[go: up one dir, main page]

WO2024010242A1 - Film antiadhésif - Google Patents

Film antiadhésif Download PDF

Info

Publication number
WO2024010242A1
WO2024010242A1 PCT/KR2023/008255 KR2023008255W WO2024010242A1 WO 2024010242 A1 WO2024010242 A1 WO 2024010242A1 KR 2023008255 W KR2023008255 W KR 2023008255W WO 2024010242 A1 WO2024010242 A1 WO 2024010242A1
Authority
WO
WIPO (PCT)
Prior art keywords
release
release layer
film
release film
paragraph
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2023/008255
Other languages
English (en)
Korean (ko)
Inventor
장민우
정재영
윤종욱
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Advanced Materials Korea Inc
Original Assignee
Toray Advanced Materials Korea 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 Toray Advanced Materials Korea Inc filed Critical Toray Advanced Materials Korea Inc
Priority to JP2023552492A priority Critical patent/JP7762214B2/ja
Priority to CN202380010694.4A priority patent/CN117677682A/zh
Publication of WO2024010242A1 publication Critical patent/WO2024010242A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners

Definitions

  • This disclosure relates to release films.
  • Release films are usually attached to an adhesive film and are used as a protective film to protect the adhesive component from foreign substances or unwanted adherends in the air, and generally have a structure in which a release layer is formed on a polyester base film.
  • release films are generally attached to point/adhesive films or tapes as a protective film, and are used to prevent unintended adhesion to adherends or contamination by dust, foreign substances, etc. until the point/adhesive is used.
  • Another use is to prevent the mold and molded product from sticking during a heat-and-pressure molding process such as printed wiring boards or in-mold molding, or to use it as a coating base for applying various resins such as ceramic slurry to the release surface of a release film, and other applications. It can be used as an intermediate material for lamination to protect various resin layers coated on a substrate.
  • the release film is used as a carrier film to thinly and uniformly apply ceramic slurry on the green sheet that makes up the MLCC (Multi-Layer Ceramic Capacitor, MLCC).
  • MLCC is a type of capacitor used to store electricity or stabilize current. Due to its small size and large capacitance, it is widely used in portable electronic devices. In particular, demand for it has increased significantly with the recent spread of smartphones and tablet PCs. I'm doing it.
  • These MLCCs are completed by alternately stacking green sheets and internal metal electrodes in tens or hundreds of layers and then connecting external electrodes, and their sizes vary from less than 1 mm to several nm.
  • the green sheet used in MLCC is formed by uniformly applying ceramic slurry on a carrier film as a support and then firing it.
  • the carrier film for forming the green sheet is a biaxial film with excellent mechanical strength, dimensional stability, heat resistance, and price competitiveness.
  • a stretched polyester film is used as a substrate, and a release film with a polymer silicone release layer applied to one side is used.
  • the release film used in MLCC is particularly required to have physical properties that can be peeled off with an appropriate peeling force.
  • This disclosure provides technology for release films.
  • the purpose of the present disclosure is to provide a release film that can implement a wide range of peel strength and exhibit excellent stability over time.
  • the present disclosure aims to provide a release film that can be formed by low temperature curing in an aqueous system.
  • the present disclosure can provide a release film.
  • the release film is a base film; And a release layer formed by applying a release coating composition to at least one surface of the base film; a release layer measured using a time-of-flight secondary ion mass spectrometer (TOF-SIMS) in the thickness direction from the surface of the release layer.
  • TOF-SIMS time-of-flight secondary ion mass spectrometer
  • the ionic strength curve of NH - may include an inflection point.
  • the ionic strength curve of NH - may have a concave shape.
  • the release layer may further include one or more of Si - , S - , C 7 H 5 O 2 - , and C 3 H 5 N 5 - ions.
  • the release layer includes Si - ions and C 7 H 5 O 2 - ions, and in the depth profile measured using TOF-SIMS in the thickness direction from the surface of the release layer, Si -
  • the ionic strength decreases, the ionic strength of C 7 H 5 O 2 - increases, and there may be a point in the release layer where the ionic strengths of the Si - ion and C 7 H 5 O 2 - ion are the same.
  • the release layer includes S - ions, and in the depth profile measured using TOF-SIMS in the thickness direction from the surface of the release layer, the ion intensity curve of S - may include an inflection point. there is.
  • the ionic strength curve of S - may have a concave shape.
  • the release layer includes C 3 H 5 N 5 - ions, and in the depth profile measured using TOF-SIMS in the thickness direction from the surface of the release layer, a position adjacent to the surface of the release layer The ionic strength of C 3 H 5 N 5 - may decrease.
  • the release film may exhibit an immediate tape release force of 5 to 32 gf/in.
  • the release film may exhibit a peeling force of 3 to 1000 gf/in at room temperature per day.
  • the release film may exhibit a green sheet peeling force of 1 to 3 gf/in.
  • the silicon content of the release layer measured using an X-ray fluorescence spectrometer may be 0.001 to 0.2 g/m 2 .
  • the surface energy of the release layer may be 19 to 30 dyne/cm.
  • the release film may be formed by curing the release coating composition at a temperature of 150°C or lower.
  • the release coating composition is a composition curable at a temperature of 150° C. or lower, and includes a silicone emulsion component (A) containing polydimethylsiloxane (PDMS); A component (B) containing two or more functional groups capable of condensation reaction with the silicone emulsion component in one molecule; And it may be an aqueous release coating composition containing an acid catalyst.
  • a component (B) containing two or more functional groups capable of condensation reaction with the silicone emulsion component in one molecule may be an aqueous release coating composition containing an acid catalyst.
  • the release film according to one aspect of the present disclosure can realize a wide range of peeling force and exhibit excellent stability over time when manufactured as a release film, and this effect is more effective when compared to a release film manufactured using a silicone-based release coating composition. It is excellent.
  • the release film according to one aspect of the present disclosure is a silicone-based film, it can be formed by low-temperature curing in an aqueous system, which is superior when compared to silicone-based films formed by conventional high-temperature curing.
  • Figure 1 shows the TOF-SIMS depth profile measurement results of a release film according to an embodiment of the present invention.
  • Figure 2 is a schematic diagram showing a conventional silicone-based release film and a release film according to an embodiment of the present invention.
  • Figure 3 is a graph showing the results of FT-IR spectrum measurement of a release film according to an embodiment of the present invention.
  • the release film includes a base film; and a release layer formed by applying a release coating composition to at least one surface of the base film.
