WO2015008759A1 - 離型フィルム - Google Patents

離型フィルム Download PDF

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Publication number
WO2015008759A1
WO2015008759A1 PCT/JP2014/068811 JP2014068811W WO2015008759A1 WO 2015008759 A1 WO2015008759 A1 WO 2015008759A1 JP 2014068811 W JP2014068811 W JP 2014068811W WO 2015008759 A1 WO2015008759 A1 WO 2015008759A1
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WO
WIPO (PCT)
Prior art keywords
film
release film
mold
resin
heat
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PCT/JP2014/068811
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English (en)
French (fr)
Japanese (ja)
Inventor
正志 中野
芳樹 明星
西松　英明
友彦 小田川
晴紀 安田
Original Assignee
倉敷紡績株式会社
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Application filed by 倉敷紡績株式会社 filed Critical 倉敷紡績株式会社
Priority to KR1020167000984A priority Critical patent/KR102218811B1/ko
Priority to JP2015527305A priority patent/JP6307078B2/ja
Priority to CN201480040329.9A priority patent/CN105358308B/zh
Publication of WO2015008759A1 publication Critical patent/WO2015008759A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/0067—Using separating agents during or after moulding; Applying separating agents on preforms or articles, e.g. to prevent sticking to each other
    • B29C37/0075—Using separating agents during or after moulding; Applying separating agents on preforms or articles, e.g. to prevent sticking to each other using release sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2025/00—Use of polymers of vinyl-aromatic compounds or derivatives thereof as moulding material
    • B29K2025/04—Polymers of styrene
    • B29K2025/06—PS, i.e. polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene

Definitions

  • the present invention relates to a release film, particularly a polystyrene-type release film excellent in transferability.
  • a plastic film is interposed as a release film.
  • a thin film layer such as a thermosetting resin, thermoplastic resin, ceramic, metal, etc.
  • a thin film layer is laminated on a plastic film for the purpose of supporting and protecting the thin film layer.
  • a plastic film may be peeled and removed as a release film. As described above, the plastic film is used for various purposes.
  • heat is often applied to a plastic film, and the case where a higher temperature is applied is increasing. Furthermore, with the recent demand for higher performance, the heat resistance required for plastic films has become severe. Specifically, for example, when a plastic film is used as a release film and interposed between a mold and a molding material to prevent fusion during press molding, the plastic film is usually stretched. Therefore, when dimensional variation (heat shrinkage) occurs in the plastic film due to heat, the film does not sufficiently follow the unevenness of the mold molding surface, and good shaping by the mold molding surface is not performed. For this reason, particularly good heat-resistant dimensional stability is required for the film.
  • Patent Document 1 discloses that mechanical strength and heat shrinkage in the longitudinal direction and the transverse direction are performed by performing specific sequential biaxial stretching on an unstretched amorphous film made of a syndiotactic polystyrene film.
  • a technique for producing a syndiotactic polystyrene film having an excellent balance of rates is disclosed.
  • the release film is required to be subjected to a surface treatment such as a matte treatment in order to further improve the releasability and / or to impart a matte property to the molded body.
  • the mat processing is a processing for forming fine irregularities on the film surface by applying heat and pressure with a mold made of metal or rubber having a desired surface shape while applying tension to the film.
  • a curl phenomenon occurs in the obtained release film in which the film is wound alone from the end.
  • a release film having a large curl in other words, a release film having a high curl rate, not only causes inconvenience in production when installed between the mold and the molding material, but also sufficiently extends the curl.
  • the release film is inferior in heat-resistant dimensional stability, the fine uneven shape on the film surface cannot be accurately transferred to the molded product, and a thick thin film can be formed where there is sufficient transfer and sweet transfer. So-called unevenness occurs.
  • the present invention is a release film composed of a biaxially oriented polystyrene film containing a syndiotactic polystyrene resin, wherein at least one surface is matted, and the curl rate of the release film is 80% or less.
  • the present invention relates to a release film.
  • heat-resistant dimensional stability means a film characteristic that sufficiently prevents film shrinkage even when the film is heated.
  • the curl resistance means a film characteristic that sufficiently prevents the occurrence of a curling phenomenon even if the film is matted.
  • the release film of the present invention is sufficiently excellent in heat-resistant dimensional stability.
