultrahigh molecular weight polyolefin film layer and the thermal expansion coefficient in the planar direction of the reinforcing layer may be a negative value, and preferably about ⁇ 1 ⁇ 10 ⁇ 6 to ⁇ 200 ⁇ 10 ⁇ 6 cm / cm / ° C. More preferably, it may be about ⁇ 5 ⁇ 10 ⁇ 6 to ⁇ 150 ⁇ 10 ⁇ 6 cm / cm / ° C.
  • the ratio (B) / (A) of the thickness (B) of the reinforcing layer to the thickness (A) of the ultrahigh molecular weight polyolefin film layer depends on the thermal expansion coefficient forming each layer.
  • (B) / (A) is 60/40 to 10 / It may be about 90, preferably about 55/45 to 15/85.
  • the surface of the ultrahigh molecular weight polyolefin film used for the release film of the present invention preferably has smoothness, but may have slipping properties, antiblocking properties, etc. necessary for handling.
  • an appropriate embossed pattern may be provided on at least one surface for the purpose of removing air during hot press molding.
  • a release agent such as a silicone release agent may be applied to the surface of the reinforcing layer side opposite to the ultrahigh molecular weight polyolefin film layer to improve the release property.
  • a TLCP film is used as (i) a base material, (ii) a coverlay film, or (iii) both a base material and a coverlay film, and printed wiring is formed by hot press molding.
  • the release film is arranged so that the reinforcing layer is in contact with the hot press plate.
  • the raw material of the thermoplastic liquid crystal polymer film used as the substrate of the printed wiring board or as the coverlay film is not particularly limited, but specific examples thereof include (1) to Examples thereof include known thermotropic liquid crystal polyesters and thermotropic liquid crystal polyester amides derived from the compounds classified as (4) and derivatives thereof.
  • thermotropic liquid crystal polyesters and thermotropic liquid crystal polyester amides derived from the compounds classified as (4) and derivatives thereof.
  • thermotropic liquid crystal polyester amides derived from the compounds classified as (4) and derivatives thereof.
  • Aromatic or aliphatic dihydroxy compounds (see Table 1 for typical examples)
  • Aromatic diamine, aromatic hydroxyamine or aromatic aminocarboxylic acid (see Table 4 for typical examples)
  • thermoplastic liquid crystal polymer used in the present invention is within the range of about 200 to about 400 ° C., particularly within the range of about 250 to about 350 ° C. for the purpose of obtaining the desired heat resistance and processability of the film. However, those having a relatively low melting point are easier to produce from the viewpoint of film production.
  • the liquid crystal polymer film is obtained by extruding a thermoplastic liquid crystal polymer. Any extrusion method can be used for this purpose, but the well-known T-die film-drawing method, inflation method and the like are industrially advantageous.
  • stretching the laminated body of the formed film and a support film can also be used.
  • stress is applied not only in the mechanical axis direction of the film (hereinafter abbreviated as MD direction) but also in the direction orthogonal thereto (hereinafter abbreviated as TD direction). And a film having a balance of mechanical properties and thermal properties in the TD direction can be obtained.
  • various TLCP films can be used as a substrate or a coverlay film regardless of the change in the thermal expansion coefficient of the TLCP film. That is, the thermal expansion coefficient of the TLCP film may be substantially constant or changed before and after hot press molding. In particular, when the release film of the present invention is used, the thermal expansion coefficient of the TLCP film varies greatly before and after hot press molding (for example, the thermal expansion coefficient (H a ) after hot press molding and hot press molding.
  • thermoplastic liquid crystal polymer film used in the present invention may have any thickness, and includes a plate or sheet of 2 mm or less.
  • the film thickness is preferably in the range of 20 to 150 ⁇ m, More preferably within the range of 50 ⁇ m.
  • the film thickness is too thin, the rigidity and strength of the film will be reduced, so when mounting electronic parts on the resulting printed wiring board, it will be deformed by pressure, resulting in poor wiring position accuracy. Cause.
  • thermoplastic liquid crystal polymer film may contain additives such as a lubricant and an antioxidant.
  • the printed wiring board can be manufactured by using the TLCP film as a base material and forming a circuit layer made of a conductor such as copper on the TLCP film by a known or conventional method.
  • Examples of such printed wiring boards include flexible printed wiring boards and multilayer printed wiring boards.
  • the coverlay film and the printed wiring board can be bonded by hot press molding.
  • a thermosetting resin such as an epoxy resin may be applied between the coverlay film and the printed wiring board, and then hot press molding may be performed.
  • the press molding temperature an appropriate temperature is selected depending on the kind of the thermoplastic liquid crystal polymer constituting the TLCP film.