  • the release film has NH - in the ion intensity curve of NH - in the depth profile measured in the thickness direction from the surface of the release layer using a time-of-flight secondary ion mass spectrometer (TOF-SIMS).
  • TOF-SIMS time-of-flight secondary ion mass spectrometer
  • Figure 1 shows the TOF-SIMS depth profile measurement results of a release film according to an embodiment of the present invention.
  • the ratio of I NH_t /I NH_max is 0.9 or less, and I NH_t > I NH_b .
  • the ratio of I NH_t /I NH_max may be less than or equal to 0.8, or less than or equal to 0.7, or less than or equal to 0.6, or less than or equal to 0.5, or less than or equal to 0.4, or less than or equal to 0.3, or less than or equal to 0.2. It may be 0.1 or less, or it may be 0.05 or more, or it may be 0.07 or more, or it may be 0.09 or more.
  • a large amount of non-silicon component may exist as a main component on the surface of the release layer.
  • non-silicon components e.g., melamine components
  • surfactants e.g., melamine components
  • other components e.g., melamine components
  • the surface of the release layer contains a small amount of non-silicon component (e.g., melamine component), and other components (e.g., melamine component and phase separation are not present). Good ingredients) may be present in large quantities.
  • non-silicon component e.g., melamine component
  • other components e.g., melamine component and phase separation are not present.
  • Good ingredients may be present in large quantities.
  • the ionic strength curve of NH - includes an inflection point.
  • the inflection point means the point at which the slope of the tangent changes when the ionic strength of NH - increases or decreases, and the ionic strength of NH - is between the point corresponding to I NH_t and the point corresponding to I NH_max in the ionic strength curve.
  • the inflection point where the increase in the ionic strength of NH - decreases between the point corresponding to I NH_t and the point corresponding to I NH_max in the ionic strength curve may be the point where the Si content in the release layer begins to decrease. there is.
  • the ionic strength curve of NH - may have a concave shape.
  • That the ionic strength curve of NH - has a concave shape means that the distribution of the silicone component from the entire surface of the release film to the base film has a concave shape. That is, the proportion of silicone component is high on the entire surface of the release film, and in the middle part of the entire release film, the content of silicone component decreases and non-silicon component (e.g., melamine component) is included as the main component, and below that, the content of silicone component is reduced. It may mean that a film exists.
  • the release layer may further include one or more of Si - , S - , C 7 H 5 O 2 - , and C 3 H 5 N 5 - ions. .
  • the release layer may include a combination of any two or more of Si - , S - , C 7 H 5 O 2 - , and C 3 H 5 N 5 - ions.
  • the release layer may include Si - , S - , C 7 H 5 O 2 - , and C 3 H 5 N 5 - ions.
  • the release layer includes Si - ions and C 7 H 5 O 2 - ions, and in the depth profile measured using TOF-SIMS in the thickness direction from the surface of the release layer, Si -
  • the point in the release layer where the ionic strengths of the Si - ion and C 7 H 5 O 2 - ion are the same is the area where non-silicon components (for example, melamine components) begin to be included in earnest compared to the silicon component. This may be the starting point.
  • non-silicon components for example, melamine components
  • the point where the Si - ion and C 7 H 5 O 2 - ion have the same ionic strength may be closer to the point corresponding to I NH_t than to the point corresponding to I NH_b , and closer to the point corresponding to I NH_t . It may be closer to the point corresponding to I NH_max .
  • the point where the ionic strength of the Si - ion and the C 7 H 5 O 2 - ion are the same is in the area containing the silicone component - the area containing the non-silicon component (e.g., melamine component) - in the release film of the base film structure. This may be the point where the non-silicon component area begins.
  • the non-silicon component e.g., melamine component
  • These points may be closer to the point corresponding to I NH_t than to the point corresponding to I NH_b , and are closer to the point corresponding to I NH_max than to the point corresponding to I NH_t , so that the difference between the silicon component and the non-silicon component This may mean a smoother concentration change rather than a rapid change in concentration, which may be due to the manufacturing process in which a release coating composition containing a silicone component and a non-silicon component is coated once to form a release layer. there is.
  • the release layer includes S - ions, and in the depth profile measured using TOF-SIMS in the thickness direction from the surface of the release layer, the ion intensity curve of S - will include an inflection point.
  • the ionic strength curve of S - may have a concave shape.
  • the release layer includes C 3 H 5 N 5 - ions, and in the depth profile measured using TOF-SIMS in the thickness direction from the surface of the release layer, adjacent to the surface of the release layer
  • the ionic strength of position C 3 H 5 N 5 - may decrease.
  • a release film may be manufactured by applying a release coating composition to at least one side of a base film to form a release layer, and the release film manufactured in this way may have the following physical properties.
  • the physical properties below can be measured by the method described in the experimental example.
  • the release film may exhibit a tape immediate peel force of 5 to 32 gf/in, and may exhibit a peel force of a value that lies between the upper and lower limits described above, for example, 7 Greater than or equal to 9 gf/in, greater than or equal to 11 gf/in, greater than or equal to 13 gf/in, greater than or equal to 15 gf/in, greater than or equal to 17 gf/in, greater than or equal to 19 gf/in, greater than or equal to 21 gf/in, greater than or equal to 23 gf/in.
  • the release film may exhibit a peeling force of 3 to 1000 gf/in at room temperature per day, and may exhibit a peeling force of a value that exists between the upper and lower limits described above, for example, , 10 gf/in or more, 50 gf/in or more, 100 gf/in or more, 200 gf/in or more, 300 gf/in or more, 400 gf/in or more, 500 gf/in or more, 600 gf/in or more, 700 greater than or equal to 800 gf/in, or greater than or equal to 900 gf/in or less than or equal to 900 gf/in, or less than or equal to 800 gf/in, or less than or equal to 700 gf/in, or less than or equal to 600 gf/in, or less than or equal to 500 gf/in, or less than or equal to 400 gf/in.
  • This release film satisfies the peeling force of a light peel, medium peel, or ultra-heavy peel release film, and can be used in a variety of fields requiring this.
  • the release film exhibits a wide tape daily peel strength at room temperature, a range that corresponds to physical properties that cannot be achieved with conventional silicone release films.
  • the release film may exhibit a green sheet peeling force of 1 to 3 gf/in, and may exhibit a peeling force of a value that exists between the upper and lower limits described above.
  • the green sheet peeling force can be measured by the method described in Experimental Example 1, and may represent the peeling force for a 3 ⁇ m thick green sheet.
