WO2008001682A1 - Film et film de démoulage - Google Patents

Film et film de démoulage Download PDF

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Publication number
WO2008001682A1
WO2008001682A1 PCT/JP2007/062575 JP2007062575W WO2008001682A1 WO 2008001682 A1 WO2008001682 A1 WO 2008001682A1 JP 2007062575 W JP2007062575 W JP 2007062575W WO 2008001682 A1 WO2008001682 A1 WO 2008001682A1
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WO
WIPO (PCT)
Prior art keywords
film
layer
methyl
pentene
copolymer
Prior art date
Application number
PCT/JP2007/062575
Other languages
English (en)
Japanese (ja)
Inventor
Tatsuya Tanizaki
Original Assignee
Mitsui Chemicals, Inc.
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 Mitsui Chemicals, Inc. filed Critical Mitsui Chemicals, Inc.
Priority to CN2007800241557A priority Critical patent/CN101479327B/zh
Priority to JP2008522529A priority patent/JP5180826B2/ja
Publication of WO2008001682A1 publication Critical patent/WO2008001682A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
    • 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

Definitions

  • the present invention relates to a film having excellent heat resistance and releasability including a layer formed from a 4_methyl_1-pentene copolymer, and a film or sheet-like laminate produced by pressure molding.
  • the present invention relates to a release film that is suitably used for manufacturing. More specifically, a coverlay, which is a protective layer, is bonded to the surface of the flexible printed circuit board (hereinafter also referred to as “FPC”) on which the electric circuit (copper foil) is formed by heating and pressing with an adhesive.
  • FPC flexible printed circuit board
  • the present invention relates to a release film that is suitably used.
  • a release film is used to prevent adhesion between the metal plates and the obtained laminate. Is commonly used. In addition, high heat resistance and excellent releasability are required for release films that are often accompanied by heating during pressure molding.
  • the release film includes a release film for manufacturing a flexible printed circuit board (hereinafter referred to as “FPC”), a release film for ACM materials used for aircraft parts, a release film for manufacturing a rigid printed circuit board, It is used as a release film for semiconductor encapsulants, a release film for FRP molding, a release film for rubber sheet curing, a release film for special adhesive tapes, etc.
  • FPC flexible printed circuit board
  • ACM materials used for aircraft parts
  • a release film for manufacturing a rigid printed circuit board It is used as a release film for semiconductor encapsulants, a release film for FRP molding, a release film for rubber sheet curing, a release film for special adhesive tapes, etc.
  • thermosetting adhesive usually, a substrate on which an electric circuit is formed and a coverlay are bonded together by a thermosetting adhesive.
  • this cover lay is provided only on one side of the substrate on which the electric circuit is formed, and on both sides or multiple layers of the substrate. In the case, it is adhered to both sides of the substrate.
  • a substrate and a coverlay coated with a thermosetting adhesive are sandwiched between metal plates and heated and pressed.
  • the release film for manufacturing FPC is used by being sandwiched between the metal plate and the cover lay.
  • release films for FPC production polytetrafluoroethylene, tetrafluoroethylene, Nororoethylene-hexafluoropropylene copolymers, fluorine polymer films such as polyvinyl fluoride, and polymethylpentene films are used.
  • the height is different between the printed portion where the electric circuit is formed and the non-printed portion where the electric circuit is not formed. Therefore, when covering with a film-shaped coverlay, voids are formed in the non-printed part, and the electric circuit is oxidized by the residual air sealed in the voids, which significantly reduces the life of the electric circuit. was there.
  • a terminal portion of an electric circuit is formed for electrical connection with other components, and the terminal portion is not covered with a coverlay but exposed. Then, the adhesive applied to the cover lay to cover the part other than the terminal part melts when bonded by heating and pressing, and often flows out to the terminal part of this electric circuit, and the adhesive coating layer As a result, there is a problem that electrical connection is poor.
  • the conventional mold release film has a large coefficient of thermal expansion relative to the substrate, cover lay, and metal plate, so when the cover lay is bonded by heating and pressure pressing, it is applied to the surface of the mold release film. Seeds will occur. For this reason, there is a problem that a gap is generated between the electric circuit and the release film due to a poor follow-up of the release film, and the appearance is sufficiently satisfactory because the seal is transferred to the FPC. There is a problem that FPC with
  • Patent Document 1 and Patent Document 2 disclose a release film for the purpose of solving the above problems.
  • these release films are satisfactory in that the effect of preventing wrinkles generated in the film is not always sufficient in the process of heating and pressurizing to bond the coverlay to the electric circuit on the substrate surface.
  • FPC with appearance cannot be obtained.
  • Patent Document 1 JP-A-2-175247
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-211602
  • the present invention relates to a film suitable for a release film, in particular, adhesion between a cover lay and a metal plate, and adhesion to other members in the heating and pressurizing steps for manufacturing an FPC.
  • a film suitable for a release film that does not cause any creases and does not form voids in non-printed parts, and does not contaminate exposed parts such as terminal parts of electrical circuits due to melting and outflow of adhesive. The best film.
  • the present inventors have obtained a film comprising a layer formed from a specific 4-methyl-11-pentene copolymer and having a specific thickness configuration and a heat shrinkage rate.
  • the present inventors have found that the problems can be solved and completed the present invention.
  • layer (B) formed from soft polyolefin having a Vicat softening temperature of 50 ° C to 150 ° C based on ASTM D1525, and
  • the film according to [1] comprising at least one of the layers (A), which is an outermost layer.
  • Vicat softening temperature based on ASTM D1525 is 50.