  • the molding temperature is 15 ° C. lower than the melting point of the thermoplastic liquid crystal polymer, And it may be performed at a temperature selected from a range of 15 ° C. higher than the melting point or less.
  • such a molding temperature may be selected within a range of about 250 to 320 ° C. (preferably about 260 to 310 ° C.).
  • the reinforcing layer side constituting the release film of the present invention is applied to the press hot plate, and the ultrahigh molecular weight polyolefin film layer side is applied to the circuit surface or coverlay film surface of the printed wiring board. Can be used by guessing.
  • the printed wiring board obtained using the release film of the present invention can extremely highly prevent circuit deformation due to hot press molding, and has a high density wiring or a thin wiring board. However, it can be used effectively without being affected by distortion due to circuit deformation.
  • the circuit board deformation ratio obtained by measuring the distance between circuits on the wiring board before and after hot pressing may be about 0.01 to 0.06%, and preferably 0.05% or less. .
  • the TLCP film is used to form a printed wiring board, a coverlay film, or both a substrate and a coverlay film, and the ultrahigh molecular weight polyolefin film sandwiches the printed wiring board or the coverlay film.
  • the TLCP film is used to form a printed wiring board, a coverlay film, or both a substrate and a coverlay film, and the ultrahigh molecular weight polyolefin film sandwiches the printed wiring board or the coverlay film.
  • it is used in combination with a reinforcing layer placed above and below the wiring board or the coverlay film.
  • the molecular orientation degree SOR (Segment Orientation Ratio) is an index that gives the degree of molecular orientation, and is different from the conventional MOR (Molecular Orientation Ratio), and takes into account the thickness of the object. This molecular orientation degree SOR is calculated as follows.
  • a liquid crystal polymer film is inserted into a microwave resonant waveguide so that the film surface is perpendicular to the traveling direction of the microwave, and the microscopic film transmitted through the film is transmitted.
  • the electric field strength of the wave is measured.
  • m value (it calls a refractive index) is computed by following Formula.
  • m (Zo / ⁇ z) X [1- ⁇ max / ⁇ o]
  • Zo is a device constant
  • ⁇ z is the average thickness of the object
  • ⁇ max is the frequency that gives the maximum microwave transmission intensity when the microwave frequency is changed
  • ⁇ o is the average thickness of zero (that is, the object is Is the frequency that gives the maximum microwave transmission intensity.
  • the degree of molecular orientation SOR is calculated by m 0 / m 90, where m 0 when the direction coincides with m 0 and m 90 when the rotation angle is 90 ° is m 90 .
  • the thermal expansion coefficient ⁇ is a coefficient obtained by dividing the expansion coefficient when heated at a constant heating rate from room temperature to near the heat distortion temperature of the film by the temperature difference, and is calculated as follows.
  • thermomechanical analyzer First, using a known thermomechanical analyzer, one end of a strip cut film is fixed, a tensile load is applied to the other end, and the amount of expansion when heated at a constant temperature increase rate is measured. Thermal expansion, assuming that the length L 0 (mm) of the film in the load direction of the film is L 1 (mm), the temperature is T 2 (° C.), and the room temperature is T 1 (° C.).
  • the coefficient ⁇ can be calculated by the following formula.
  • ⁇ [(L 1 ⁇ L 0 ) / (T 2 ⁇ T 1 )] / L 0 ( ⁇ 10 ⁇ 6 cm / cm / ° C.)
  • L 0 20 mm
  • T 2 150 ° C.
  • T 1 25 ° C.
  • the tensile load is 1 g.
  • Circuit dimension change rate The distance between the circuits on the wiring board before and after hot pressing was measured and calculated as a percentage of the value obtained by dividing the change in distance before and after hot pressing by the distance after hot pressing.
  • the film was obtained by observing the thermal behavior of the film using a differential scanning calorimeter. That is, after the TLCP film was heated at a rate of 10 ° C./min to be completely melted, the melt was rapidly cooled to 50 ° C. at a rate of 10 ° C./min, and then heated again at a rate of 10 ° C./min. The position of the endothermic peak that occasionally appears was recorded as the melting point.
  • Example 1 As the ultrahigh molecular weight polyolefin film layer, the degree of molecular orientation SOR is 1.01, the average thermal expansion coefficient is ⁇ 221.5 ⁇ 10 ⁇ 6 cm / cm / ° C., and the shear modulus at the hot press lamination temperature is 1.5.
  • a copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid (molar ratio of p-hydroxybenzoic acid unit to 6-hydroxy-2-naphthoic acid unit: 73/27), and has a melting point of 280 ° C.
  • a thermoplastic liquid crystal polymer was melt-extruded, and a film having a film thickness of 50 ⁇ m and a melting point of 280 ° C. was obtained by an inflation film molding method while controlling the longitudinal and lateral stretch ratios. The obtained film was further left to stand in a hot air dryer at 260 ° C. for 3 hours for heat treatment to obtain a film having a melting point of 290 ° C.