  • the release film of the present invention is further excellent in curl resistance.
  • the release film of the present invention can achieve the transfer onto the finely concavo-convex shaped molded body with sufficient accuracy.
  • the polystyrene-based release film according to the present invention (hereinafter simply referred to as “PS-based release film”) is a biaxially oriented film containing a syndiotactic polystyrene-based resin.
  • Biaxial orientation means that the polymer molecules constituting the film are oriented mainly in two directions different from each other in the in-plane direction of the film, preferably in two directions substantially perpendicular to each other. For example, it can be achieved by simultaneous biaxial stretching described later.
  • the syndiotactic polystyrene resin (hereinafter simply referred to as “SPS resin”) contained in the PS release film of the present invention is a styrene polymer having a so-called syndiotactic structure.
  • the syndiotactic structure is a syndiotactic structure, that is, a three-dimensional structure in which phenyl groups or substituted phenyl groups that are side chains with respect to the main chain formed from carbon-carbon bonds are alternately located in opposite directions. It means structure.
  • the tacticity (stereoregularity) of the SPS resin can be quantified by an isotope carbon nuclear magnetic resonance method ( 13 C-NMR method).
  • the tacticity of the SPS resin measured by the 13 C-NMR method is the ratio of the presence of a plurality of consecutive structural units, for example, a dyad for two, a triad for three, a pentad for five.
  • the SPS resin in the present invention is usually 75% or more, preferably 85% or more, racemic triad, 60% or more, preferably 75% or more, or 30% or more, preferably 50%, racemic pentad. It is a styrenic polymer having the above syndiotacticity.
  • Styrenic polymers as SPS resins include polystyrene, poly (alkyl styrene), poly (aryl styrene), poly (halogenated styrene), poly (halogenated alkyl styrene), poly (alkoxy styrene), poly (alkoxy styrene). Vinyl benzoate ester), hydrogenated polymers thereof and the like, and mixtures thereof, or copolymers based on these.
  • poly (alkyl styrene) examples include poly (methyl styrene), poly (ethyl styrene), poly (isopropyl styrene), poly (tertiary butyl styrene), poly (vinyl styrene), and the like.
  • poly (aryl styrene) examples include poly (phenyl styrene) and poly (vinyl naphthalene).
  • poly (halogenated styrene) examples include poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene), and the like.
  • poly (halogenated alkylstyrene) examples include poly (chloromethylstyrene).
  • examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).
  • the weight average molecular weight of the SPS resin constituting the PS release film according to the present invention is 10,000 to 3,000,000, preferably 30,000 to 1,500,000, particularly preferably 50,000 to 500,000.
  • the glass transition temperature of the SPS resin is 60 to 140 ° C., preferably 70 to 130 ° C.
  • the melting point of the SPS resin is 200 to 320 ° C., preferably 220 to 280 ° C.
  • the SPS resin can be obtained as a commercial product or can be produced by a known method.
  • it can be obtained as “Zarek” (142ZE, 300ZC, 130ZC, 90ZC) manufactured by Idemitsu Kosan Co., Ltd.
  • the SPS resin is within the above-mentioned range. It may be contained.
  • the PS-type release film of the present invention is not limited to the above SPS-based resin, as long as it does not adversely affect the heat-resistant dimensional stability, curl resistance, heat-resistant deformation, film-forming property, heat-resistant strength stability, etc. It may contain.
  • polystyrene resins such as polystyrene resins other than the SPS resins, styrene-butadiene block copolymers (SBR), hydrogenated styrene-butadiene-styrene block copolymers (SEBS), and the like.
  • Synthetic rubber such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polytrimethylene terephthalate; polyphenylene sulfite; polyarylate; polyether sulfone; polyphenylene ether .
  • the polystyrene resin other than the SPS resin includes a so-called isotactic polystyrene resin and an atactic polystyrene resin.
  • the content of the SPS resin relative to the total amount in the PS release film is preferably 60% by weight or more, more preferably 80% by weight or more, and most preferably 95% by weight from the viewpoint of further improving the heat-resistant dimensional stability. % Or more.
  • the total ratio thereof may be within the above range.
  • the PS release film of the present invention may contain additives such as a lubricant, an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, an inorganic filler, a colorant, a crystal nucleating agent and a flame retardant.