  • the release film according to one aspect of the present disclosure has the advantage of being able to implement a variety of tape peeling force levels (grades) at room temperature per day, and at the same time, a certain range of light peeling force based on the tape immediate peeling force or green sheet peeling force. Accordingly, one release film can be used in industrial fields that require 1-day peeling force at room temperature as a tape for various purposes, and in industrial fields that require light peeling force based on tape immediate peeling force or green sheet peeling force. It can be used for various purposes.
  • the release film may have a silicon content of the release layer of about 0.001 to about 0.2 g/m 2 as measured using an X-ray fluorescence spectrometer.
  • the release film may exhibit a residual adhesion rate of about 94%, about 95%, or about 96% or more, and the residual adhesion rate may be measured by the method described in Experimental Example 4.
  • an adhesive such as pressure sensitive adhesive (PSA) or optically clear adhesive (OCA) is attached to the release film and then the release film is peeled off.
  • PSA pressure sensitive adhesive
  • OCA optically clear adhesive
  • uncured components present in the release layer of the release film are transferred, which may cause problems that interfere with the adhesive properties of the adhesive. Since the release film of the present disclosure satisfies a residual adhesion rate of about 95% or more, it has the advantage of being usable even in fields that require high standards.
  • the release film may have a surface energy of the release layer of about 19 to about 30 dyne/cm or about 19.5 to about 27 dyne/cm, with a surface energy value falling between the upper and lower limits described above. It may represent.
  • the surface energy of the release layer can be measured by the method described in Experimental Example 5.
  • the release film may have a residual amount of volatile organic compounds of about 5 ppm or less, and thus can be used as an eco-friendly material.
  • the method for producing the release film is not particularly limited as long as the release layer is formed using a release coating composition.
  • a release coating composition is applied to at least one side of the base film, heated and dried to cure the component (B) and the silicone emulsion component included in the release coating composition to form a release layer, thereby obtaining a release film. It is possible.
  • the method of applying the release coating composition may be a known method widely used in the release film field, for example, gravure coating method, bar coating method, spray coating method, spin coating method, knife coating method.
  • a method such as a roll coating method, a die coating method, an in-line coating method, an off-line coating method, etc., but it is not limited thereto.
  • the applied release coating composition may be heat-cured by heat drying, where the heating temperature is 110°C to 160°C, 120°C to 160°C, 130°C to 160°C, 140°C to 160°C, It may be 150°C to 160°C, 145°C to 155°C, or 150°C to 155°C, and may be a temperature within the range described above.
  • the heating time may be 5 seconds to 60 seconds, 10 seconds to 40 seconds, 15 seconds to 30 seconds, or 20 seconds to 25 seconds, and may be a time within the range described above.
  • a post-curing process may be further included to cure the uncured component after drying the release coating composition by heating.
  • the post-curing process may involve rolling a release film prepared by heat drying into a roll and then processing it at 40°C to 60°C for 1 to 5 days.
  • the treatment temperature may be 40°C to 60°C, 45°C to 55°C, 47°C to 53°C, 49°C to 53°C, 50°C to 53°C, or 50°C to 51°C
  • the treatment time is 1 to 5 days. days, 1.5 to 4.5 days, 2 to 4 days, 2.5 to 3.5 days, or 3 to 3.5 days.
  • the release layer of the release film may be formed to have a dry thickness of 0.01 to 2 ⁇ m, or 50 nm to 500 nm.
  • the release film may be used for an adhesive, a semi-curable adhesive, a protective film, a coating substrate, a laminated liner, a ceramic sheet for a multilayer ceramic capacitor, a semi-cured resin for a printed circuit, or a prepreg.
  • the base film constituting the release film may be a known film widely used in the conventional release film field, but is not limited thereto.
  • the base film may be formed from a polyester-based polymer, but the base film to which the release coating composition is applied is not limited to the polyester-based film.
  • polyester polymers include polyethylene terephthalate polymer, polybutylene terephthalate polymer, polyethylene naphthalate polymer, polyphenylene sulfide polymer, polyether ether ketone polymer, polyphthalamide polymer, polyimide polymer, polysulfone polymer, It may be a polyethersulfone polymer, a polyetherimide polymer, or a combination thereof, but is not limited thereto.
  • the polyester polymer may be a polyester obtained from a condensation reaction of an aromatic dicarboxylic acid and an aliphatic glycol.
  • the aromatic dicarboxylic acid is isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid (e.g., p-oxybenzoic acid, etc.), or It may be a combination of these, but is not limited thereto.
  • the aliphatic glycol may be ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, or a combination thereof, but is not limited thereto.
  • polyester polymer two or more of the aromatic dicarboxylic acid and aliphatic glycol may be used in combination, and a copolymer containing a third component may also be used, but heat resistance and chemical resistance
  • a copolymer containing a third component may also be used, but heat resistance and chemical resistance
  • the base film may have a thickness of 10 to 200 ⁇ m, but is not limited thereto.
  • the release coating composition may be applied to at least one side of the base film to form a release layer.
  • the release coating composition according to one aspect of the present disclosure uses component (B) as a main chain component constituting the release layer after curing.
  • component (B) is used, a strong release layer coating film can be obtained due to high crosslinking density. , it is possible to achieve a degree of curing that exceeds that of existing silicone-based release coating compositions. This is because in the release film for the ceramic green sheet manufacturing process for the manufacture of MLCC, it is effective to harden the release layer coating in order to control the peeling force to the desired level.
  • FIG. 2 is a schematic diagram showing film formation by low-temperature curing of a conventional silicone-based release coating composition and an aqueous release coating composition according to an embodiment of the present invention at a temperature of 150°C or lower. Referring to FIG. 2, when using a conventional silicone-based release coating composition at a temperature of 150°C or lower, it can be seen that the bonding strength with the base film (eg, PET film) is low (see the drawing on the left).
  • the base film eg, PET film
  • the film manufacturing process includes an offline process of unwinding the finished film fabric, coating it, then rewinding it to produce a film, and a process of extruding the polymer to form a sheet and then film.
  • it can be divided into an in-line process that turns the polymer into a film with an intermediate coating.
  • the drying temperature in the offline process is up to about 150°C
  • the in-line process can have a drying temperature of about 210 to 240°C in the film stretching process. Therefore, in offline processes, only non-aqueous solvents (i.e. solvent-based solvents) have been used for curing at temperatures below 150°C.