  • This film is used as a base film, and a 18 ⁇ m thick copper foil is set on the top and bottom of the base film. After holding the press temperature at 290 ° C., the press pressure at 4 MPa, and the press time for 60 minutes, cooling to 100 ° C. to release the press pressure A copper-clad laminate was obtained. Further, a printed wiring board was obtained by processing a circuit according to the evaluation pattern of IPC B-25 as a printed wiring.
  • thermoplastic liquid crystal polymer was melt-extruded, and a film having a film thickness of 25 ⁇ m and a melting point of 280 ° C. was obtained by an inflation molding method while controlling the longitudinal and lateral stretch ratios. Perforations with a diameter of 20 mm were arbitrarily opened in this film and used as a coverlay film.
  • Example 2 As the ultrahigh molecular weight polyolefin film layer, the degree of molecular orientation SOR is 1.02, the average coefficient of thermal expansion is ⁇ 85.4 ⁇ 10 ⁇ 6 cm / cm / ° C., and the shear modulus at the hot press lamination temperature is 1.5.
  • Example 3 As the reinforcing layer, a stainless steel foil having an average thermal expansion coefficient of 16 ⁇ 10 ⁇ 6 cm / cm / ° C. (manufactured by JFE Steel Co., Ltd., “SUS304H”, thickness 50 ⁇ m) is used as a constituent material of the release film. Except that, a flexible printed wiring board was obtained in the same manner as in Example 1. Table 6 shows the releasability of the release film and the circuit dimension change rate of the flexible printed wiring board.
  • Example 4 As an ultrahigh molecular weight polyethylene film layer, a flexible printed wiring board was obtained in the same manner as in Example 1 except that three sheets used in Example 1 were stacked to have a thickness of 150 ⁇ m. Table 6 shows the releasability of the release film and the circuit dimension change rate of the flexible printed wiring board.
  • Example 1 instead of the ultra-high molecular weight polyolefin film layer, the degree of molecular orientation SOR is 1.20, the average coefficient of thermal expansion is 270 ⁇ 10 ⁇ 6 cm / cm / ° C., and the shear modulus at hot press lamination temperature is 1 ⁇ 10 5.
  • a flexible printed wiring board was obtained in the same manner as in Example 1 except that a release film was formed using a high-density polyethylene sheet of Pa (made by Okura Kogyo Co., Ltd., thickness: 100 ⁇ m). Table 6 shows the releasability of the release film and the circuit dimension change rate of the flexible printed wiring board.
  • Example 2 instead of the ultrahigh molecular weight polyolefin film layer, the degree of molecular orientation SOR is 1.00, the average coefficient of thermal expansion is 100 ⁇ 10 ⁇ 6 cm / cm / ° C., and the shear modulus at the hot press lamination temperature is 1 ⁇ 10 8.
  • a flexible printed wiring board was obtained in the same manner as in Example 2 except that a release film was formed using a fluororesin sheet (Nitto Denko Co., Ltd., “Nitoflon”, thickness 100 ⁇ m) that was Pa. Table 6 shows the releasability of the release film and the circuit dimension change rate of the flexible printed wiring board.
  • Example 3 As the ultrahigh molecular weight polyolefin film layer, the molecular orientation degree SOR is 1.00, the average thermal expansion coefficient is 295 ⁇ 10 ⁇ 6 cm / cm / ° C., and the shear elastic modulus at the hot press lamination temperature is 2 ⁇ 10 6 Pa.
  • a flexible printed wiring board was obtained in the same manner as in Example 1 except that a release film was formed using a certain ultra-high molecular weight polyethylene sheet (manufactured by Yodogawa Hutech Co., Ltd., “UPE”, thickness 100 ⁇ m). Table 6 shows the releasability of the release film and the circuit dimension change rate of the flexible printed wiring board.
  • Example 5 As the reinforcing layer, a liquid crystal polymer film having an average coefficient of thermal expansion of ⁇ 5 ⁇ 10 ⁇ 6 cm / cm / ° C. (manufactured by Kuraray Co., Ltd., “FA”, thickness 50 ⁇ m) is used to form a release film.
  • a flexible printed wiring board was obtained in the same manner as in Example 1 except that the material was used. Table 6 shows the releasability of the release film and the circuit dimension change rate of the flexible printed wiring board.
  • Example 6 As shown in Table 6, in Example 1 and Example 2, since a resin layer having a specific thermal expansion coefficient and a reinforcing layer were combined, even when hot press molding was performed, the circuit dimensional change rate was low, and the hot press The dimensional stability of the circuit board before and after molding can be improved. Furthermore, when the material of the reinforcing layer was made of stainless steel (Example 3) or when the ultrahigh molecular weight polyethylene film layer was thick (Example 4), the circuit dimension change rate could be further improved.
  • Comparative Examples 1 to 5 the circuit dimension change rate by hot press molding is higher than that of the example, and even when the circuit dimension does not change, the change rate is the same as that of Examples 1 and 2.
  • the circuit dimensions were changed 3 times or more and 10 times or more of Example 4.
  • the coverlay film was given some form defects such as minor wrinkles, deformation, breakage, and wrinkles.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)

