WO2020242276A1 - Release film - Google Patents
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- WO2020242276A1 WO2020242276A1 PCT/KR2020/007091 KR2020007091W WO2020242276A1 WO 2020242276 A1 WO2020242276 A1 WO 2020242276A1 KR 2020007091 W KR2020007091 W KR 2020007091W WO 2020242276 A1 WO2020242276 A1 WO 2020242276A1
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- release
- release film
- srz
- film
- melamine resin
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- 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
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
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- 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
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- 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
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- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/201—Adhesives in the form of films or foils characterised by their carriers characterised by the release coating composition on the carrier layer
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- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2461/32—Modified amine-aldehyde condensates
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- 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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
-
- 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
- C08J2483/00—Characterised by the use of 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; Derivatives of such polymers
- C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
- C08J2483/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Definitions
- the present invention relates to a release film, and more particularly, it is free from blocking and curling, is suitable for the MLCC manufacturing process due to its low surface roughness, and does not cause curls despite the high coating thickness, so when applied to the MLCC manufacturing process, ceramic sheet It relates to a release film that can contribute to reducing the production cost and defect rate of MLCC by preventing the lifting and lamination defects.
- a release film is a protective film for protecting an adhesive component from foreign substances or unwanted adherends in the atmosphere by attaching a pressure-sensitive adhesive film, and a release layer containing a polymer silicone as a main component is provided on one side of the base film.
- MLCC laminated ceramic capacitors
- MLCC laminated ceramic capacitors
- a release film is used as a carrier film for manufacturing a thin ceramic sheet. That is, after coating the ceramic slurry on the release film, the dried ceramic slurry is peeled off from the release film, thereby obtaining a thin ceramic sheet.
- the surface roughness indicating the surface roughness of the release film is the most important characteristic because projections or irregularities on the release film cause pin hole defects in the ceramic sheet. For this reason, the industry continues to make efforts to lower the surface roughness.
- the surface roughness of the polyester film used as the substrate is 20 to 50 nm, but the coating thickness of the release layer is as thin as 100 nm, so the surface roughness of the release film is usually determined by the surface roughness of the substrate. Therefore, in order to lower the surface roughness of the release film, it is common to prepare a polyester film having a lower surface roughness and use it as a substrate.
- a polyester film manufacturing process special particles are required to lower the surface roughness, and the yield and productivity of the film are also poor, so applying such a film as a substrate inevitably causes an increase in the production cost of the release film.
- the coating thickness of the release layer sufficiently thick compared to the surface roughness of the base material.
- the coating thickness exceeds (about 200 nm) of the polymer silicone, a so-called blocking phenomenon in which the release layer has adhesiveness occurs due to the low viscoelasticity of the polymer silicone, and the winding process (the process of winding the film in a roll form) becomes impossible.
- the present invention has been devised to solve the above problems and meet the requirements of the prior art, and an object of the present invention is to provide a release layer having an effect of lowering the surface roughness of the base material and release property, thereby providing a lower surface roughness than the conventional It is intended to provide a release film.
- Another object of the present invention is to provide a release film capable of preventing lamination and lifting of ceramic sheets when applied to MLCC because curl does not occur at room temperature and high temperature.
- the above object includes a base material, a release layer formed on one side of the base material, and the release layer is achieved by a release film formed of a release coating composition comprising melamine resin, polydimethylsiloxane and polyether copolymer resin, and polyethylene glycol.
- the release layer is characterized in that the weight ratio of melamine resin, polydimethylsiloxane and polyether copolymer resin, and polyethylene glycol is 1.0: 0.01 to 0.10: 0.1 to 1.0.
- the release coating composition further comprises an acid catalyst and an organic solvent, and further comprises 0.1 to 10 parts by weight of an acid catalyst based on 100 parts by weight of the melamine resin.
- the substrate has a ten point average roughness (SRz) of 500 nm or less.
- SRz ten point average roughness
- the thickness after drying of the release layer is 0.5 to 3.0 times the ten point average roughness (SRz) of the substrate.
- the melamine resin is characterized in that it comprises a melamine resin having two or more alkoxy or alkoxyalkyl groups.
- the melamine resin is characterized by having at least two or more functional groups of a methoxy group, a methoxymethyl group and a butoxymethyl group.
- the polyether is characterized in that it contains at least one of polyethylene glycol or polypropylene glycol.
- the polydimethylsiloxane and polyether copolymer resin is characterized in that hydroxy groups are bonded to both ends.
- the release film is characterized in that the residual adhesion rate is 90% or more.
- the release film is characterized in that the room temperature curl (Curl) generation amount is 0 to 1mm.
- the release film is characterized in that the high-temperature curl generation amount is 0 to 1 mm.
- the release film satisfies the following Equation 1,
- F_SRz is the ten point average roughness of the surface of the release layer
- B_SRz is the ten point average roughness of one surface of the substrate that does not contact the release layer.
- a release film having a lower surface roughness of the release layer compared to the substrate can be obtained by only one coating process, and there is an effect such as being free from blocking and curling compared to the prior art.