  • the release coating composition according to one aspect of the present disclosure includes a component (B) containing two or more functional groups capable of condensation reaction with the silicone emulsion component, thereby achieving a high degree of curing at a temperature of 150 ° C. or lower. While doing so, excellent physical properties such as rub-off characteristics can be realized. Therefore, it may be possible to use water-based emulsions even in offline processes.
  • component (B) e.g., melamine component
  • a phase separation curing reaction is induced, making it possible to produce a film with excellent adhesion and a high degree of curing (see the drawing on the right).
  • the component (B) may form a Si-O-R-N bond structure (where R is an alkyl group having 1 to 4 carbon atoms) through a silicone emulsion component condensation reaction.
  • R can be -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, or -CH 2 CH 2 CH 2 CH 2 -.
  • the functional group included in component (B) may be an amine group or an amine-derived functional group.
  • component (B) is not particularly limited as long as it contains two or more functional groups capable of condensation reaction with the silicone emulsion component in one molecule, but may be a melamine component, and generally includes melamine and formaldehyde. It is manufactured by the reaction of , and may be an alkyl etherified melamine compound obtained by reacting the methylolated melamine thus produced with an alcohol of an appropriate carbon number under acid catalyst conditions.
  • component (B) may refer to a melamine compound having the structure of Formula 1 below, an oligomer thereof, a polymer thereof, and/or a combination thereof.
  • X represents a hydrogen atom, -CH 2 OH, or -CH 2 -OR, and each may be the same or different.
  • R represents an alkyl group having 1 to 8 carbon atoms, and each may be the same or different. Additionally, at least one X may be -CH 2 -O-CH 3 .
  • component (B) a variety of commercially available and widely used products can be used as component (B), such as Cymel 300, Cymel 301, Cymel 303LF, Cymel 350, or Cymel 370N (or more , Allnes products) can be used, but are no longer limited. Commercially available products can be used alone or in combination of two or more.
  • the content of component (B) may be about 0.2 to about 1.0% by weight based on the total weight of the entire composition, specifically about 0.2 to about 0.8% by weight, about 0.3 to about 0.7% by weight, about It may be from 0.4 to about 0.6 weight percent, or from about 0.5 to about 0.6 weight percent. If component (B) is used in excessive amounts below the above minimum value, the desired curing effect, that is, the effect of lowering the green sheet peeling force of the release film by keeping the release layer hard, is weakened, and the peeling force may not be adjusted as desired. In addition, if component (B) is not properly cured, the aging stability of the release film may decrease, so it is recommended that the content of component (B) satisfies the content ratio with the acid catalyst mentioned below.
  • the total acid value in component (B) may be 390 to 780 mg KOH/g, specifically 400 KOH/g or more, 450 KOH/g or more, 500 KOH/g or more, 550 KOH/g or more, 600 KOH/g or more.
  • the silicone emulsion component may be used as a binder or peel force modifier in the release coating composition.
  • Component (B) has a low molecular weight of the monomer, so it forms a dense cross-linked structure after curing and has a high cross-linking density, increasing the hardness of the release layer during coating. As the hardness of the release layer increases, the peeling power of the green sheet decreases. There is a problem with losing. To solve this problem, by curing together a silicone emulsion component that contains a functional group with release properties such as Si-CH 3 and has soft characteristics, the hardness can be liberated and the softness of the release layer can be increased. there is.
  • the peeling power of the release film also increases, and the present disclosure provides a wide range of peeling power, especially a wide range of tapes, due to the combination of component (B) and the silicone emulsion component. It shows the effect of achieving peeling power for 1 day at room temperature.
  • the silicone emulsion component can form a Si-O-N bond structure through a condensation reaction with component (B), and the formed copolymer of the component (B)-silicone emulsion component and its structure increases the softness of the release layer and stability over time. can increase.
  • the melamine component of Chemical Formula 1 described above may have up to a total of 6 functional groups.
  • the NX 2 group of the melamine component may form a Si-ON bond structure through a condensation reaction with the silicone emulsion component.
  • the peeling force is increased by adding a silicone polymer component, but if the content of the silicone polymer component exceeds 50% by weight based on the total weight of the entire composition, serious problems with stability over time occur. This is because over time, the silicone polymer component that should be present on the surface of the release layer is impregnated into the inside of the release layer.
  • component (B) and the silicone emulsion component become a copolymer and form a cross-linked network structure, so the functional groups showing release properties move from the surface of the release layer to the inside. It can be maintained without being impregnated, and thus can exhibit excellent stability over time.
  • the silicone emulsion component is not limited as long as it can combine with component (B) to form a cross-linked network structure and impart softness.
  • the silicone emulsion component is not particularly limited, but may not contain side chains other than the main chain.
  • the silicone emulsion component may not include polyalkylene glycol (eg, polyethylene glycol, PEG).
  • polyalkylene glycol eg, polyethylene glycol, PEG
  • the silicone emulsion component may not contain hydroxyl groups, polyether groups, and polyester groups.
  • the silicone emulsion component may not contain an alkenyl group.
  • the release properties are limited to medium peeling (200g or more based on TESA7475 tape), so films using compositions containing this may be limited to use only in medium peeling areas such as MLCC.
  • the silicone emulsion component does not contain side chains such as polyalkylene glycol, hydroxyl group, polyether group, polyester group, alkenyl group, etc.
  • the surface of the release layer can be formed with the Si-CH 3 component, as in the case of using existing silicone-based curing, so it can be used not only for heavy peeling applications such as MLCC, but also for various purposes such as light peeling areas. This is possible.
  • the silicone emulsion component may be, but is not limited to, polydimethylsiloxane (PDMS).
  • PDMS polydimethylsiloxane
  • the silicone emulsion component may be, but is not limited to, branched polydimethylsiloxane.
  • the ratio of Si-Vi to Si-H in the silicone emulsion components may be 1:1.5 to 1:2.5.
  • the ratio of Si-Vi to Si-H in the silicone emulsion components may be 1:1.6 to 1:2.3.
  • Si-Vi means a silicon-vinyl group bond
  • Si-H means a silicon-hydrogen bond. If the ratio of Si-Vi:Si-Hi among the silicone emulsion components is less than 1:1.5, when the composition is cured, curing may be insufficient, resulting in poor residual adhesion and poor adhesion to the substrate.