Abstract

La présente invention se rapporte à un film de démoulage qui peut s’appliquer à une large gamme de films polymères thermoplastiques à cristaux liquides. Le film de démoulage comporte une couche de film polyoléfine à poids moléculaire ultra-élevé et une couche de renforcement qui sont stratifiées ensemble. Dans la couche de film polyoléfine à poids moléculaire ultra-élevé, le degré d’orientation moléculaire SOR dans le sens de la longueur du film est supérieur ou égal à 0,95 mais inférieur à 1,05, et la moyenne du coefficient de dilatation thermique dans le sens du plan du film est une valeur négative. Dans ladite couche de renforcement, la moyenne du coefficient de dilatation thermique dans le sens du plan de la couche de renforcement est une valeur positive. Ledit film de démoulage est utilisé pour le moulage par compression à chaud lors du processus de fabrication de cartes de circuit imprimé utilisant un film comprenant un polymère thermoplastique à cristaux liquides en tant que (i) matériau de base, (ii) film de revêtement, ou (iii) à la fois matériau de base et film de revêtement.
PCT/JP2009/002564 2008-06-23 2009-06-08 Film de démoulage WO2009157143A1 (fr)

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JP2008163015A JP2011175988A (ja) 2008-06-23 2008-06-23 離型フィルム

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Cited By (4)