- the present invention has an effect of having a release layer having a high coating thickness, which is suitable for the MLCC manufacturing process, and can be used for manufacturing a ceramic sheet having a lower thickness, since the surface roughness is low compared to the prior art.
- the present invention has a special resin mixing ratio, so that curl does not occur despite a high coating thickness, so when applied to the MLCC manufacturing process, the ceramic sheet can be prevented from lifting and lamination failure, thereby contributing to the reduction of the production cost and defect rate of MLCC. Has the effect of.
- FIG. 1 is a schematic cross-sectional view of a release film according to an embodiment of the present invention.
- copolymer is used to refer to a polymer formed by copolymerization of two or more monomers. Such copolymers include binary copolymers, terpolymers or higher order copolymers.
- FIG. 1 is a schematic cross-sectional view of a release film according to a preferred embodiment of the present invention.
- a release film according to an embodiment of the present invention includes a base material and a release layer 20 formed on one side of the base material, and is released by heat drying and curing after coating a release coating composition on one side of the base material. Layers can be formed.
- the substrate 10 may be a polyester film as long as it is a commercial polyester film, and a biaxially stretched polyethylene terephthalate film having a thickness of 20 to 100 ⁇ m may be used.
- SRz which is a ten point average roughness measured by a contact type three-dimensional roughness meter
- SRz is 500 nm or less.
- the surface roughness of the release film is high, and when used in the MLCC process, pinhole defects in the ceramic sheet may be caused.
- a release layer having a higher coating thickness is required, so there is a problem in that economic efficiency is inferior.
- the release coating composition constituting the release layer 20 may include a melamine resin, a copolymer resin of polydimethylsiloxane and polyether, and polyethylene glycol.
- melamine resin is the main component of the release layer, and by giving the release layer a high modulus of elasticity, it suppresses the blocking phenomenon of the release film and makes the winding process smooth.
- the melamine resin includes a melamine resin having two or more alkoxy or alkoxyalkyl groups. If the number of alkoxy or alkoxyalkyl groups in the melamine resin is one or not, the resin is not cured and the release layer cannot be formed. More preferably, it is preferable to include at least two of a methoxy group, a methoxymethyl group and a butoxymethyl group. In the case of melamine having an alkoxyalkyl group having a longer chain than a butoxymethyl group, since a high amount of heat is required for curing the melamine resin, there is a problem that the substrate undergoes thermal deformation such as wrinkles during the curing process.
- the polydimethylsiloxane and polyether copolymer resin makes the release film have excellent releasability, and has a function of having excellent durability by tightly bonding with the melamine resin, which is the main component.
- the polydimethylsiloxane and polyether copolymer resin have hydroxyl groups at both ends for bonding with the melamine resin. It is preferable that the polyether unit in the copolymer skeleton contains at least one of polyethylene glycol and polypropylene glycol. If the chain length of the polyether resin constituting the copolymer is longer than that of polypropylene glycol, the compatibility with the melamine resin is lowered, and a high amount of heat is required for curing.Therefore, the substrate undergoes thermal deformation such as wrinkles during curing. have.
- polyethylene glycol is the greatest technical feature of the present invention. By adding it, the heat shrinkage of the release layer is significantly reduced, and a release film that does not cause curls even after a long heat treatment at high temperature can be prepared.
- polyethylene glycol Although there is no particular restriction on the polyethylene glycol, it is preferable to use a polyethylene glycol having a hydroxy group having a molecular weight of 400 or less, which is relatively low in viscosity, quick reaction, and economical.
- the content ratio (weight ratio) of a melamine resin, a copolymer resin of polydimethylsiloxane and polyether, and polyethylene glycol is preferably 1.0: 0.01 to 0.10: 0.1 to 1.0.
- the content of the polydimethylsiloxane and polyether copolymer resin is less than the above preferable range, there is a problem that the release of the release film is insufficient and the ceramic sheet is not peeled smoothly. If it exceeds the above preferable range, the release layer is formed while using the release film. There is a problem that some of the resins are transferred to the ceramic sheet.
- the release coating composition constituting the release layer may include an acid catalyst in addition to the above components.
- the acid catalyst is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the melamine resin. If the content of the acid catalyst is less than 0.1 parts by weight, it requires a high amount of heat to cure the release layer, so it may cause thermal deformation of the curing process substrate. If it exceeds 10 parts by weight, the pot life of the release coating composition is short and it is cured before coating. There is a problem that happens.
- the release coating composition constituting the release layer may include an organic solvent in addition to the above components.
- Any organic solvent that is compatible with melamine resin can be used.
- One or two or more of ethyl acetate, butyl acetate, propyl acetate, isopropyl acetate, hexane, heptane, octane, and isooctane may be used in combination.
- the release coating composition is configured by appropriately adjusting the total solid content and viscosity to be suitable for the coating process, and when using a gravure coating, it is preferable to have a solid content of 1 to 10% and a viscosity of 50 cps or less.
- the release coating composition there is no particular limitation on the method of coating the release coating composition, and bar coating, gravure coating, die coating, comma coating, etc. may be used.
- a hot air dryer for drying and curing, and a cured release film can be obtained by heating at a temperature of 140° C. for 30 seconds.