  • the content of the silicone emulsion component is 0.02 to 9% by weight, 0.02 to 8% by weight, 0.03 to 7% by weight, 0.04 to 6% by weight, or 0.05 to 6% by weight, based on the total weight of the entire composition. It can be. If the silicone emulsion component is used in excess of the above maximum value, component (B) cannot be sufficiently cured and the uncured silicone emulsion component or component (B) rises to the surface of the release layer, causing rub-off of the release film. Properties (i.e., adhesion or adhesion of the release layer to the base film) may appear poor. If the silicone emulsion component is used in an excessively small amount below the above minimum value, the crosslinked network structure due to the curing reaction may not be properly formed, and the desired peel strength or stability over time may not be achieved.
  • the silicone emulsion component may further include a metal catalyst.
  • the metal catalyst may be an alkali metal catalyst, an alkaline earth metal catalyst, or a rare earth metal catalyst, but is not limited thereto.
  • the metal catalyst may be a platinum catalyst, but is not limited thereto.
  • the weight ratio of component (B) and the silicone emulsion may be 100:10 to 100:900 based on solid content, and may be a weight ratio that exists between the upper and lower limits described above.
  • the acid catalyst is not limited as long as it is known to catalyze the crosslinking reaction of component (B) or the crosslinking reaction between component (B) and the silicone emulsion component, and may be appropriately selected and used.
  • acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; oxalic acid, acetic acid, formic acid, methanesulfonic acid, trifluoromethanesulfonic acid, isoprenesulfonic acid, camphorsulfonic acid, hexanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, and decanesulfonic acid.
  • hexadecane sulfonic acid dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, p-toluenesulfonic acid, melamine zinc iodide (melamine ZnI 2 ), melamine trisulfonic acid (MTSA), cumenesulfonic acid, Dodecylbenzenesulfonic acid, naphthalenesulfonic acid, nonylnaphthalenesulfonic acid, methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, 2-ethylhexyl acid phosphate, Decyl acid phosphate, lauryl acid phosphate
  • the weight ratio of component (B) and acid catalyst may be 100:5 to 100:30, 100:10 to 100:20, or 100:10 to 100:15, and may be between the upper and lower limits described above. It may be a weight ratio that exists. If the content of the acid catalyst is excessively less than the minimum value of the weight ratio, the curing reaction will not occur properly, and if it is used in an excessive amount exceeding the maximum value, overcuring may occur, which may result in poor stability over time in both cases. Therefore, in order to achieve excellent stability over time, it is recommended that the weight ratio of component (B) and the acid catalyst satisfy the above range.
  • the release coating composition may be a water-based release coating composition.
  • an aqueous system may mean an aqueous solution or an aqueous dispersion, and the solvent component of the composition may be water alone or a combination of water and an organic solvent as described below.
  • the water-based release coating composition is an water-based base, when forming a release layer, emissions of volatile organic compounds (VOC) can be fundamentally reduced and environmentally friendly requirements can be satisfied.
  • VOC volatile organic compounds
  • it can be easily used by mixing with water-based additives such as water-based antistatic agents, and has the advantage of being able to implement both antistatic properties and release properties of the release film with a one-component solution.
  • the release coating composition may further include an aqueous solvent.
  • the aqueous solvent may be water or a combination of water and an organic solvent.
  • the combination ratio of water and organic solvent is water:organic solvent weight ratio of 50:50 or more, 60:40 or more, 70:30 or more, 80:20 or more, 85:15 or more, 90:10 or more, 95:5 or more, Or it could be 99:1 or higher.
  • the organic solvent may be a known organic solvent widely used in the release film field, and is not particularly limited as long as it is a solvent that has good compatibility with water.
  • organic solvents include isopropyl alcohol, isobutyl alcohol, hexane, acetone, ethyl acetate, ethylene glycol, propylene glycol, butyl glycol, dipropylene glycol, polyethylene glycol, gamma-butyrolactone, and combinations thereof. It may be one or more selected from the group consisting of, but is not limited thereto.
  • the release coating composition may further include one or more of an antistatic agent, a conductivity improver, a pH adjuster, a surfactant, and an antifouling agent within a range that does not change the physical properties (e.g., edges) of the release layer to be achieved. .
  • the antistatic agent may not only provide antistatic ability to the release layer but also have the effect of preventing adsorption of foreign substances.
  • the ceramic green sheet manufacturing process there is a process of cutting and cutting the ceramic green sheet.
  • the ceramic green sheet is in the form of agglomerated beads like particles, so the bead drop phenomenon occurs during the process of cutting the green sheet. Therefore, the antistatic ability can prevent beads from falling off due to static electricity during the process of cutting the release film together with the ceramic green sheet, thereby contributing to the fairness of ceramic green sheet manufacturing.
  • the antistatic agent may be a known antistatic agent widely used in the release film field and is not particularly limited.
  • antistatic agents include poly(3,4-ethylenedioxythiophene) (PEDOT), poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), polyaniline, polypyrrole, quaternary ammonium salts, sulfonates, and phosphates. It may be selected from the group consisting of, but is not limited thereto.
  • the antistatic agent may be included in the release coating composition in the form of an aqueous solution containing a solid antistatic agent component (the solid content may be 1.0% to 2.0% or 1.5% to 2.0%), where the antistatic agent is
  • the content of the aqueous solution containing may be about 0.1 to about 30% by weight, about 1 to about 25% by weight, or about 5 to about 20% by weight, based on the total weight of the entire composition, and is within the upper or lower limit values described above. It may be a content that exists in between. If the content of the antistatic agent exceeds the above maximum value and is used in excessive amounts, defects may occur in the appearance of the release layer, and these defects may appear as bluespots.
  • the antistatic agent may be included in the above amount to provide a surface resistance of about 10 4 to 10 10 ohm/sq to the release layer.
  • the release coating composition may further include a conductivity enhancer to achieve a desired level of surface resistance, that is, antistatic ability.
  • a conductivity enhancer to achieve a desired level of surface resistance, that is, antistatic ability.
  • the content of the conductivity enhancer is about 1 to 20% by weight, about 1 to 15% by weight, about 1 to 10% by weight, about 1 to 8% by weight, about 1.5 to 8% by weight, based on the total weight of the entire composition.