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WO2012090733A1 (fr) * 2010-12-27 2012-07-05 株式会社クラレ Carte de circuit, et procédé de fabrication associé
WO2018110361A1 (fr) * 2016-12-16 2018-06-21 東レフィルム加工株式会社 Film détachable et film protecteur
CN112203403A (zh) * 2019-07-08 2021-01-08 Tdk株式会社 印刷配线板、多层印刷配线板和印刷配线板的制造方法
US11932737B2 (en) 2019-08-02 2024-03-19 Airtech International, Inc. Polymer compositions for extrusion and additive manufacturing processes

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JP6309451B2 (ja) * 2012-09-20 2018-04-11 株式会社クラレ 回路基板およびその製造方法
JP6848387B2 (ja) * 2016-11-21 2021-03-24 三菱ケミカル株式会社 偏光子保護フィルム

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JPH11302417A (ja) * 1998-04-22 1999-11-02 Kuraray Co Ltd ポリマーフィルムおよびその製造方法
JP2007008153A (ja) * 2005-05-30 2007-01-18 Nitto Denko Corp 圧着離型シートおよび巻回体
JP2007062175A (ja) * 2005-08-31 2007-03-15 Tokyo Tokushu Shigyo Kk プレス成形用フィルム、プレス成形方法および回路板の製造方法
WO2008012940A1 (fr) * 2006-07-24 2008-01-31 Kuraray Co., Ltd. Film antiadhésif pour la fabrication d'une plaque de circuit imprimé

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JPS61130041A (ja) * 1984-11-28 1986-06-17 ポリプラスチックス株式会社 寸法安定性の良好な成形品の製造方法
JPH11302417A (ja) * 1998-04-22 1999-11-02 Kuraray Co Ltd ポリマーフィルムおよびその製造方法
JP2007008153A (ja) * 2005-05-30 2007-01-18 Nitto Denko Corp 圧着離型シートおよび巻回体
JP2007062175A (ja) * 2005-08-31 2007-03-15 Tokyo Tokushu Shigyo Kk プレス成形用フィルム、プレス成形方法および回路板の製造方法
WO2008012940A1 (fr) * 2006-07-24 2008-01-31 Kuraray Co., Ltd. Film antiadhésif pour la fabrication d'une plaque de circuit imprimé

Cited By (15)

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Publication number Priority date Publication date Assignee Title
KR101935062B1 (ko) * 2010-12-27 2019-01-03 주식회사 쿠라레 회로 기판 및 그 제조 방법
US10244619B2 (en) 2010-12-27 2019-03-26 Kurarau Co., Ltd. Circuit board
US9363890B2 (en) 2010-12-27 2016-06-07 Kuraray Co., Ltd. Circuit board and method of manufacturing same
JP5970377B2 (ja) * 2010-12-27 2016-08-17 株式会社クラレ 回路基板およびその製造方法
CN105934104A (zh) * 2010-12-27 2016-09-07 株式会社可乐丽 电路基板及其制造方法
US10653001B2 (en) 2010-12-27 2020-05-12 Kuraray Co., Ltd. Release material
JPWO2012090733A1 (ja) * 2010-12-27 2014-06-05 株式会社クラレ 回路基板およびその製造方法
KR20190003817A (ko) * 2010-12-27 2019-01-09 주식회사 쿠라레 회로 기판 및 그 제조 방법
WO2012090733A1 (fr) * 2010-12-27 2012-07-05 株式会社クラレ Carte de circuit, et procédé de fabrication associé
CN105934104B (zh) * 2010-12-27 2019-04-23 株式会社可乐丽 电路基板及其制造方法
KR102045172B1 (ko) * 2010-12-27 2019-11-14 주식회사 쿠라레 회로 기판
JPWO2018110361A1 (ja) * 2016-12-16 2019-10-24 東レフィルム加工株式会社 離型フィルムおよび保護フィルム
WO2018110361A1 (fr) * 2016-12-16 2018-06-21 東レフィルム加工株式会社 Film détachable et film protecteur
CN112203403A (zh) * 2019-07-08 2021-01-08 Tdk株式会社 印刷配线板、多层印刷配线板和印刷配线板的制造方法
US11932737B2 (en) 2019-08-02 2024-03-19 Airtech International, Inc. Polymer compositions for extrusion and additive manufacturing processes

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TW201008770A (en) 2010-03-01

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