- the thickness of the release layer after drying and curing is completed is preferably 0.5 to 3.0 times the ten point average roughness (SRz) of the substrate.
- the release layer of such a thickness has a flat surface layer covering the protrusion of the substrate, so that the surface roughness of the release layer is lower than that of the conventional release film.
- the thickness of the release layer after drying is the coating thickness measured by observing the cross section with a scanning electron microscope after preparing the release film.
- the thickness of the release layer is less than the above preferable range, the effect of reducing the surface roughness through the release coating is insignificant, causing pinhole defects in the ceramic sheet when used. If the thickness of the release layer exceeds the above preferable range, blocking in the release film winding process Will occur.
- the relationship between the ten point average roughness (F_SRz) of the surface of the release layer and the ten point average roughness (B_SRz) of the surface opposite to the release coating layer of the base material satisfies the following equation.
- the residual adhesion rate of the release film is 90% or more, and if the residual adhesion rate of the release film is less than 90%, short circuit failure of the MLCC occurs as some components of the release coating layer are transferred to the ceramic sheet during the use of the release film. Can cause.
- the release film has a room temperature curl of 0 to 1 mm, and a high temperature curl of 0 to 1 mm.
- the amount of curling in the release film exceeds the above range, there is a problem that lamination of the ceramic sheet is defective or lifted in the process of forming and laminating the ceramic sheet on the release film.
- the release layer since the release layer has the function of alleviating the surface roughness of the substrate, it is possible to provide a release film having a lower surface roughness compared to the prior art. Also, the heat shrinkage of the release layer is small, so that curls are prevented even when heated at high temperatures A release film that does not occur can be provided.
- the release film according to the present invention may be suitable for use as a carrier film for forming a ceramic sheet during the manufacturing process of a multilayer ceramic capacitor (MLCC), and may contribute to improving process defects such as pinholes and meandering, and have a lower thickness. As ceramic sheet production becomes possible, it can greatly contribute to improving the physical properties of MLCC.
- MLCC multilayer ceramic capacitor
- a polyethylene terephthalate film (manufacturer: Toray Advanced Materials, product name: EXCEL) having a core point average roughness (SRz) of 130 nm, 400 nm, and 900 nm, respectively, was used as the base film, and as shown in Table 1, each Example and Comparative Example were divided into Applied. And the surface roughness of both sides of the base film is the same.
- a release coating composition was prepared by mixing the components (a) to (e) at a weight ratio, respectively, as in the Examples and Comparative Examples of Table 1 below.
- Examples 1 to 9 and Comparative Example 1 by coating the release coating composition prepared above with a Mayer bar (manufactured by Cheminstruments, #5 mesh) on one side of the base film and then curing by heating at 150°C for 30 seconds using a hot air dryer. After drying of ⁇ 7, a release film having a release layer thickness was prepared, respectively.
- a Mayer bar manufactured by Cheminstruments, #5 mesh
- SRz which is a ten point average roughness, was measured from the release films prepared in Examples and Comparative Examples using a contact type three-dimensional surface roughness meter (KOSAKA SE3300, cutoff 0.25).
- the surface of the release layer (F_SRz) and the opposite surface of the release layer (B_SRz) were measured and compared.
- Each release film prepared in Examples and Comparative Examples was stacked on each base film so that the release layer was in contact with the base film surface, and the presence or absence of blocking was evaluated after leaving for 24 hours under a load of 100 gf/cm 2.
- the superimposed release film was visually observed under a fluorescent lamp, and it was judged as'good' when no marks due to blocking were observed, and'defective' when blocking marks were observed.
- an adhesive tape manufactured by Nitto, product name: 31B
- Nitto, product name: 31B was attached to the surface of the ceramic sheet and the peeling force was measured when peeling it at a 180° angle and a 10 mpm speed.
- An AR-1000 device manufactured by cheminstrument was used to measure the peel force.
- the release films according to Examples and Comparative Examples were cut into a square having a side length of 10 cm, and then the release layer was placed on a flat glass plate with the release layer on top, and curls were measured. The height of the part raised the highest from the glass plate was measured with a ruler and marked.
- the release films according to Examples and Comparative Examples were heated at 150° C. for 30 minutes using a hot air dryer, and then curl was measured in the same manner as for room temperature curl.
- a standard adhesive tape (TESA7475) was rubbed and attached to the release films according to Examples and Comparative Examples by reciprocating once with a 2 kg roller. After peeling the attached tape, the peeling force was measured when peeling again after attaching to the base film not subjected to release coating.
- the peeling force was measured at 0.3mpm, 180° angle, and the peeling force at the time of peeling was measured, and the measuring instrument was an AR-1000 product of Cheminstrument.
- a standard adhesive tape (TESA7475) was rubbed and adhered to the base film not subjected to release coating by reciprocating once with a 2 kg roller. The peeling force when peeling this was measured.
- the residual adhesion rate was calculated by the formula of [Sample peel force]/[Standard peel force]*100%.