  • Weight percent may be about 1.5 to 6 weight%, about 2 to 6 weight%, about 2.5 to 6 weight%, about 3 to 6 weight%, or about 4 to 6 weight%. If the content of the conductivity improver is used in excess of the above maximum value, curing of the release layer may be hindered and the appearance and rub-off characteristics of the release layer may not be achieved at the desired level. If used excessively, the effect may be minimal.
  • the conductivity improver may be a known conductivity improver widely used in the conventional release film field and is not particularly limited.
  • conductivity enhancers include ethylene glycol, dimethyl sulfoxide, N-methyl-2-pyrrolidone, propylene glycol, butyl glycol, dipropylene glycol dimethyl ether, gamma-butyrolactone, sulfolane, dimethyl carbonate, and sorbitol. It may be selected from the group consisting of, but is not limited thereto.
  • the pH adjuster can adjust the pH of the entire composition to a desired level.
  • the release coating composition may contain an acidic antistatic agent, and if the composition becomes acidic, neutral or basic components such as surfactants or silicone emulsion components may not function properly, so pH adjustment is necessary in this case. If the pH of the entire release coating composition is not adjusted, the stability of the composition itself over time may rapidly deteriorate, and the transfer of the release layer may become poor depending on the time elapsed after the composition is manufactured. For example, when the release coating composition was prepared and immediately applied to the base film to form a release layer, the appearance was good, but when the release layer was formed about 4 hours after production, the appearance of the release layer became mottled. phenomenon may appear.
  • the pH adjuster may be a well-known pH adjuster widely known in the release film field, and is not particularly limited.
  • the pH adjuster may be one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia water, but is not limited thereto.
  • the pH adjuster may be a basic pH adjuster.
  • the content of the pH adjuster may be 0.05 to 0.3% by weight, 0.1 to 0.3% by weight, or 0.15 to 0.25% by weight, based on the total weight of the entire composition, and is between the upper or lower limit values described above. It may be the content. If the pH adjuster is used in excess of the above maximum value, it may interfere with curing of the release layer.
  • the surfactant may improve the wetting or spreadability of the release coating composition on the base film and improve compatibility between component (B) and the silicone emulsion component.
  • component (B) when water is used as the sole solvent in an aqueous release coating composition, two or more different types of surfactants can be used.
  • the surfactant is a known surfactant widely known in the release film field and may be a component that can lower surface tension, but is not particularly limited.
  • the surfactant may be a cationic surfactant, an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, a silicone-based surfactant, a modified silicone-based surfactant, a fluorine-based surfactant, or a combination thereof. It is not limited.
  • the cationic surfactant may be, for example, an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, or an alkylbenzyldimethylammonium salt, but is not limited thereto.
  • the anionic surfactant may be, for example, fatty acid salt, alkylbenzene sulfonate, alkyl sulfonate, alkyl ether sulfonate, alkyl polyoxyethylene sulfonate, or monoalkyl phosphate, but is limited thereto. It doesn't work.
  • amphoteric surfactant may be, for example, alkyldimethylamine oxide, or alkylcarboxybetaine, but is not limited thereto.
  • nonionic surfactants include, for example, fatty acid ethanolamide, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, sorbitol, sorbitan, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, It may be polyoxyethylene fatty acid ester, glycerin fatty acid ester, propylene glycol fatty acid ester, or polyoxyalkylene modified silicone, but is not limited thereto.
  • the silicone-based surfactant may be, for example, polyether-modified silicone, or polyglycerin-modified silicone, but is not limited thereto.
  • the structures of these modified silicones are classified into side chain modified type, both terminal modified type (ABA type), single end modified type (AB type), both terminal side chain modified type, straight chain block type (ABn type), branched type, etc.
  • modified silicon of any of these structures may be used.
  • the fluorine-based surfactant may be one or more selected from the group consisting of fluorine, a fluorine-containing silane-based compound, and a fluorine-containing organic compound, but is not limited thereto.
  • the content of the surfactant may be 0.05 to 0.2% by weight, 0.1 to 0.2% by weight, or 0.15 to 0.2% by weight, based on the total weight of the entire composition, and lies between the upper or lower limits described above. It may be the content that does.
  • the antifouling agent can control the surface energy of the release layer and provide antifouling properties. If the surface energy difference between the base film and the release layer is small, the wettability and peelability of the release layer with respect to the base film may be reduced, but the antifouling agent can have the effect of preventing this by lowering the surface energy of the release layer. In addition, since component (B) included in the release coating composition of the present disclosure has almost no slip properties (sliding properties), the antifouling agent can provide slip properties to the release layer.
  • the antifouling agent may be one or more selected from the group consisting of fluorine, a silane-based compound containing a fluorine group, and an organic compound containing a fluorine group, but is not limited thereto.
  • the antifouling agent may not include self-emulsifying silicone.
  • Self-emulsifying silicone does not dissolve well in water, so if it contains it, it is difficult to use as an aqueous solvent. Therefore, the release coating composition according to the present disclosure may not contain self-emulsifying silicone instead of containing a silicone emulsion component. there is.
  • the content of the antifouling agent may be 0.1 to 0.3% by weight, 0.15 to 0.25% by weight, or 0.2 to 0.25% by weight, based on the total weight of the entire composition, and lies between the upper and lower limits described above. It may be the content that does. If the antifouling agent is used in excess of the above minimum value, problems may occur in which stains remain when the release film is peeled, and green sheet slurry particles may remain in the release layer after the release film is peeled from the green sheet. there is.
  • a release coating composition was prepared by mixing the following ingredients. However, the content of the silicone emulsion component was prepared in different amounts based on 100 parts by weight of component (B) according to Table 1.
  • the release coating composition prepared in this way was applied to at least one side of a 50 ⁇ m thick polyethylene terephthalate base film (manufacturer: Toray Advanced Materials, product name: It was cured by heating and drying, and a release film with a release layer formed on the substrate was produced.
  • a release coating composition was prepared in the same manner as in the Example, except that the silicone emulsion component was excluded in Comparative Example 1, and in Comparative Examples 2 to 5, the same amount of silicone emulsion component was included as in Examples 1, 4, 6, and 7, respectively. And the melamine component was excluded.
  • a release film with a release layer was manufactured using the release coating composition of the comparative example in the same manner as in the above example.