  • the PS release film of the present invention preferably further contains a lubricant and an antioxidant.
  • the lubricant examples include hydrocarbon resins, fatty acids, fatty acid amides, fatty acid esters, fatty alcohols, partial esters of fatty acids and polyhydric alcohols, and composite lubricants.
  • hydrocarbon resins fatty acids, fatty acid amides, fatty acid esters, fatty alcohols, partial esters of fatty acids and polyhydric alcohols, and composite lubricants.
  • the content of the lubricant is preferably from 0.01 to 3.0% by weight, particularly from 0.02 to 1.0% by weight, based on the SPS resin in the PS film, from the viewpoint of the release property of the release film. .
  • the total amount thereof may be within the above range.
  • an antioxidant used for the purpose of preventing yellowing in the field of PS release film can be used.
  • a phenolic antioxidant, a phosphorus antioxidant, a sulfur antioxidant Agents and the like can be used.
  • the antioxidant preferably contains at least a phenolic antioxidant.
  • an antioxidant, particularly a phenolic antioxidant the heat-resistant dimensional stability and the curl resistance can be further improved.
  • a phenolic antioxidant is an organic compound containing a phenol skeleton, and a phenol skeleton-containing organic compound conventionally used as a phenolic antioxidant in the field of PS film can be used.
  • the phenolic antioxidant can be obtained as a commercial product.
  • Commercially available phenolic antioxidants include, for example, Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Adekastab AO-60, Adekastab AO-80, Adekastab AO-330 (both manufactured by ADEKA), Irganox 245 (BASF) Product), Sianox 1790 (manufactured by CYTEC), and the like.
  • the phosphorus antioxidant is an organic compound containing a phosphorus atom, and a phosphorus atom-containing organic compound conventionally used as a phosphorus antioxidant in the field of PS film can be used.
  • Phosphorous antioxidants can be obtained as commercial products. Examples of commercially available phosphorus antioxidants include Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.), Adekastab PEP-36 (manufactured by ADEKA), Irgafos 38, Irgafos 168 (both manufactured by BASF), and the like.
  • the sulfur-based antioxidant is an organic compound containing a sulfur atom, and a sulfur atom-containing organic compound conventionally used as a sulfur-based antioxidant in the field of PS film can be used.
  • the sulfur-based antioxidant can be obtained as a commercial product. Examples of commercially available sulfur-based antioxidants include Sumilyzer MB (manufactured by Sumitomo Chemical Co., Ltd.) and Adeka Stub AO-412S (manufactured by ADEKA).
  • the content of the antioxidant is 0.01 to 3.0% by weight, particularly 0.02 to 1.0% by weight, based on the SPS resin in the PS film, from the viewpoint of heat-resistant dimensional stability and curl resistance. % Is preferred.
  • the total amount thereof may be within the above range.
  • the content of the phenolic antioxidant is preferably within the above range from the viewpoint of further improving the heat-resistant dimensional stability and curling resistance.
  • the PS release film of the present invention can be produced by the following method. For example, the SPS and other polymers and additives contained as desired are mixed in a predetermined ratio, melted and kneaded to produce a precursor film (unstretched film), and then the obtained precursor film is simultaneously used. Sequentially used for biaxial stretching and mat processing.
  • Precursor film production A well-known method can be employ
  • the thickness of the precursor film is not particularly limited, and is, for example, 20 to 2000 ⁇ m, preferably 30 to 1000 ⁇ m.
  • the heat setting treatment is usually performed after simultaneous biaxial stretching treatment.
  • the glass transition temperature of the film can be increased, the thermal expansion coefficient can be decreased, or the absolute value of the thermal shrinkage ratio can be decreased.
  • the stretching method includes a sequential biaxial stretching method and a simultaneous biaxial stretching method, and a simultaneous biaxial stretching method is performed.
  • simultaneous biaxial stretching instead of simultaneous biaxial stretching, after performing stretching in one of the MD and TD directions, and then performing sequential biaxial stretching in which stretching is performed in the other direction, thermal expansion in the direction in which stretching was performed first The rate of decrease in the rate becomes smaller, the thermal shrinkage rate becomes worse, and the heat-resistant dimensional stability is lowered.