  • C ⁇ having a layer (B) formed from soft polyolefin having a temperature of 150 ° C. and at least two layers (A), and
  • [5] 4-methyl-1, 1-pentene other than 3 to 20 carbon atoms, 1-octene,:!-Decene, 1-tetradecene, and 1-octadecene are at least one selected from the above [1 ] To [3].
  • the total thickness of the layer (A) is 25 of the total thickness of the film. /. ⁇ 80. /.
  • the film of the present invention comprising a layer formed from a specific 4-methyl-1 pentene copolymer and having a specific thickness configuration and thermal shrinkage ratio is excellent in heat resistance and releasability. It can be suitably used as a release film.
  • a release film when used as a release film during the manufacture of FPC, when the substrate and coverlay are heated and pressed to bond, the adhesion between the metal plate and the coverlay, and the adhesive flows out to other members.
  • no gaps are formed in the non-printed part during molding, and exposed parts such as the terminal part of the electric circuit are not contaminated by the melted out of the adhesive.
  • the layer containing a specific soft polyolefin provides a good cushioning property for following the unevenness on the substrate surface on which the release film has formed an electric circuit, and does not protrude when heated and pressurized. Problems such as a decrease in FPC product yield and workability due to adhesion to the substrate surface on which few electrical circuits are formed or a metal plate used for heating and pressing There is no problem.
  • FIG. 1 is a cross-sectional view of a film of the present invention.
  • FIG. 2 is a cross-sectional view showing an example of a state in which a flexible printed circuit board is molded using the film of the present invention.
  • FIG. 3 is a cross-sectional view showing an example of a terminal exposed portion of a flexible printed circuit board formed using the film of the present invention.
  • FIG. 4 is a diagram showing an example of a film production apparatus of the present invention.
  • the film of the present invention has at least one layer (A) formed from 4-methyl-1-pentene copolymer, and the total thickness of the layer (eight) is 40 111 to 90 111. And the heat shrinkage of the entire film is 1. / 0 to 5% film.
  • the 4_methyl_1-n-ene copolymer used in the present invention is a structural unit derived from 95.5% by mass to 99.5% by mass of 4-methyl-1 pentene, and 0.5% by mass to 4%. It is a crystalline copolymer having structural units derived from olefins having 3 to 20 carbon atoms other than 5% by mass of 4-methyl-1 pentene.
  • 4-methinolay 1 pentene-derived constitutional unit is 96 mass% to 99 mass% and 4-methyl-1 pentene other than 4-methyl-1 pentene is 3 to 20 olefin-derived constitutional units 1 mass% to 4 mass%, more preferably 4 —
  • the structural unit derived from methyl-1-pentene is 97% by mass to 98% by mass, and the structural unit derived from olefin having 3 to 20 carbon atoms other than 4-methyl-1 pentene is 2% by mass to 3% by mass.
  • the film of the present invention is used as a release film for the production of FPC, if the structural unit derived from olefins having 3 to 20 carbon atoms other than 4-methyl-1 1 ⁇ ⁇ nten is less than the above upper limit value In addition, it is possible to prevent the release film from being creased, and if it is equal to or more than the lower limit, the release film has good cushioning properties, and is caused by the printed portion and the non-print portion of the electric circuit surface. The release film can be deformed following the unevenness.
  • Olefins having 3 to 20 carbon atoms other than 4_methyl_1_pentene used in the present invention include propylene, 1-butene, 1-hexene, 1-octene, 1-decene and 1-tetradecene. And at least one olefin selected from 1-octadecene. Of these, 1-decene, 1-tetradecene and 1-octadecene are preferred because good toughness with good copolymerizability with 4_methyl-1-pentene can be obtained.
  • the 4-methyl-1 pentene copolymer used in the present invention has a menoleto flow rate force of 0.5 g / 10 min to 200 g / 10 min based on ASTM D1238 (temperature 260.C, load 5. Okg). It is preferably 5 g / 10 min to lOOg / 10 min, more preferably lOg / 10 min to 50 g / 10 min. If the melt flow rate is 200 g / 10 min or less, sufficient mechanical strength can be obtained. On the other hand, the melt flow rate of 0.5 g / 10 min or more is preferable because good moldability can be obtained.
  • Tm is 220. C-240. It is preferable to be in the range of C. A force S in the range of 225 ° C to 240 ° C is more preferable.
  • the Vicat soft temperature obtained by measurement according to ASTM D1525 is preferably in the range of 160 ° C to 200 ° C. A force S in the range of C is more preferred.
  • the 4_methyl_1-pentene copolymer used in the present invention can be produced by a conventionally known method, and the polymerization catalyst and the polymerization method are not particularly limited.
  • Examples of the catalyst include a Ziegler type catalyst (based on a combination of a supported or non-supported halogen-containing titanium compound and an aluminum compound), a Philips type catalyst (based on a supported chromium oxide), a Kaminsky type catalyst ( And a supported or non-supported meta-orthocene compound and an organoaluminum compound, particularly an alumoxane).
  • a Ziegler type catalyst based on a combination of a supported or non-supported halogen-containing titanium compound and an aluminum compound
  • Philips type catalyst based on a supported chromium oxide
  • a Kaminsky type catalyst And a supported or non-supported meta-orthocene compound and an organoaluminum compound, particularly an alumoxane.
  • the polymerization method there are a slurry polymerization method, a gas phase fluidized bed polymerization method, a solution polymerization method in the presence of the catalyst, or a high-pressure Balta polymerization method at a pressure of 20 MPa or more and a polymerization temperature of 100 ° C or more. Can be mentioned.
  • the film of the present invention may be a single layer film of the layer (A).
  • the film of the present invention is formed from a soft polyolefin having a Vicat softening temperature of 50 ° C to 150 ° C based on ASTM D1525. It may be a multilayer film having layer (B) and at least one layer (A) being the outermost layer.