- Example 1 63 131 0.48 Good 0 0 96 Good 4.4
- Example 2 63 142 0.44 Good 0 0.2 94 Good 3.5
- Example 3 67 126 0.53 Good 0 0 93 Good 3.1
- Example 4 71 119 0.60 Good 0 0.2 95 Good 3.3
- Example 5 59 131 0.45 Good 0 0 95 Good 3.6
- Example 6 109 124 0.88 Good 0 0 93 Good 4.9
- Example 7 91 126 0.72 Good 0 0 93 Good 4.4
- Example 8 33 127 0.26 Good 0 0.2 93 Good 2.2
- Example 9 109 411 0.27 Good 0 0.4 93 Good 1.9 Comparative Example 1 65 127 0.51 Good 0 0.2 97 Good 14.1 Comparative Example 2 67 119 0.56 Good 0 0.2 84 Good 2.9
- the release films according to Examples 1 to 9 prepared from the release coating composition having a preferred configuration provided by the present invention showed good properties in various evaluation results. Due to the relatively high thickness of the release coating, the ten point average roughness (F_SRz) of the surface of the release layer was lowered compared to the ten point average roughness (B_SRz) of the surface of the substrate, and as a result, pinhole defects did not occur even when manufacturing the ceramic sheet. can confirm. In addition, despite the relatively high thickness of the release layer, it can be seen that the amount of curling at room temperature and high temperature has a preferable range of 1 mm or less.
- the content of (b) polydimethylsiloxane and polyether copolymer resin affects the residual adhesion rate and the peeling force of the ceramic sheet.
- the residual adhesion rate of the release film is usually 90% or more, and if it is less than 90%, it is known that short failure may occur after MLCC production.
- the peeling force when peeling the ceramic sheet is usually 5gf/in.If this is exceeded, the ceramic sheet is not partially peeled off during the peeling of the ceramic sheet during the MLCC manufacturing process, and tearing or wrinkles are mixed. I can. It can be seen that the release films according to Examples 1 to 9 prepared from the release coating composition having a preferred configuration provided by the present invention show values in a preferable range in both the residual adhesion rate and the ceramic sheet peeling force.
- polyethylene glycol has a function of lowering room temperature and high temperature curl, but unlike Examples 1 to 9 having a preferable content provided in the present invention, Comparative Example 3 lacks the content of polyethylene glycol. As a result, it can be confirmed that curls at room temperature and high temperature are severely generated.
- the content of the polyethylene glycol (a) is higher than the content of the melamine resin, so that the release layer is not sufficiently cured, and thus the residual adhesion rate is less than the preferred range.
- the ten point average roughness (F_SRz) of the release coating layer surface is 110 nm. It can be seen that the pinhole defect of the ceramic sheet does not occur as it is formed extremely low below.
- the release film of Comparative Example 5 exceed the range of Equation 1
- the thickness of the release coating layer was thinner than that of B_SRz, and as the F_SRz of the release layer showed a high value of 139 nm, it could be confirmed that pinhole defects in the ceramic sheet were caused .
- the release film of Comparative Example 6, which is less than the range of Equation 1 has a thicker release coating layer than B_SRz, and thus blocking occurs in the release film winding process.
- a release film having a lower surface roughness of the release layer compared to the substrate can be obtained with only one coating process. Differently, it is possible to obtain a release film free from blocking and curling.
- the release film according to the present invention is suitable for the MLCC manufacturing process, and may contribute to manufacturing a ceramic sheet having a lower thickness without pinhole or lamination defects.
- the release film according to the present invention can contribute not only to improving the defect rate in the process but also improving the physical properties of the finished product, the MLCC.
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Abstract
The present invention relates to a release film, which is free from blocking and curling, has a low surface roughness so as to be suitable for an MLCC manufacturing process, and does not curl even at a high coating thickness so as to prevent, when applied to the MLCC manufacturing process, floating of a ceramic sheet and defective stacking, and thus can contribute to a reduction in production costs and defective rate.
Description
본 발명은 이형 필름에 관한 것으로서, 보다 상세하게는 블로킹 및 컬 현상에서 자유롭고, 표면조도가 낮아 MLCC 제조 공정에 적합하고, 높은 코팅두께에도 불구하고 컬이 발생하지 않아 MLCC 제조 공정에 적용 시 세라믹시트의 들뜸 및 적층 불량을 방지하여 MLCC의 생산비용과 불량률 감소에 기여할 수 있는 이형 필름에 관한 것이다.The present invention relates to a release film, and more particularly, it is free from blocking and curling, is suitable for the MLCC manufacturing process due to its low surface roughness, and does not cause curls despite the high coating thickness, so when applied to the MLCC manufacturing process, ceramic sheet It relates to a release film that can contribute to reducing the production cost and defect rate of MLCC by preventing the lifting and lamination defects.
일반적으로, 이형 필름은 통상 점착제피막이 부착되어 점착성분을 대기 중의 이물 또는 원치 않는 피착제로부터 보호하기 위한 보호필름으로, 기재필름의 일면에 고분자 실리콘을 주성분으로 하는 이형층을 구비한다.In general, a release film is a protective film for protecting an adhesive component from foreign substances or unwanted adherends in the atmosphere by attaching a pressure-sensitive adhesive film, and a release layer containing a polymer silicone as a main component is provided on one side of the base film.