  • uniaxial stretching is performed instead of biaxial stretching, the coefficient of thermal expansion in the non-stretched direction is not reduced, and the heat-resistant dimensional stability is lowered.
  • the MD direction is a so-called flow direction, and means the direction (longitudinal direction) of the precursor film taken from the extruder.
  • the TD direction is a so-called width direction and means a direction orthogonal to the MD direction.
  • the stretching ratio, stretching temperature, and stretching speed are not particularly limited as long as the object of the present invention is achieved, but the following ranges are preferable. This is because the thermal shrinkage rate is further improved.
  • the draw ratio is within a range in which breakage of 2.0 times or more does not occur in both the MD direction and the TD direction, and is particularly preferably 2.0 to 5.0 times, more preferably 2.2 to 4.0 times. .
  • the draw ratios in the MD direction and the TD direction are preferably approximated. Specifically, when the draw ratio in the MD direction is P MD and the draw ratio in the TD direction is P TD , “P TD ⁇ P MD ” is preferably ⁇ 0.6 to +0.6, more preferably ⁇ 0 .3 to +0.3.
  • the draw ratio of MD direction is a ratio based on MD direction length just before extending
  • the stretching ratio in the TD direction is a ratio based on the length in the TD direction immediately before stretching.
  • the stretching temperature is Tg P or more and Tg P + 30 ° C. or less, where Tg P (° C.) is the glass transition temperature of the SPS resin constituting the film, and is preferably from the viewpoint of further improving the heat-resistant dimensional stability. Tg P ° C or higher and Tg P + 25 ° C or lower. If the stretching temperature is too low or too high, the heat-resistant dimensional stability is lowered.
  • the stretching temperature is the atmospheric temperature at which stretching is performed.
  • the Tg P of the SPS resin is the sum of the values obtained by multiplying the glass transition temperature of each polymer by the content ratio of the polymer.
  • the stretching speed is 50 to 10,000% / min in both the MD direction and the TD direction, preferably 100 to 5000% / min, and more preferably 100 to 3000% / min.
  • the stretching speed is a value calculated by ⁇ (dimension after stretching / dimension before stretching) -1 ⁇ ⁇ 100 (%) / stretching time.
  • the heat setting treatment is a treatment for fixing the orientation of the polymer molecules by holding the stretched film at a temperature equal to or higher than the stretching temperature.
  • the heat setting treatment temperature is Tg P + 70 ° C. or higher and Tm P or lower when the glass transition temperature of the SPS resin constituting the film is Tg P (° C.) and the melting point is Tm P (° C.). From the viewpoint of further improving the stability, Tg P + 75 ° C. or higher and Tm P ⁇ 20 ° C. or lower are preferable. If the heat setting treatment temperature is too low or too high, the heat shrinkage rate becomes high and the heat-resistant dimensional stability is lowered.
  • the heat setting treatment temperature is an atmospheric temperature for holding the film.
  • the Tm P of the SPS resin is the sum of values obtained by multiplying the melting point of each polymer by the content ratio of the polymer.
  • the heat setting process may be a tension type heat setting process in which the heat setting process is performed while maintaining the tension during the biaxial stretching process, or the heat setting process is performed by relaxing the tension simultaneously with the process.
  • the heat fixing process may be performed, or after performing the heat fixing process (first heat fixing process) while maintaining the tension, the tension is relaxed and the heat fixing process (second heat fixing process). You may implement the composite heat setting process which performs.
  • a relaxation heat setting process is performed.
  • the heat setting temperature is set within the above range.
  • the relaxation magnification is 0 in both the MD direction and the TD direction from the viewpoint of reducing the absolute value of the heat shrinkage rate, further improving the heat-resistant dimensional stability, and flatness of the film. It is preferably 0.8 to 1.00 times, more preferably 0.85 to 1.00 times, and most preferably 0.90 to 0.98 times.
  • the relaxation magnifications in the MD direction and the TD direction are preferably approximated.
  • Q MD is the relaxation factor in the MD direction
  • Q TD is the relaxation factor in the TD direction
  • “Q TD ⁇ Q MD ” is preferably ⁇ 0.1 to +0.1, more preferably ⁇ 0.
  • the relaxation magnification in the MD direction is a magnification based on the MD direction length immediately after stretching.
  • the relaxation magnification in the TD direction is a magnification based on the length in the TD direction immediately after stretching.