  • Soft polyolefin is heating when the film of the present invention is used as a release film. And at the time of pressurization, it gives the release film a characteristic that is soft.
  • Vicat softening temperature of soft polyolefin according to ASTM D1525 is 50 ° C to 150 ° C, preferably 60. C ⁇ 150. C, more preferably 70. C ⁇ 150. C, ASTM D1238 (Load 5. Okg, Temperature 260.G) Based on this, the maleolate flow rate is 0.5 g / l 0 min to 200 g / 10 min, preferably 5 g / l 0 min to lOO g / 10.
  • the melting point (Tm) measured by DSC is from 80 ° C to 240 ° C, preferably from 100 ° C to 240 ° C.
  • the soft polyolefin is used to impart a so-called cushioning property to the release film.
  • the soft polyolefin improves the followability of the unevenness of the substrate surface on which the electric circuit is formed on the surface during FPC manufacturing, and prevents the adhesive from flowing out from the end surface of the coverlay onto the electric circuit. To do.
  • the soft polyolefin satisfying the above conditions specifically, a homopolymer or copolymer of one or more olefins selected from ethylene, propylene, butene, pentene, hexene and methylpentene. , Copolymers of ethylene and acrylic acid esters, copolymers of ethylene and methacrylic acid esters, copolymers of ethylene and acrylic acid, copolymers of ethylene and methacrylic acid, and partial ion crosslinking thereof And a blend of a plurality of ethylene and acrylic acid or an acrylate copolymer, and other examples include soft polyolefin disclosed in JP-A-2-175247. These may be used alone or in combination of two or more.
  • a propylene / butene 1 copolymer and an ethylene 'ethyl acrylate copolymer can be particularly preferably used in that they have appropriate flexibility and cushioning properties.
  • these soft polyolefins can be used in a single layer, and can also be used as a multilayer of two or more layers.
  • These soft polyolefins can be easily obtained from, for example, Mitsuka Kagaku Co., Ltd., trade name: Tafmer XR, Mitsui DuPont Polychemical Co., Ltd., trade name: Evaf Rex etc. can be mentioned.
  • the film of the present invention has a constitutional unit derived from 95.5 mass% to 99.5 mass% of 4-methyl-1 pentene and carbon atoms other than 0.5 mass% to 4.5 mass% of 4-methyl-1 pentene. It has at least one layer (A) formed from a 4-methyl-1-pentene copolymer having a structural unit derived from -20 olefins, and the total thickness of the layer (A) is 40 ⁇ m to 90 It is a film having a thickness of 1 ⁇ m and a thermal shrinkage of 1% to 5%.
  • the film of the present invention is characterized by having the layer (A). Therefore, the film of the present invention is a single-layer film composed only of the layer (A) or a multilayer film having at least one layer (A).
  • the layer (A) is excellent in releasability, so that at least one layer (A) is preferably the outermost layer.
  • the layer (A) does not impair the object of the present invention, as a polymer other than 4-methylolene 1 ⁇ ene-based copolymer, for example, a fluorine-based resin such as polytetrafluoroethylene, polyphenylene sulfide, etc.
  • the layer (A) preferably contains 90% to 100% by weight of 4-methyl-1-pentene copolymer, and 95% to 100% by weight. It is particularly preferable that the content is 100% by mass.
  • the layer (B) which is preferably a multilayer film having a layer (B) formed from soft polyolefin, may be a multilayer having two or more layers.
  • the layer (B) is a polymer other than the soft polyolefin as long as the object of the present invention is not impaired.
  • polymethylpentene polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc.
  • Polyester 1, Polyamide 1, Polyamide 1, 6, 6, Polyamide 11, Polyamide 12, etc. may be included, but the layer (B) preferably contains 90% to 100% by weight of soft polyolefin. Inclusion force of 95% by mass to 100% by mass S is more preferable, and inclusion of 100% by mass is particularly preferable.
  • the multilayer film of the present invention may have a layer (C) other than the layer (A) and the layer (B), as long as the object of the present invention is not impaired.
  • the resin that can be used for the layer (C) is preferably a thermoplastic resin having high heat resistance. Examples thereof include polyolefins such as polypropylene, polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), and polyamides such as polyamide 16, polyamide 6, 6, polyamide 11 and polyamide 12. These resins can be easily obtained from the market.
  • Prime Polymer Co., Prime Polypro, Mitsubishi Engineering Plastics Co., Ltd., trade name; Novapet, Toray Co., Ltd., trade name: Amilan, etc. can be cited. These resins may be used alone or in combination of two or more.
  • the multilayer film of the present invention is a laminate having a two-layer structure of layer (A) Z layer (B) and layer (A) Z layer (C), layer (A) Z layer (B) Z layer (C), layer (A) / layer (C) / layer (A) and layer (A) / layer (B) A laminate having a three-layer structure of Z layer (A).
  • the layer (A) acts as a release layer
  • the layer (B) acts as a cushion layer.
  • the layer (B) has an appropriate cushioning property, the coverlay is surely pushed into the non-printed part in the pressing process of FPC manufacturing, and there is no gap at all. FPC molding is achieved.
  • the thickness of the layer (A) is preferably 40 ⁇ m to 90 ⁇ m. m is more preferred
  • the total thickness is preferably 40 ⁇ m to 90 ⁇ m, and more preferably 40 ⁇ m to 80 ⁇ m.
  • the layer (A) is the outermost layer on both sides, it is preferable that the thickness of these layers (A) is the same so that the multilayer film does not warp, that is, does not bend like a bow.