이형 필름의 또 다른 특수한 용도로는 적층세라믹커패시터(이하 MLCC) 제조 공정용이 있다. MLCC는 박막의 세라믹시트와 금속전극을 수 백층 적층함으로써 제조되는데, 이 때 박막의 세라믹시트를 제조하기 위한 캐리어필름으로써 이형 필름이 사용된다. 즉, 이형 필름 상에 세라믹 슬러리를 코팅한 후 건조된 세라믹슬러리를 이형 필름으로부터 박리해 냄으로써 박막의 세라믹시트를 얻는 것이다. 이러한 MLCC 공정에 적용되는 이형 필름의 경우 이형 필름 상의 돌기 또는 요철이 세라믹시트의 핀홀(Pin hole) 불량을 유발하므로 이형 필름의 표면 거칠기를 나타내는 표면조도가 가장 중요한 특성이다. 이 때문에 당 업계에는 표면조도를 낮추기 위한 노력들을 계속해 오고 있다.Another special use of the release film is for the manufacturing process of laminated ceramic capacitors (hereinafter referred to as MLCC). MLCC is manufactured by laminating several hundred layers of a thin ceramic sheet and a metal electrode. In this case, a release film is used as a carrier film for manufacturing a thin ceramic sheet. That is, after coating the ceramic slurry on the release film, the dried ceramic slurry is peeled off from the release film, thereby obtaining a thin ceramic sheet. In the case of a release film applied to such an MLCC process, the surface roughness indicating the surface roughness of the release film is the most important characteristic because projections or irregularities on the release film cause pin hole defects in the ceramic sheet. For this reason, the industry continues to make efforts to lower the surface roughness.
당 업계의 일반적인 이형 필름은 기재로 사용되는 폴리에스터 필름의 표면조도가 20 내지 50nm인데 비해 이형층의 코팅두께가 100nm 수준으로 얇으므로 이형 필름의 표면조도는 통상 기재의 표면조도에 의해 결정된다. 따라서 이형 필름의 표면조도를 낮추기 위해서는 보다 낮은 표면조도를 갖는 폴리에스터 필름을 제조하여 기재로 사용하는 방법이 보편적이다. 그러나 폴리에스터 필름제조공정 상 표면조도를 낮추는 데에는 특수한 입자를 요하고, 필름의 수율 및 생산성 또한 떨어지므로 이러한 필름을 기재로 적용하는 것은 필연적으로 이형 필름 제조비용 상승을 유발한다.In general release films in the art, the surface roughness of the polyester film used as the substrate is 20 to 50 nm, but the coating thickness of the release layer is as thin as 100 nm, so the surface roughness of the release film is usually determined by the surface roughness of the substrate. Therefore, in order to lower the surface roughness of the release film, it is common to prepare a polyester film having a lower surface roughness and use it as a substrate. However, in the polyester film manufacturing process, special particles are required to lower the surface roughness, and the yield and productivity of the film are also poor, so applying such a film as a substrate inevitably causes an increase in the production cost of the release film.
이에 이형 필름의 표면조도를 낮추기 위하여 기재의 표면조도에 비해 이형층의 코팅두께를 충분히 두껍게 코팅하는 방법을 당 업계 종사자라면 쉽게 생각해 볼 수 있으나 통상의 이형층은 고분자 실리콘을 주성분으로 하고 있어 일정 수준의 코팅두께(약 200nm)를 넘어서게 되면 고분자 실리콘의 낮은 점탄성으로 인해 이형층이 점착성을 띠는 이른바 블로킹 현상이 발생하여 권취 공정(필름을 롤 형태로 감는 공정)이 불가능하게 된다.Therefore, in order to lower the surface roughness of the release film, it is easy for those skilled in the art to consider a method of coating the coating thickness of the release layer sufficiently thick compared to the surface roughness of the base material. When the coating thickness exceeds (about 200 nm) of the polymer silicone, a so-called blocking phenomenon in which the release layer has adhesiveness occurs due to the low viscoelasticity of the polymer silicone, and the winding process (the process of winding the film in a roll form) becomes impossible.
이러한 블로킹 현상을 유발하지 않으면서도 보다 낮은 표면조도를 갖는 이형 필름을 얻기 위한 방법으로서 기재 상에 별도의 평활화층을 코팅하고 평활화층 위에 다시 이형층을 코팅하는 방법이 제안된 바 있다(대한민국 공개특허 제10-2016-0127036호). 이와 같은 다층 코팅에 있어 평활화층이 충분히 치밀한 조직을 갖는 경우 코팅층의 점성이 낮으므로 블로킹을 유발하지 않고도 표면조도를 낮출 수 있다는 장점이 있다. 그러나 이러한 방법은 별도의 코팅공정을 요하므로 공정비용이 상승하고 수율이 떨어지는 단점이 있다.As a method for obtaining a release film having a lower surface roughness without causing such a blocking phenomenon, a method of coating a separate smoothing layer on the substrate and coating the release layer again on the smoothing layer has been proposed (Korea Patent Publication No. 10-2016-0127036). In such a multilayer coating, when the smoothing layer has a sufficiently dense structure, the viscosity of the coating layer is low, so there is an advantage that the surface roughness can be lowered without causing blocking. However, since this method requires a separate coating process, there are disadvantages in that the process cost increases and the yield decreases.