  • Matting refers to transferring the surface shape of a mold to the film surface by applying heat and pressure between a set of molds having a desired surface shape while applying tension to the film. This is a process for forming fine irregularities for matting.
  • the film to be matted is a film that has undergone a biaxial stretching process by the method described above.
  • the curling phenomenon can be sufficiently prevented, and the release property of the release film can be reduced during press molding using the release film. While further improving, it is possible to accurately transfer the fine concavo-convex shape on the surface of the release film to the molded body.
  • a mold pressing method in which two heated flat plate upper and lower molds are pressed, and passing between two hot rolls while pressing.
  • a roll press method or the like can be used.
  • One set of molds can be used in combination with one flat mold and one roll.
  • the mold may be made of any material as long as the surface shape of the mold can be transferred to the film.
  • the mold may be made of metal, rubber, or film. Only the surface portion having the contact surface may be made of metal or rubber.
  • embodiments for performing the above-described mold pressing method or roll pressing method will be described. Instead of heating the film with the mold or roll in the above-described mold pressing method or roll pressing method, immediately before pressing with the mold or roll. Alternatively, the film itself may be directly heated with an IR heater or the like.
  • Matting is performed on at least one side of the film, and is preferably performed on both sides of the film from the viewpoint of curling resistance.
  • the mat processing being performed on both sides of the film means that a mold having a matte property described later is used as both molds in a set of molds. Thereby, the matte property is provided to both surfaces of the film. Matting is performed on one side of the film when one of a set of molds has a matte type described below and the other has no matte type. It means to do. Thereby, matte property is provided only to one side of the film.
  • a matte mold is used as at least one of the set of molds, preferably both molds.
  • the mold having a matte property is a mold in which a surface roughness is given to the contact surface with the film so that the matted film surface has a surface roughness (Ra) described later.
  • the surface roughness of the contact surface with the film is the same as or greater than the surface roughness (Ra) described later of the matted film surface.
  • the temperature that a set of molds gives to both sides of the film is independently 100 ° C. to 250 ° C., preferably 120 ° C. to 220 ° C.
  • the pressing pressure is 0.5 to 300 kgf / cm 2 , preferably 1 to 200 kgf / cm 2 .
  • the pressure is 0.1 to 500 kgf / cm, preferably 1 to 100 kgf / cm.
  • the film tension is usually 1 to 300 N, preferably 10 to 200 N.
  • the tension is a tension applied to a 1 m wide film.
  • the film speed is usually 0.1 to 10 m / min, preferably 0.2 to 5 m / min.
  • the curling rate can be controlled by adjusting the mat processing conditions while adjusting the surface roughness of the mold, the processing temperature of the film, the pressing pressure, and the film tension within the above ranges.
  • the curl rate can be reduced by reducing the difference in surface roughness and / or temperature difference that a set of molds imparts to the film.
  • the curl rate is made more effective.
  • the curl rate is made more effective.
  • a temperature difference between a pair of molds on both sides of the film for example, a set temperature difference between the upper mold and the lower mold, particularly 30 ° C.
  • the curling rate can be reduced by reducing the press pressure and / or the film tension.
  • the curling rate can be further effectively reduced by setting the pressing pressure to 1 to 100 kgf / cm 2 , preferably 1 to 50 kgf / cm 2 .
  • the tension of the film can be further effectively reduced.
  • the curl rate of the PS release film of the present invention is 80% or less, preferably 60% or less, more preferably 30% or less. If the curl rate is too large, the end part will be bent during press molding, and a streak-like pattern will be generated in the molded product due to the end part bend, and the surface shape of the release film will be sufficiently transferred around it. Not.
  • the curl rate is the ratio of the projected area that decreases due to the occurrence of curling when a test piece (200 mm ⁇ 200 mm) is allowed to stand for 30 minutes at an atmospheric temperature of 180 ° C. It is measured by the method. The higher the curl rate, the greater the warp of the film, and the lower the curl rate, the smaller the warp of the film.
  • the projected area of the test piece can be calculated from an image obtained by taking a photograph from directly above the test piece.
  • the PS-type release film of the present invention usually has an absolute value of heat shrinkage at 180 ° C. of 8% or less, preferably 6% or less, more preferably 3% or less.