  • the thickness of the layer (A) is equal to or more than the lower limit, occurrence of wrinkles can be prevented, The cushioning property can be maintained when the amount is not more than the above upper limit value.
  • the layer (B) has a thickness of 30 to 100 ⁇ m, preferably 40 to 90 ⁇ m.
  • the thickness of the layer (B) is not less than the above lower limit value because cushioning properties can be maintained.
  • the amount is not more than the above upper limit value because the amount of the layer (B) protruding when heated and pressurized can be reduced.
  • the ratio of the total thickness of the layer (A) to the total thickness of the film is 25% to 80%, preferably 30% to 60%, and more preferably 30 to 60%. 50%.
  • the heat shrinkage ratio of the entire film of the present invention is 1% to 5%, preferably 1% to 3%, and more preferably 1.5% to 2.5%. If the heat shrinkage rate is 1% or more, particularly when the film of the present invention is used as a release film when a force bary is adhered to an FPC, it is preferable that the surface of the film is not creased. Further, if the heat shrinkage rate is 5% or less, it is preferable that no gap is formed between the electric circuit surface and the release film when the coverlay is bonded.
  • the thermal contraction rate in the film of the present invention is the ratio of the film contracted with respect to the length of the film before heating when the film of the present invention is contracted by heating. That is, the length L1 of the film measured at room temperature before heating, and the length corresponding to the L1 measured after 30 minutes after leaving at room temperature 170 ° C for 30 minutes after cooling at room temperature As L 2, the value obtained by the following formula (1) is defined as the heat shrinkage rate.
  • the heat shrinkage rate of the film of the present invention is a value in the stretching direction of the film. That is, the length of the film when measuring the thermal shrinkage is the length in the direction parallel to the stretching direction of the film.
  • the film of the present invention is continuously stretched using a stretching roll as it is in the MD direction, that is, the length in the extrusion direction.
  • the film of the present invention may be biaxially stretched. Biaxial stretching may be sequential or simultaneous biaxial stretching.
  • the thermal contraction rate in the case of biaxial stretching is a value in each stretching direction.
  • the extrusion direction is a direction parallel to the die line generated on the film surface, and can be easily specified from the die line.
  • the film of the present invention it is preferable that at least one of the film surfaces formed from the layer (A) is embossed. JI of the film surface layer after this embossing
  • the surface roughness Ry based on S B0601 is from 0.01 to 20 ⁇ , preferably from 0.1 to 10 ⁇ m, more preferably from 0.:! To 5 zm, particularly preferably from 0.1 111 to 2 111. .
  • the surface roughness of the film surface layer is within the above range, good releasability can be obtained.
  • the film of the present invention has an elastic modulus ( ⁇ ′) force at a temperature of 150 ° C. 1.5 ⁇ 10 7 to 8.5
  • the elastic modulus ( ⁇ ′) at a temperature of 150 ° C. indicates a dynamic storage elastic modulus at a temperature of 150 ° C. in the stretching direction.
  • a dynamic storage elastic modulus measuring device such as TA (RSA-II ) Measurement temperature:-150 to 200 ° C, heating rate: 3 ° C / min, measurement mode: tension, measurement frequency: elastic modulus at a temperature of 150 ° C (1Hz) ⁇ ') can be obtained.
  • the temperature of the release film when heated to adhere a cover layer to the FPC is close to 150 ° C. Therefore, when the elastic modulus at a temperature of 150 ° C. is not less than the above lower limit value, the release film can prevent occurrence of wrinkles, and if it is not more than the above upper limit value, the release film has good cushioning properties. You can get power.
  • the film of the present invention comprises a structural unit derived from 95.5% to 99.5% by weight of 4_methyl_1_pentene and 0.5% to 4.5% by weight of 4_methyl_1 ⁇
  • it has at least one layer (A) formed from a 4-methyl-1-pentene copolymer having a structural unit derived from olefin having 3 to 20 carbon atoms, and the total thickness of the layer (A) 4
  • the film has a thermal shrinkage ratio of 1% to 5% in the whole film of 0 ⁇ m to 90 ⁇ m.
  • the film of the present invention is publicly known, for example, by laminating a single layer of each layer formed by an extrusion method using a T-die device, a co-extrusion method, a heating press method or a solvent casting method, and then thermocompression bonding. It can be manufactured by this method.
  • the extrusion method or co-extrusion method using a T-die device makes it possible to easily and uniformly control the film thickness by adjusting the thickness of each layer and the distance between the die orifices in the die lip. It is excellent in that it can.
  • the extrusion or coextrusion method using a T-die device is the mold release for FPC manufacturing. It is preferable as a method for producing a film.
  • the coextrusion molding method since the mixing in the molten state is often performed at the adhesive interface between the resins, a laminated film having excellent adhesive strength can be obtained.
  • the temperature of the extruder and the T-die is 260 to 330 °.
  • an extruder and a T-die can be extruded at a temperature of 230 to 30 ° C.
  • this multilayer film can also be made into a multilayer film by integrating each layer with an adhesive, and an adhesive such as urethane, isocyanate, or epoxy is applied between each layer in the form of a thin film. Can be molded by pressure bonding.
  • an adhesive resin such as maleic anhydride-grafted polyethylene or maleic anhydride-grafted polypropylene may be extruded between the resin layers at the same time as the resin layers.
  • a method of hot pressing or hot rolling a previously formed film or sheet in the order described above can be employed.
  • the film having a heat shrinkage rate of 1% to 5% of the present invention is a single layer film
  • the film is stretched.
  • the layer (B) formed from the soft polyolefin can be obtained. It is obtained by producing a multilayer film in which at least one layer (A) is the outermost layer and then stretching the multilayer film.