또한 단층의 코팅 공정으로 상기 목적한 바를 이루기 위한 방법으로는 블로킹을 유발하지 않는 치밀한 구조를 갖는 멜라민 수지와 이형성 조절에 용이한 폴리오르가노실록산 수지를 혼합하여 이형층을 구성하는 방법이 제안된 바 있다(대한민국 공개특허 제10-2018-0020945호). 그러나 이러한 이형 필름은 멜라민 수지의 열수축으로 인하여 이형 필름이 코팅층 쪽으로 휘는 이른바 컬(curl)현상이 발생하고 특히 고온, 장시간 가열 시 컬 현상이 두드러지는 문제가 있고, 이형 필름에서 컬이 발생할 경우 이형 필름에 세라믹시트를 성형 및 적층하는 공정에서 세라믹시트의 적층 불량이나 들뜸 현상이 발생하는 문제가 있다.In addition, as a method for achieving the above objective by a single layer coating process, a method of forming a release layer by mixing a melamine resin having a dense structure that does not cause blocking and a polyorganosiloxane resin that is easy to control releasability has been proposed. Yes (Republic of Korea Patent Publication No. 10-2018-0020945). However, such a release film has a so-called curl phenomenon in which the release film bends toward the coating layer due to heat shrinkage of the melamine resin. Particularly, there is a problem that the curl phenomenon is remarkable when heated at high temperature and for a long time, and when curl occurs in the release film, the release film In the process of forming and laminating the ceramic sheet, there is a problem that lamination defects or lift-off of the ceramic sheet occur.
본 발명은 상기와 같은 문제점을 해결하고 종래의 요구사항에 부응하기 위해 안출된 것으로서, 본 발명의 목적은 이형성과 기재의 표면조도를 낮추는 효과를 함께 갖는 이형층을 구비함으로써 종래 대비 표면조도가 낮은 이형 필름을 제공하고자 하는 것이다.The present invention has been devised to solve the above problems and meet the requirements of the prior art, and an object of the present invention is to provide a release layer having an effect of lowering the surface roughness of the base material and release property, thereby providing a lower surface roughness than the conventional It is intended to provide a release film.
본 발명의 다른 목적은 상온 및 고온에서 컬이 발생하지 않아 MLCC에 적용 시 세라믹시트의 적층 불량 및 들뜸을 방지할 수 있는 이형 필름을 제공하고자 하는 것이다.Another object of the present invention is to provide a release film capable of preventing lamination and lifting of ceramic sheets when applied to MLCC because curl does not occur at room temperature and high temperature.
본 발명의 상기 및 다른 목적과 이점은 바람직한 실시예를 설명한 하기의 설명으로부터 보다 분명해 질 것이다.The above and other objects and advantages of the present invention will become more apparent from the following description of preferred embodiments.
상기 목적은, 기재, 기재의 일면에 형성된 이형층을 포함하며, 이형층은 멜라민 수지, 폴리디메틸실록산과 폴리에테르 공중합체 수지 및 폴리에틸렌글리콜을 포함하는 이형 코팅 조성물로 형성된 이형 필름에 의해 달성된다.The above object includes a base material, a release layer formed on one side of the base material, and the release layer is achieved by a release film formed of a release coating composition comprising melamine resin, polydimethylsiloxane and polyether copolymer resin, and polyethylene glycol.
여기서, 이형층은 멜라민 수지, 폴리디메틸실록산과 폴리에테르 공중합체 수지 및 폴리에틸렌글리콜의 중량비가 1.0 : 0.01~0.10 : 0.1~1.0인 것을 특징으로 한다.Here, the release layer is characterized in that the weight ratio of melamine resin, polydimethylsiloxane and polyether copolymer resin, and polyethylene glycol is 1.0: 0.01 to 0.10: 0.1 to 1.0.
바람직하게는, 이형 코팅 조성물은 산촉매와 유기 용제를 더 포함하되, 멜라민 수지 100중량부에 대하여 0.1 내지 10중량부의 산촉매를 더 포함하는 것을 특징으로 한다.Preferably, the release coating composition further comprises an acid catalyst and an organic solvent, and further comprises 0.1 to 10 parts by weight of an acid catalyst based on 100 parts by weight of the melamine resin.
바람직하게는, 기재의 십점평균조도(SRz)는 500nm 이하인 것을 특징으로 한다.Preferably, the substrate has a ten point average roughness (SRz) of 500 nm or less.
바람직하게는, 이형층의 건조 후 두께는 기재의 십점평균조도(SRz)의 0.5 내지 3.0배인 것을 특징으로 한다.Preferably, the thickness after drying of the release layer is 0.5 to 3.0 times the ten point average roughness (SRz) of the substrate.