  • barium titanate (BaTiO 3 ; manufactured by Sakai Chemical Industry Co., Ltd., product name: BT-03), 5 parts by mass of polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., product name: Esrec B ⁇ KBM-2), and dioctyl phthalate.
  • Kanto Chemical Co., Ltd., product name: dioctyl cica phthalate grade 1 69 parts by mass of toluene and 46 parts by mass of ethanol were added to 2 parts by mass, and mixed and dispersed using a ball mill to prepare a ceramic slurry.
  • the ceramic slurry was uniformly applied to the surface of the release layer of the release film produced and stored at room temperature for 48 hours using an applicator. Afterwards, it was dried in a dryer at 80°C for 1 minute. Finally, a ceramic green sheet with a thickness of 3 ⁇ m was obtained on the release film, and a release film to which the ceramic green sheet was attached was manufactured.
  • the release film with the ceramic green sheet attached was stored for 24 hours and 90 days under conditions of room temperature of 23°C and humidity of 50%. Then, an acrylic adhesive tape (product name: 31B tape, manufactured by Nitto Denko) was attached to the side of the ceramic green sheet opposite to the release film, and then cut to a width of 25 mm, which was used as a measurement sample.
  • an acrylic adhesive tape product name: 31B tape, manufactured by Nitto Denko
  • XRF X-ray fluorescence analyzer
  • Nitto31B tape a standard tape
  • the sample was treated with a concentration of 20 g/cm 2 at room temperature. It was compressed under load for 24 hours.
  • the tape attached to the release coating surface was collected without contamination, then adhered to a polyethylene terephthalate (PET) film surface with a flat and clean surface, and then pressed back and forth once with a 2kg tape roller, and then the peeling force was measured.
  • PET polyethylene terephthalate
  • Nitto31B tape which had never been used, was adhered to a PET film surface with a flat and clean surface, and was pressed back and forth once with a 2kg tape roller, and then the peeling force was measured.
  • the peeling force was measured as follows, and the residual adhesion rate was calculated from equation 1.
  • Measurement method 180° peeling angle, peeling speed 30mm/min.
  • Residual adhesion rate (%) [Peeling force of adhesive tape peeled after adhering to the surface of the release layer/Peeling force of the adhesive tape not in contact with the surface of the release layer] ⁇ 100
  • Distilled water and methylene iodide (diiodomethane) were dropped on the release coating surface of the release film prepared in the above examples and comparative examples using a contact angle meter (KRUSS product name: DSA-100) to measure the respective contact angles.
  • the surface energy was calculated by substituting the contact angle value into the Owens-Wendt model.
  • the degree of change in the surface of the release layer was observed with the naked eye after rubbing the release layer of the release film prepared in the above examples and comparative examples back and forth 10 times by applying force with the thumb.
  • the rub-off characteristics were evaluated as follows.
  • Example 1 Silicone emulsion ingredient weight ratio (based on solid content) Green sheet peeling force (1 day after manufacturing) Green sheet peeling force (90 days after manufacturing) Tape immediate peel strength (gf/in) Tape peel strength per day at room temperature silicone content (g/ m2 ) residual adhesion rate (%) surface energy (dyne/cm) Rub-off I NH_t /I NH_max Comparative Example 1 100:0 2.8 2.9 40.4 840.1 00.006 96 26.1 ⁇ 0.98 Example 1 100:10 2.7 2.8 31.7 629.2 0.008 96 25.9 ⁇ 0.85 Example 2 100:40 2.5 2.5 15.3 370.4 0.03 95 21.1 ⁇ 0.81 Example 3 100:60 2.5 2.5 14.9 197.4 0.06 95 20.3 ⁇ 0.79 Example 4 100:260 2.1 2.1 9.7 45.1 0.11 94 20.5 ⁇ 0.61
  • Example 5 100:440 1.7 1.8 8.1 21.3 0.12 95 19.4 ⁇ 0.52
  • Example 6 100:530 1.5 1.5
  • the release film obtained using the release coating composition according to one aspect of the present disclosure exhibits excellent residual adhesion rate and rub-off characteristics compared to the case of using the comparative example, and at the same time, it can be used at various tape room temperatures. A peel strength of 1 day was achieved. Therefore, it can have advantages that can be utilized in various industrial fields. In addition, it can be confirmed that low-temperature curing is possible through excellent residual adhesion rate and Rub-off characteristics.
  • Comparative Examples 2 to 5 which are release films containing a silicone-based release coating composition conventionally used in the relevant technical field, the residual adhesion rate and surface The energy was not good and the rub-off characteristics were very poor.
  • silicone emulsion alone had a low residual adhesion rate and poor rub-off properties, making curing at low temperatures difficult.
  • the insufficient curing power can be improved through the combination of the melamine component and the silicone emulsion component, while the release property can be increased by the silicone emulsion.
  • the silicone emulsion has a large molecular weight and the reaction site is located at each end of the molecule.
  • melamine While low-temperature curing is difficult with basically 2 to 3 reaction sites, melamine has a low monomer molecular weight and can have up to 6 reaction sites, making it highly reactive, providing excellent rub-off that was difficult to achieve with existing silicone-based release coating compositions. characteristics were achieved.
  • An example according to one aspect of the present disclosure showed a green sheet peeling force almost similar to that on the first day after manufacturing even when the peeling force was measured on a green sheet 90 days after manufacturing, showing very excellent stability over time.
  • the example according to one aspect of the present disclosure exhibits a residual adhesion rate of at least 94% or more.
  • the FT-IR spectrum was measured in the release layer prepared with the release coating composition of Example 1 and a silicone-based release coating composition including a conventional self-emulsifying silicone. Specifically, Bruker's VERTEX70 device was used, and the release coating compositions of Examples and Comparative Examples were applied to a glass plate, cured by heating and drying in a hot air dryer at 150°C for 30 seconds, and then 0.1 g of the coating layer was collected with a ceramic knife and measured using a measuring device. The spectrum was measured using the ATR method. The FT-IR spectrum measurement results are shown in Figure 3.
  • the release layer of the present disclosure has a high absorption peak intensity in that region due to the influence of the Si-O stretching absorption band of about 1020 cm -1 and about 1090 cm -1 and the Si-C stretching absorption band of about 800 cm -1 . You can see that it represents . Through this peak intensity, it can be interpreted that the release layer contains components derived from PDMS.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Paints Or Removers (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne un film antiadhésif. Le film antiadhésif selon un aspect de la présente invention peut mettre en œuvre une force de pelage d'une large plage et présente une excellente stabilité temporelle.
PCT/KR2023/008255 2022-07-06 2023-06-15 Film antiadhésif Ceased WO2024010242A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2023552492A JP7762214B2 (ja) 2022-07-06 2023-06-15 離型フィルム｛ｒｅｌｅａｓｅ ｆｉｌｍ｝
CN202380010694.4A CN117677682A (zh) 2022-07-06 2023-06-15 离型膜