  • a stretching method a conventionally known method can be appropriately employed, and stretching can be performed by a method such as a tenter method or a tool stretching method.
  • a method such as a tenter method or a tool stretching method.
  • Is in the range of 50 ° C to 200 ° C, preferably 100 ° C to 150 ° C.
  • the stretching ratio is usually 1% to 5%, preferably 2% to 4%.
  • the stretching can be performed by uniaxial stretching or biaxial stretching, and the biaxial stretching may be performed sequentially or simultaneously.
  • a raw material film obtained by an extrusion molding method or a coextrusion molding method may be stretched using a roll.
  • the raw material film obtained by the extrusion molding method or the coextrusion molding method is brought into contact with the surface of at least two or more independently rotating tools having different peripheral speeds, the raw material film is first passed.
  • the peripheral speed (m / min) of the roll with which the raw film comes into contact later is made faster than the peripheral speed (m / min) of the roll in contact.
  • the peripheral speed of the mouth is controlled so that the speed at which the raw material film passes through the roll surface that comes into contact later is faster than the speed at which the raw film passes through the roll surface that comes into contact later.
  • the film is stretched when the film passes between the two or more rolls.
  • a roll having a mirror surface or an embossing roll may be used.
  • an embossing roll it is preferable to use a roll processed to have an average roughness (Ra) of 1 ⁇ m to 200 ⁇ m, preferably 2 ⁇ m to 100 ⁇ m.
  • FIG. 4 showing an example of the film production apparatus of the present invention
  • 4-methyl-1-pentene copolymer and soft polyolefin melted by three extruders 20 are multi-hold type three-layer coextrusion. It is extruded through a T-die 21 and once cooled to 50 ° C. to 150 ° C. by a cooling port 22 to form a film. The film then has a temperature of 50. C ⁇ 200. C.
  • Calorie fever is heated at Ronole 23, followed by temperature 50 ° C to 200 ° C 1st
  • the embossing process is performed by the embossing roll 24 and then the second embossing roll 25, and the peripheral speed of the second embossing roll is made faster than the peripheral speed of the first embossing roll.
  • the film is stretched between the first embossing roll and the second embossing roll by making the speed passing between the second press roll 27 and the second embossing roll 25 faster than the speed passing between the first embossing roll 24.
  • the film 8 of the present invention can be obtained.
  • the film is later brought into contact with the peripheral speed of the roll surface that comes into contact with the film first.
  • the roll temperature at that time is in the range of 50 ° C. to 200 ° C., preferably 100 ° C. to 150 ° C.
  • the peripheral speed of the roll surface that comes into contact with the film later, that is, the processing speed is 5 m / min to 100 m / min, preferably 10 mZ to 70 mZ.
  • an annealing treatment at a temperature lower than the melting point of the resin is performed after the stretching treatment in order to prevent spontaneous shrinkage during storage of the release film. Also good.
  • the film forming step and the film stretching step can be performed separately.
  • the film forming step and the stretching step are performed separately, in order to prevent natural shrinkage of the film obtained by forming, the film is subjected to an annealing treatment at a temperature below the melting point of the resin and then stretched. May be performed.
  • the film forming step and the stretching step can be carried out continuously. Equipment for performing such a process is generally commercially available.
  • the film of the present invention is excellent in heat resistance and releasability, and can be suitably used as a release film.
  • release films for FPC production release films for ACM materials used for aircraft parts, release films for rigid printed circuit board production, release films for semiconductor encapsulants, release molds for FRP molding Examples include films, release films for curing rubber sheets, and release films for special adhesive tapes.
  • the film of the present invention is suitably used as a release film for FPC production. Power to use S
  • thermosetting adhesive to bond a substrate on which an electric circuit is formed and a force burley layer between metal plates by heating and pressing.
  • the release film of the present invention is sandwiched between them.
  • FIG. 1 is a cross-sectional view of the multilayer film of the present invention.
  • FIG. 2 is a cross-sectional view of a state during pressing when forming an FPC using the release film of the present invention.
  • the release film of the present invention By using the release film of the present invention, the gaps in the non-printed part are completely pushed in and closely integrated by the coverlay.
  • 8 represents the film of the present invention, and 9 represents FPC.
  • the release film of the present invention is deformed before the thermosetting adhesive applied by the coverlay at the time of press molding starts to flow by heating, and further, the cushioning property of the intermediate layer (B) and the maximum Since the outer layer (A) has excellent releasability, as shown in FIG. 3, the film 8 of the present invention, which is a release film, adheres closely to the end face of the coverlay 6 and the copper foil surface 10 of the electric circuit.
  • FPC can be molded in a state where the boundary between the exposed part and the coverlay covering part where the adhesive does not flow out is clear.
  • the release film of the present invention is less prone to generate a wrinkle in the release film during heating and pressure forming for bonding the coverlay, and therefore the unevenness of the electric circuit surface at the portion where the wrinkle has occurred. There is no generation of voids due to poor follow-up of the release film, and no FPC is transferred to the FPC, and an FPC with a very good appearance can be obtained.
  • the layer (B) has little protrusion, so that the layer (B) can be used for a substrate surface on which an electric circuit is formed, or for heating and pressure forming. Adhering to the metal plate used will not cause problems such as a decrease in FPC product yield and workability.
  • the MFR of the resin is load 5.0kg and temperature 260 according to ASTM D1238. Measured with C.
  • the density of the resin was measured by a density gradient tube method according to ASTM D1505.
  • the melting point of the resin was measured with a DSC apparatus (Seiko Instruments).
  • the Vicat softening temperature of the resin was measured according to ASTM D1525 using a 1/6 inch thick plate of each resin obtained by injection molding.