바람직하게는, 멜라민 수지는 둘 이상의 알콕시 또는 알콕시알킬기를 갖는 멜라민 수지를 포함하는 것을 특징으로 한다.Preferably, the melamine resin is characterized in that it comprises a melamine resin having two or more alkoxy or alkoxyalkyl groups.
바람직하게는, 멜라민 수지는 메톡시기, 메톡시메틸기 및 부톡시메틸기 중 적어도 둘 이상의 작용기를 갖는 것을 특징으로 한다.Preferably, the melamine resin is characterized by having at least two or more functional groups of a methoxy group, a methoxymethyl group and a butoxymethyl group.
바람직하게는, 폴리에테르는 폴리에틸렌글리콜 또는 폴리프로필렌글리콜 중 적어도 하나를 포함하는 것을 특징으로 한다.Preferably, the polyether is characterized in that it contains at least one of polyethylene glycol or polypropylene glycol.
바람직하게는, 폴리디메틸실록산과 폴리에테르 공중합체 수지는 양 말단에 하이드록시기가 결합되어 있는 것을 특징으로 한다.Preferably, the polydimethylsiloxane and polyether copolymer resin is characterized in that hydroxy groups are bonded to both ends.
바람직하게는, 이형 필름의 잔류접착률은 90% 이상인 것을 특징으로 한다.Preferably, the release film is characterized in that the residual adhesion rate is 90% or more.
바람직하게는, 이형 필름은 상온 컬(Curl) 발생량이 0 내지 1mm 인 것을 특징으로 한다.Preferably, the release film is characterized in that the room temperature curl (Curl) generation amount is 0 to 1mm.
바람직하게는, 이형 필름은 고온 컬(curl) 발생량이 0 내지 1mm인 것을 특징으로 한다.Preferably, the release film is characterized in that the high-temperature curl generation amount is 0 to 1 mm.
바람직하게는, 이형 필름은 하기 수학식 1을 만족하되, Preferably, the release film satisfies the following Equation 1,
(수학식 1)(Equation 1)
0.25 < (F_SRz/B_SRz) < 0.900.25 <(F_SRz/B_SRz) <0.90
이고, 여기서 F_SRz는 이형층 표면의 십점평균조도이고, B_SRz는 이형층과 맞닿지 않는 기재의 일면의 십점평균조도인 것을 특징으로 한다.Where F_SRz is the ten point average roughness of the surface of the release layer, and B_SRz is the ten point average roughness of one surface of the substrate that does not contact the release layer.
본 발명에 따르면, 기재에 비해 낮은 이형층 표면조도를 갖는 이형필름을 한 차례의 코팅 공정만으로 얻을 수 있으며, 종래 대비 블로킹 및 컬 현상에서 자유로운 등의 효과가 있다. According to the present invention, a release film having a lower surface roughness of the release layer compared to the substrate can be obtained by only one coating process, and there is an effect such as being free from blocking and curling compared to the prior art.
나아가, 본 발명은 높은 코팅두께의 이형층을 가짐으로써 종래 대비 표면조도가 낮아 MLCC 제조 공정에 적합하고, 보다 낮은 두께의 세라믹시트 제조에 사용될 수 있는 등의 효과가 있다.Furthermore, the present invention has an effect of having a release layer having a high coating thickness, which is suitable for the MLCC manufacturing process, and can be used for manufacturing a ceramic sheet having a lower thickness, since the surface roughness is low compared to the prior art.
나아가, 본 발명은 특수한 수지 배합비를 가짐으로써 높은 코팅두께에도 불구하고 컬이 발생하지 않아 MLCC 제조 공정에 적용 시 세라믹시트의 들뜸 및 적층 불량을 방지하여 MLCC의 생산비용과 불량률 감소에 기여할 수 있는 등의 효과가 있다. Furthermore, the present invention has a special resin mixing ratio, so that curl does not occur despite a high coating thickness, so when applied to the MLCC manufacturing process, the ceramic sheet can be prevented from lifting and lamination failure, thereby contributing to the reduction of the production cost and defect rate of MLCC. Has the effect of.
다만, 본 발명의 효과들은 이상에서 언급한 효과로 제한되지 않으며, 언급되지 않은 또 다른 효과들은 아래의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.However, the effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.
도 1은 본 발명의 일 실시형태에 따른 이형 필름의 단면 모식도이다.1 is a schematic cross-sectional view of a release film according to an embodiment of the present invention.
이하, 본 발명의 실시예와 도면을 참조하여 본 발명을 상세히 설명한다. 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위해 예시적으로 제시한 것일 뿐, 본 발명의 범위가 이들 실시예에 의해 제한되지 않는다는 것은 당업계에서 통상의 지식을 가지는 자에 있어서 자명할 것이다.Hereinafter, the present invention will be described in detail with reference to embodiments of the present invention and drawings. These examples are only illustratively presented to illustrate the present invention in more detail, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited by these examples. .