  • the absolute value of the heat shrinkage rate is within the above range for both the MD direction and the TD direction.
  • the absolute value of the heat shrinkage rate is too large, the heat-resistant dimensional stability is lowered, and when used as a release film for press molding, the molding surface of the mold cannot be formed sufficiently.
  • the heat shrinkage rate is a heat shrinkage rate in each of the MD direction and the TD direction when the test piece (200 mm ⁇ 200 mm) is left at an ambient temperature of 180 ° C. for 30 minutes, and will be described in detail later. Measured by the method.
  • a positive value means shrinkage
  • a negative value means expansion.
  • the PS release film of the present invention has at least one surface matted, and as a result, has a surface roughness (Ra) of 0.5 ⁇ m to 8.0 ⁇ m, particularly 0.6 ⁇ m to 5.0 ⁇ m. preferable.
  • the PS release film of the present invention is preferably matted on both sides from the viewpoint of curling resistance, and as a result, each surface independently has a surface roughness (Ra) within the above range. From the viewpoint of curling resistance, in the most preferred embodiment, the difference in surface roughness between both surfaces is 1.5 ⁇ m or less, preferably 1.0 ⁇ m or less, more preferably 0.5 ⁇ m or less.
  • the surface roughness of the film in the present invention is a value measured according to JIS B-0601: 1994.
  • the thickness of the PS release film of the present invention is not particularly limited, and is, for example, 10 to 150 ⁇ m, preferably 25 to 75 ⁇ m, and particularly preferably 35 to 60 ⁇ m.
  • the PS release film of the present invention is particularly useful as a release film (transfer film) that requires transferability.
  • the mold and the molding material are formed by interposing the film between the mold and the molding material during press molding.
  • the surface shape of the film can be accurately transferred while preventing fusion with the film.
  • the mold release film of the present invention is sufficiently prevented from changing in dimensions, for example, even when the mold forming surface has irregularities with a depth of 1 mm, the forming surface can be accurately shaped.
  • the type of plastic constituting the molding material is not particularly limited.
  • epoxy resin, phenol resin, silicon resin, melamine resin, urea resin, alkyd resin, polyimide resin, polyester resin, polyurethane resin, acrylic resin, etc. can be used. It is.
  • the mold temperature during pressing is usually 80 to 200 ° C.
  • the press pressure is usually 1 to 150 kg / cm 2 .
  • the pressing time is usually 0.5 to 60 minutes.
  • Examples 1 to 5 / Comparative Examples 1 to 2 A mixture of the following components was melt extruded from a T die at a resin temperature of 280 ° C. with an extruder, and then cooled to obtain an unstretched film (precursor film). The unstretched film was subjected to a stretching process under the conditions described below.
  • the stretching step consisted of stretching treatment and heat setting treatment, and the heat setting treatment was a relaxation type heat setting treatment at a predetermined temperature and a relaxation ratio.
  • the stretching process is simultaneous biaxial stretching.
  • syndiotactic polystyrene resin As a mixture component, syndiotactic polystyrene resin, antioxidant and lubricant were used in both Examples and Comparative Examples.
  • syndiotactic polystyrene resin “Zarek 142ZE” (manufactured by Idemitsu Kosan Co., Ltd., glass transition temperature 95 ° C., melting point 247 ° C.) was used.
  • the antioxidant a phenolic antioxidant was used, and as the lubricant, an amide lubricant was used.
  • the blending ratio was 0.2 parts by weight of ADK STAB AO-60 and 0.2 parts by weight of lubricant with respect to 100 parts by weight of syndiotactic polystyrene resin.
  • the stretching conditions are as follows in both Examples and Comparative Examples.
  • the draw ratio is 3.3 x 3.4 times (MD x TD)
  • Stretching temperature 115 ° C
  • Stretching speed 500% / min
  • Heat setting temperature 215 ° C
  • Relaxation magnification 0.92 ⁇ 0.92 (MD ⁇ TD)
  • the stretched film obtained above was cut to a width of 1 m, and then subjected to mat processing by pressing with two flat molds to obtain a release film.
  • the processing conditions are as shown in Table 1.
  • the upper mold uses the mold itself with a given surface roughness
  • the lower mold gives a silicon rubber layer with a given surface roughness to the mold surface. We used what we did.