  • an extruder with a T-die or a co-extrusion machine was used for the production of the film.
  • the set temperature of the extruder and the set temperature of the T-die were 290 ° C.
  • the width of the film obtained by extrusion is 600 mm.
  • a film 30 cm long in the extrusion direction (hereinafter referred to as the MD direction) and 30 cm long in the direction perpendicular to the MD direction (hereinafter referred to as the TD direction) was cut out from any position of the film and tested.
  • a film was obtained.
  • the length in the MD direction at room temperature of the test film before heating described later was defined as LI (cm).
  • the test film was heated for 30 minutes in an air oven at a temperature of 170 ° C. and then taken out and cooled at room temperature for 30 minutes. Test after cooling
  • the length of the film in the MD direction at room temperature was defined as L2 (cm).
  • the value obtained by the following formula (1) was defined as the heat shrinkage rate of
  • an extruder with a T-die or a co-extrusion machine was used for the production of the film.
  • Extruder The set temperature of T and the set temperature of the T-die were set to 290 ° C.
  • the width of the film obtained by extrusion is 600 mm. Every 5 m, a total of 10 films 30 cm long in the MD direction and 21 cm long in the TD direction were cut out and used as test films.
  • This test film was set at position 8 shown in FIG. 2 and subjected to heating and pressurizing steps.
  • the process conditions were a temperature of 160 ° C., a pressure of 2 MPa, and a heating and pressurization time of 30 minutes.
  • an extruder with a T-die or a co-extrusion machine was used for the production of the film.
  • the set temperature of the extruder and the set temperature of the T-die were 290 ° C.
  • the width of the film obtained by extrusion is 600 mm.
  • a total of four films having a length of 10 cm in the MD direction and a length of 10 cm in the TD direction were cut out from arbitrary positions on this film, and this was designated as a test film [S 1].
  • test films [Sl] to be stacked on [C] were arranged so as not to overlap each other.
  • an extruder with a T-die or a co-extrusion machine was used for the production of the film.
  • Extruder The set temperature of T and the set temperature of the T-die were set to 290 ° C.
  • the width of the film obtained by extrusion is 600 mm.
  • a film having a length of 10 cm in the MD direction and a length of 10 cm in the TD direction was cut out from an arbitrary position of the film, and this was used as a test film.
  • the surface roughness of the surface layer of the film was determined based on JIS B0601 with a standard length of 5 cm from the center of the test film.
  • the elastic modulus ( ⁇ ′) of the film was evaluated by measuring the dynamic storage elasticity at a temperature of 150 ° C. in the MD direction of the film.
  • an extruder with a T-die or a co-extrusion machine was used.
  • the set temperature of the extruder and the set temperature of the T-die were 290 ° C.
  • the width of the film obtained by extrusion is 600 mm. From an arbitrary position of this film, a film having a length of 0.13 mm in the MD direction and a length of 5 mm in the TD direction was cut out and used as a test film.
  • the dynamic storage elastic modulus at a temperature of 150 ° C. in the MD direction of the test film was measured with a dynamic storage elastic modulus measuring apparatus (TAA, RSA-II).
  • the measurement conditions are: measurement temperature range: —150 ° C. to 200 ° C., heating rate: 3 ° C./minute, measurement mode: tension, measurement frequency: 1 Hz. From the measurement results, the elastic modulus ( ⁇ ) of the film at a temperature of 150 ° C. was obtained.
  • the layer (A) / layer (B) Z layer (A) was combined in a co-extruded T-die. Further, a multilayer film consisting of three layers was produced while taking this composite with a roll (20 mZ).
  • the surface of the obtained multilayer film was embossed with two embossing tools having an average roughness (Ra) of 25 ⁇ m. Ronole temperature 130. C, Embossing speed was 20m / min. Many The peripheral speed of the second embossing roll that comes in contact with the multilayer film later was set to 1.03 times the peripheral speed of the first embossing roll that comes in contact with the layer film first.
  • the obtained multilayer film was set in the heating and pressurizing steps shown in FIG. 2, and the coverlay was adhered to the electric circuit surface formed on the substrate to produce an FPC.
  • the temperature was 160 ° C
  • the pressure was 2 MPa
  • the heating and pressurization time was 30 minutes.
  • the coverlay has a polyimide Finolem force and is 25 x m thick.
  • an epoxy adhesive with a flow start temperature of 80 ° C was applied to the coverlay in a thickness of 30 ⁇ m.
  • MFR ethylene-ethyl acrylate copolymer
  • Example 2 the multilayer film was heated and pressed under the same conditions as in Example 1 to adhere the force burley to the electric circuit surface formed on the substrate.
  • (B3) propylene ⁇ 1-butene ⁇ 4_methyl -1-pentene copolymer (propylene content; 36 mol%, 1-butene content; 14 mol%, 4_methyl -1 pentene containing Yuryou; 50 mole 0/0, density 0. 880gZcm3, MFR; 27gZlO min, Vicat softening temperature; and 80 ° 0 50 wt%, linear low density polyethylene (density: 0.
  • this multilayer film was heated and pressurized under the same conditions as in Example 1, whereby the force barlay was adhered to the electric circuit surface formed on the substrate.
  • Table 1 shows the results evaluated in the same manner as in Example 1.
  • the multilayer film was formed in the same procedure as in Example 1 under the conditions shown in Table 1, except that the thickness of layer (A) was changed to 20 ⁇ m by changing the extrusion amounts of the first and third extruders. Manufactured.
  • this multilayer film was heated and pressurized under the same conditions as in Example 1 to adhere the force barlay to the electric circuit surface formed on the substrate.
  • Table 1 shows the results evaluated in the same manner as in Example 1.