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020220083053A KR102521827B1 (ko) 2022-07-06 2022-07-06 이형 필름
KR10-2022-0083053 2022-07-06

Publications (1)

Publication Number Publication Date
WO2024010242A1 true WO2024010242A1 (fr) 2024-01-11

Family

ID=86128304

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2023/008255 Ceased WO2024010242A1 (fr) 2022-07-06 2023-06-15 Film antiadhésif

Country Status (5)

Country Link
JP (1) JP7762214B2 (fr)
KR (1) KR102521827B1 (fr)
CN (1) CN117677682A (fr)
TW (1) TWI853606B (fr)
WO (1) WO2024010242A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102521827B1 (ko) * 2022-07-06 2023-04-17 도레이첨단소재 주식회사 이형 필름

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180020945A (ko) * 2015-06-23 2018-02-28 린텍 가부시키가이샤 세라믹 그린 시트 제조 공정용 박리 필름
KR20200015881A (ko) * 2018-08-03 2020-02-13 아라까와 가가꾸 고교 가부시끼가이샤 수계 대전방지 이형 코팅제 조성물 및 대전방지 이형 필름
KR20200137357A (ko) * 2019-05-30 2020-12-09 도레이첨단소재 주식회사 이형 필름
KR20210022163A (ko) * 2018-08-10 2021-03-02 도요보 가부시키가이샤 세라믹 그린시트 제조용 이형 필름
KR20210146894A (ko) * 2019-03-26 2021-12-06 린텍 가부시키가이샤 박리 시트
KR102521827B1 (ko) * 2022-07-06 2023-04-17 도레이첨단소재 주식회사 이형 필름

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000343664A (ja) * 1999-06-09 2000-12-12 Teijin Ltd 離形フィルム
KR20190076955A (ko) * 2016-10-25 2019-07-02 미쯔비시 케미컬 주식회사 이형 필름
JP6852720B2 (ja) * 2017-10-12 2021-03-31 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム
JP6977748B2 (ja) * 2018-08-10 2021-12-08 東洋紡株式会社 セラミックグリーンシート製造用離型フィルム

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180020945A (ko) * 2015-06-23 2018-02-28 린텍 가부시키가이샤 세라믹 그린 시트 제조 공정용 박리 필름
KR20200015881A (ko) * 2018-08-03 2020-02-13 아라까와 가가꾸 고교 가부시끼가이샤 수계 대전방지 이형 코팅제 조성물 및 대전방지 이형 필름
KR20210022163A (ko) * 2018-08-10 2021-03-02 도요보 가부시키가이샤 세라믹 그린시트 제조용 이형 필름
KR20210146894A (ko) * 2019-03-26 2021-12-06 린텍 가부시키가이샤 박리 시트
KR20200137357A (ko) * 2019-05-30 2020-12-09 도레이첨단소재 주식회사 이형 필름
KR102521827B1 (ko) * 2022-07-06 2023-04-17 도레이첨단소재 주식회사 이형 필름

Also Published As

Publication number Publication date
TWI853606B (zh) 2024-08-21
JP7762214B2 (ja) 2025-10-29
CN117677682A (zh) 2024-03-08
KR102521827B1 (ko) 2023-04-17
TW202408803A (zh) 2024-03-01
JP2024529593A (ja) 2024-08-08

Similar Documents

Publication Publication Date Title
KR102766810B1 (ko) 세라믹 그린 시트 제조 공정용 박리 필름
WO2020209450A1 (fr) Film de libération contenant un groupe fluoré
WO2017171489A1 (fr) Procédé de fabrication d'un film d'isolation
KR20180020946A (ko) 세라믹 그린 시트 제조 공정용 박리 필름
WO2015047014A1 (fr) Pellicule anti-adhésive et son procédé de fabrication
WO2018135865A1 (fr) Film de protection de partie inférieure de panneau delo, et appareil d'affichage électroluminescent organique le comprenant
WO2023038425A1 (fr) Composition de revêtement antiadhésif
WO2022131500A1 (fr) Composition de revêtement antiadhésif en silicone et film antiadhésif la comprenant
CN113557111B (zh) 陶瓷生片制造工序用剥离膜
WO2024010242A1 (fr) Film antiadhésif
WO2020080707A1 (fr) Ruban pour traitement de tranche
WO2022220349A1 (fr) Film antiadhésif en silicone antistatique double face
WO2019147099A1 (fr) Composition de solution de revêtement antistatique et film polyester antistatique utilisant ladite composition
WO2020189882A1 (fr) Film antistatique de libération de silicone
WO2019045336A1 (fr) Film adhésif de silicone de type sans substrat
WO2015102336A1 (fr) Film polyester et son procédé de fabrication
WO2024010241A1 (fr) Composition de revêtement antiadhésif
WO2017116201A1 (fr) Film anti-adhésif et son procédé de fabrication
WO2022215831A1 (fr) Composition de résine thermodurcissable, produit durci et préimprégné de celle-ci, et feuille stratifiée, feuille stratifiée de feuille métallique, et carte de circuit imprimé ayant ledit produit durci ou pré-imprégné durci
WO2022145643A1 (fr) Composition de revêtement adhésif à base de silicone et film adhésif la comprenant
WO2015102354A1 (fr) Film polyester et son procédé de fabrication
WO2019132451A1 (fr) Résine de polyester et film de polyester l'utilisant
WO2015099451A1 (fr) Feuille de résine isolante pour la formation d'une carte de circuit imprimé souple, son procédé de fabrication et carte de circuit imprimé la comprenant
WO2022186427A1 (fr) Film antiadhésif
WO2025110382A1 (fr) Film de polyester et composant le comprenant

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 12023552228

Country of ref document: PH

ENP Entry into the national phase

Ref document number: 2023552492

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 202380010694.4

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23835710

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 23835710

Country of ref document: EP

Kind code of ref document: A1