  • the curl rate 200mm ⁇ 200mm cut film is left in a hot air circulation oven set at 180 ° C in a hot air circulation oven for 30 minutes in a suspended state, then taken out and placed on a flat surface.
  • the total area of the film after heating is measured by stretching the curled film.
  • the surface roughness of the film is an arithmetic average height (Ra) measured according to JIS B-0601: 1994.
  • the upper surface is a film surface that comes into contact with the upper die during mat processing, and the lower surface is a fill surface that comes into contact with the lower die.
  • a positive value for heat shrinkage means shrinkage. It should be noted that if the absolute value of the heat shrinkage is 3% or less, a very preferable level ( ⁇ ), a preferable level ( ⁇ ) if it is 6% or less, a level ( ⁇ ) that causes no practical problem if it is 8% or less, If it exceeds 8%, it is a practically problematic level (x).
  • the transfer films release films having transfer properties obtained in Examples 1 to 5, Comparative Example 1 and Comparative Example 2 were used. Specifically, as shown in FIG. 1, when the epoxy resin flake 1 is hot press-molded by the upper and lower molds 2, 3, the transfer film 4 is interposed between the flake 1 and the molds 2, 3. The transfer film 4 was held and fixed outside the mold. The transfer film 4 was arranged so that the surface to which the roughness was given by the silicon rubber layer was on the upper and lower molds 2 and 3 side. During pressing, the approach of the dies 2 and 3 was limited by the spacer 5. The press conditions were as follows.
  • A The transfer surface of the epoxy molding was free from streaks and unevenness, and the surface of the transfer film was transferred as it was; ⁇ : The transfer surface of the epoxy molded body had almost no streak-like pattern or unevenness, and the surface of the transfer film was almost transferred; ⁇ : The transfer surface of the epoxy molded product had a slight streak pattern and unevenness, and the transfer of the transfer film surface was slightly insufficient (no problem in practical use); X: The transfer film bent on the transfer surface of the epoxy molding was transferred as a step, resulting in transferability having a practical problem.
  • the release film of the present invention is sufficiently excellent in heat-resistant dimensional stability, has a good curl rate, is excellent in moldability (following property) and releasability, and imparts good matte properties to the molded product. I can do it.
  • the release film of the present invention is more useful as a release film used in such a single wafer system.
  • the mold release film of the present invention is a mold such as a flat plate mold or a molding roll when manufacturing a printed circuit board, a ceramic electronic component, a semiconductor package, a lens component, a thermosetting resin product, a thermoplastic resin product, a decorative plate, and the like. It is useful as a release film interposed between the film and the molding material.
  • the release film of the present invention is a so-called transfer film, and is useful as a film for transferring a matte tone provided on the surface of the film to the surface of a molding material.
  • the release film of the present invention is laminated for the purpose of supporting and protecting the thin film layer in the process of forming a thin film layer such as a thermosetting resin, thermoplastic resin, ceramic, metal, or a predetermined processing process. It is useful as a process film to be peeled and removed.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
PCT/JP2014/068811 2013-07-16 2014-07-15 離型フィルム WO2015008759A1 (ja)

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KR101851371B1 (ko) * 2016-03-04 2018-06-07 (주)엘켐 패턴 형성 방법
KR20210018185A (ko) 2018-06-08 2021-02-17 구라시키 보세키 가부시키가이샤 이형 필름 및 이형 필름 제조 방법

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JP6738672B2 (ja) * 2016-07-04 2020-08-12 倉敷紡績株式会社 離型フィルムおよび半導体パッケージの製造方法
JP7029973B2 (ja) * 2018-02-16 2022-03-04 日本電産サンキョー株式会社 ゲル状部材の製造方法
JP6667836B1 (ja) * 2019-03-20 2020-03-18 株式会社コバヤシ 金型と離型フィルムとの組合せ、離型フィルム、金型、及び成形体の製造方法

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KR20210018185A (ko) 2018-06-08 2021-02-17 구라시키 보세키 가부시키가이샤 이형 필름 및 이형 필름 제조 방법

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JPWO2015008759A1 (ja) 2017-03-02
CN105358308B (zh) 2018-11-09
CN105358308A (zh) 2016-02-24
JP6307078B2 (ja) 2018-04-04
KR20160032105A (ko) 2016-03-23

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