  • the multilayer film was formed in the same procedure as in Example 1 under the conditions shown in Table 1, except that the thickness of layer (A) was changed to 35 ⁇ m by changing the extrusion amounts of the first and third extruders. Manufactured.
  • this multilayer film was heated and pressed under the same conditions as in Example 1 to adhere the force burley to the electric circuit surface formed on the substrate.
  • Table 1 shows the results evaluated in the same manner as in Example 1.
  • the layer (A) was a single layer film with a thickness of 50 ⁇ .
  • a monolayer film was produced in the same procedure as in Example 1 under the conditions shown in 1.
  • this single-layer film was heated and pressed under the same conditions as in Example 1 to adhere the force burley to the electric circuit surface formed on the substrate.
  • Table 1 shows the results evaluated in the same manner as in Example 1.
  • this multilayer film was heated and pressed under the same conditions as in Example 1, whereby the force burley was adhered to the electric circuit surface formed on the substrate.
  • Table 1 shows the results evaluated in the same manner as in Example 1.
  • this multilayer film was heated and pressed under the same conditions as in Example 1, whereby the force burley was adhered to the electric circuit surface formed on the substrate.
  • Table 1 shows the results evaluated in the same manner as in Example 1.
  • this multilayer film was heated and pressed under the same conditions as in Example 1 to adhere the force burley to the electric circuit surface formed on the substrate.
  • Table 1 shows the results evaluated in the same manner as in Example 1.
  • the multilayer film was formed in the same procedure as in Example 1 under the conditions shown in Table 2, except that the thickness of layer (A) was changed to 5 ⁇ m by changing the extrusion amounts of the first and third extruders. Manufactured. Next, this multilayer film was heated and pressurized under the same conditions as in Example 1 to adhere the force burley to the electric circuit surface formed on the substrate.
  • Table 2 shows the results evaluated in the same manner as in Example 1.
  • the multilayer film was formed in the same procedure as in Example 1 under the conditions shown in Table 2, except that the thickness of layer (A) was changed to 50 ⁇ m by changing the extrusion amounts of the first and third extruders. Manufactured.
  • this multilayer film was heated and pressed under the same conditions as in Example 1 to adhere the force burley to the electric circuit surface formed on the substrate.
  • Table 2 shows the results evaluated in the same manner as in Example 1.
  • this multilayer film was heated and pressed under the same conditions as in Example 1 to adhere the force burley to the electric circuit surface formed on the substrate.
  • Table 2 shows the results evaluated in the same manner as in Example 1.
  • Example 1 (0% by mass, MFR; 24 g / 10 min, melting point; 226 ° C), and in the same manner as in Example 1 except that B2 was used instead of B1, and a multilayer film was produced in the same manner as in Example 1. did.
  • this multilayer film was heated and pressed under the same conditions as in Example 1, whereby the force burley was adhered to the electric circuit surface formed on the substrate.
  • Table 2 shows the results evaluated in the same manner as in Example 1.
  • A5 4_methyl_1_pentene copolymer (1-decene content; 5.0% by mass, MFR; 24gZlO content, melting point; 226 ° C), and instead of B1, A multilayer film was produced in the same procedure as in Example 1 under the conditions shown in Table 2 except that B3 was used.
  • the multilayer film was heated and pressurized under the same conditions as in Example 1 to obtain force.
  • the burley was bonded to the electric circuit surface formed on the substrate.
  • Table 2 shows the results evaluated in the same manner as in Example 1.
  • this multilayer film was heated and pressed under the same conditions as in Example 1, whereby the force burley was adhered to the electric circuit surface formed on the substrate.
  • Table 2 shows the results evaluated in the same manner as in Example 1.
  • this multilayer film was heated and pressed under the same conditions as in Example 1, whereby the force burley was adhered to the electric circuit surface formed on the substrate.
  • Table 2 shows the results evaluated in the same manner as in Example 1.
  • this multilayer film was heated and pressed under the same conditions as in Example 1, whereby the force burley was adhered to the electric circuit surface formed on the substrate.
  • Table 2 shows the results evaluated in the same manner as in Example 1.
  • An unstretched multilayer film was produced in the same manner as in Example 1 except that the peripheral speeds of the first embossing roll and the second embossing roll were the same.
  • a multilayer film was produced in the same manner as in Example 1 except that the peripheral speed of the second embossing roll was 1.15 times the peripheral speed of the first embossing roll and the film was stretched 15% in the MD direction.
  • this multilayer film was heated and pressed under the same conditions as in Example 1 to adhere the force burley to the electric circuit surface formed on the substrate.
  • the finished flexible printed circuit board had poor adhesion between the coverlay and the substrate body, and air-borne portions were generated. In addition, the pattern resulting from the stretching unevenness was transferred to the flexible printed circuit board, and the appearance of the flexible printed circuit board was poor. Table 2 shows the evaluation results.
  • the layer (A) was a single layer film with a thickness of 20 ⁇ .
  • a monolayer film was produced in the same procedure as in Example 1 under the conditions shown in 2.
  • this single-layer film was heated and pressed under the same conditions as in Example 1, whereby the force burley was adhered to the electric circuit surface formed on the substrate.
  • Table 2 shows the results evaluated in the same manner as in Example 1.
  • a single-layer film was produced in the same procedure as in Example 1 under the conditions shown in Table 2, except that only the first extruder was used to obtain a single-layer film having a layer (A) thickness of 150 ⁇ m.
  • this single-layer film was heated and pressed under the same conditions as in Example 1, whereby the force burley was adhered to the electric circuit surface formed on the substrate.
  • Table 2 shows the results evaluated in the same manner as in Example 1.
  • the film of the present invention comprising a layer formed from a specific 4-methyl-1 pentene copolymer and having a specific thickness configuration and thermal shrinkage ratio is excellent in heat resistance and releasability. It can be suitably used as a release film. In particular, it can be used as a release film during the manufacture of FPC, preventing adhesion between the metal plate and the coverlay and preventing the adhesive from leaking out and adhering to other components, and non-printing during molding. No gaps are formed in the parts, and exposed parts such as the terminal parts of the electric circuit are not contaminated by the melted out of the adhesive.
  • the release film has good cushioning properties and has unevenness on the surface of the FPC.

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  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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Abstract

L'invention concerne un film munie d'une couche de copolymère de 4-méthyl-1-pentène spécifié et présentant une configuration d'épaisseur spécifiée et un coefficient de retrait thermique spécifié. L'invention concerne un film dont les propriétés de résistance à la chaleur et de démoulage sont excellentes, notamment un film approprié pour être utilisé comme film de démoulage appliqué dans la fabrication d'un stratifié par moulage sous pression. Pendant les étapes de chauffage et de pressurisation comprises dans la fabrication des plaques à circuits imprimés flexibles, l'utilisation dudit film comme film de démoulage permet d'éviter une adhésion de la couche de couverture à la feuille métallique et un écoulement d'adhésif conduisant à une adhésion à d'autres éléments ; une telle utilisation permet, de plus, d'éviter une génération de vides dans des parties non imprimées sur la plaque, et une contamination de parties exposées, telles que les parties de bornes, du circuit électrique par écoulement par fusion de l'adhésif. Une formation de faux plis du film de démoulage peut également être évitée, de telle sorte qu'une génération de vides due à une défaillance de couverture du film de démoulage peut être évitée et qu'ainsi des plaques à circuits imprimés flexibles présentant un bon aspect peuvent être obtenues.
PCT/JP2007/062575 2006-06-27 2007-06-22 Film et film de démoulage WO2008001682A1 (fr)

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JP2008522529A JP5180826B2 (ja) 2006-06-27 2007-06-22 フィルム及び離型フィルム

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JP2010208104A (ja) * 2009-03-09 2010-09-24 Mitsui Chemicals Inc 半導体封止プロセス用離型フィルム、およびそれを用いた樹脂封止半導体の製造方法
JP2012218257A (ja) * 2011-04-07 2012-11-12 Sumitomo Bakelite Co Ltd 繊維強化樹脂成形品の製造方法、および繊維強化樹脂成形品
WO2014027672A1 (fr) * 2012-08-16 2014-02-20 住友ベークライト株式会社 Pellicule de blindage em et procédé permettant de couvrir un composant électronique
JP2015159214A (ja) * 2014-02-25 2015-09-03 住友ベークライト株式会社 電磁波シールドフィルム及びフレキシブルプリント基板
JP2015189151A (ja) * 2014-03-28 2015-11-02 アキレス株式会社 離型フィルム
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JP2010098075A (ja) * 2008-10-15 2010-04-30 Nippon Mektron Ltd フレキシブル回路基板の製造方法及びフレキシブル回路基板
JP2010195893A (ja) * 2009-02-24 2010-09-09 Mitsui Chemicals Inc 通気フィルム
JP2010208104A (ja) * 2009-03-09 2010-09-24 Mitsui Chemicals Inc 半導体封止プロセス用離型フィルム、およびそれを用いた樹脂封止半導体の製造方法
JP2012218257A (ja) * 2011-04-07 2012-11-12 Sumitomo Bakelite Co Ltd 繊維強化樹脂成形品の製造方法、および繊維強化樹脂成形品
WO2014027672A1 (fr) * 2012-08-16 2014-02-20 住友ベークライト株式会社 Pellicule de blindage em et procédé permettant de couvrir un composant électronique
WO2014027673A1 (fr) * 2012-08-16 2014-02-20 住友ベークライト株式会社 Pellicule de blindage em et procédé permettant de couvrir un composant électronique
JP2014057040A (ja) * 2012-08-16 2014-03-27 Sumitomo Bakelite Co Ltd 電磁波シールド用フィルム、および電子部品の被覆方法
JP2015159214A (ja) * 2014-02-25 2015-09-03 住友ベークライト株式会社 電磁波シールドフィルム及びフレキシブルプリント基板
JP2015189151A (ja) * 2014-03-28 2015-11-02 アキレス株式会社 離型フィルム
WO2018179655A1 (fr) * 2017-03-29 2018-10-04 日本メクトロン株式会社 Film de démoulage et procédé de fabrication de carte de circuit imprimé souple
KR20210121205A (ko) 2019-03-28 2021-10-07 미쓰이 가가쿠 토세로 가부시키가이샤 프린트 배선기판 제조공정용 이형필름, 프린트 기판의 제조방법, 프린트 기판 제조장치 및 프린트 기판
WO2022034834A1 (fr) * 2020-08-12 2022-02-17 住友ベークライト株式会社 Film de démoulage et procédé de fabrication d'un produit moulé
JPWO2022034834A1 (fr) * 2020-08-12 2022-02-17
JP7283639B2 (ja) 2020-08-12 2023-05-30 住友ベークライト株式会社 離型フィルムおよび成型品の製造方法
CN112778681A (zh) * 2020-12-31 2021-05-11 苏州市新广益电子有限公司 一种柔性印刷电路板制造专用脱模膜
CN112778681B (zh) * 2020-12-31 2023-09-29 苏州市新广益电子股份有限公司 一种柔性印刷电路板制造专用脱模膜

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JPWO2008001682A1 (ja) 2009-11-26
CN101479327B (zh) 2012-05-30

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