달리 정의되지 않는 한, 본 명세서에서 사용되는 모든 기술적 및 과학적 용어는 본 발명이 속하는 기술 분야의 숙련자에 의해 통상적으로 이해되는 바와 동일한 의미를 갖는다. 상충되는 경우, 정의를 포함하는 본 명세서가 우선할 것이다. 또한 본 명세서에서 설명되는 것과 유사하거나 동등한 방법 및 재료가 본 발명의 실시 또는 시험에 사용될 수 있지만, 적합한 방법 및 재료가 본 명세서에 기재된다.Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. Also, although methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present invention, suitable methods and materials are described herein.
본 명세서에 사용된 바와 같이, "포함하다(comprise)", "포함하는(comprising)", "구비하다(include)", "구비하는(including) ", "함유하는(containing)", "~을 특징으로 하는(characterized by)", "갖는다(has)", "갖는(having)"이라는 용어들 또는 이들의 임의의 기타 변형은 배타적이지 않은 포함을 커버하고자 한다. 예를 들어, 요소들의 목록을 포함하는 공정, 방법, 용품, 또는 기구는 반드시 그러한 요소만으로 제한되지는 않고, 명확하게 열거되지 않거나 그러한 공정, 방법, 용품, 또는 기구에 내재적인 다른 요소를 포함할 수도 있다. 또한, 명백히 반대로 기술되지 않는다면, "또는"은 포괄적인 '또는'을 말하며 배타적인 '또는'을 말하는 것은 아니다.As used herein, "comprise", "comprising", "include", "including", "containing", "~ The terms characterized by", "has", "having" or any other variation thereof are intended to cover inclusions that are not exclusive. For example, a process, method, article, or apparatus comprising a list of elements is not necessarily limited to those elements, and is not explicitly listed or may include other elements inherent to such process, method, article, or apparatus. May be. Further, unless expressly stated to the contrary, "or" refers to an inclusive'or' and not an exclusive'or'.
본 발명을 설명하고/하거나 청구함에 있어서, 용어 "공중합체"는 둘 이상의 단량체의 공중합에 의해 형성된 중합체를 언급하기 위해 사용된다. 그러한 공중합체는 이원공중합체, 삼원공중합체 또는 더 고차의 공중합체를 포함한다.In describing and/or claiming the present invention, the term “copolymer” is used to refer to a polymer formed by copolymerization of two or more monomers. Such copolymers include binary copolymers, terpolymers or higher order copolymers.
먼저, 본 발명의 바람직한 실시형태에 따른 이형 필름의 단면 모식도인 도 1을 참고하여 본 발명의 일 양상에 따른 이형 필름에 대해서 상세하게 설명한다.First, a release film according to an aspect of the present invention will be described in detail with reference to FIG. 1, which is a schematic cross-sectional view of a release film according to a preferred embodiment of the present invention.
도 1을 참고하면, 본 발명의 일 실시형태에 따른 이형 필름은 기재와 기재의 일면에 형성된 이형층(20)을 포함하고, 기재의 일면에 이형 코팅 조성물을 코팅한 후 가열 건조 및 경화시킴으로써 이형층을 형성할 수 있다.Referring to FIG. 1, a release film according to an embodiment of the present invention includes a base material and a release layer 20 formed on one side of the base material, and is released by heat drying and curing after coating a release coating composition on one side of the base material. Layers can be formed.
일 실시예에서, 기재(10)는 폴리에스테르 필름으로서 상용의 폴리에스테르 필름이라면 어느 것을 사용해도 무관하며, 두께 20 내지 100㎛의 이축 연신된 폴리에틸렌테레프탈레이트 필름이 사용될 수 있다. In one embodiment, the substrate 10 may be a polyester film as long as it is a commercial polyester film, and a biaxially stretched polyethylene terephthalate film having a thickness of 20 to 100 μm may be used.
기재인 폴리에스테르 필름의 표면조도는 접촉식 3차원 조도 측정기에 의해 측정되는 십점평균조도인 SRz가 500nm 이하인 것이 바람직하다. SRz가 500nm를 초과하는 경우 본 발명에서 제안하는 이형층을 구비하더라도 이형 필름의 표면조도가 높아 MLCC 공정에 사용 시 세라믹시트의 핀홀 불량을 유발할 수 있다. 또한 표면조도를 낮추기 위해서는 보다 높은 코팅두께를 갖는 이형층을 필요로 하게 되므로 경제성이 떨어지는 문제점이 있다.As for the surface roughness of the polyester film as a substrate, it is preferable that SRz, which is a ten point average roughness measured by a contact type three-dimensional roughness meter, is 500 nm or less. When the SRz exceeds 500 nm, even if the release layer proposed in the present invention is provided, the surface roughness of the release film is high, and when used in the MLCC process, pinhole defects in the ceramic sheet may be caused. In addition, in order to lower the surface roughness, a release layer having a higher coating thickness is required, so there is a problem in that economic efficiency is inferior.
일 실시예에서 이형층(20)을 구성하는 이형 코팅 조성물은 멜라민 수지, 폴리디메틸실록산과 폴리에테르의 공중합체 수지 및 폴리에틸렌글리콜을 포함할 수 있다.In one embodiment, the release coating composition constituting the release layer 20 may include a melamine resin, a copolymer resin of polydimethylsiloxane and polyether, and polyethylene glycol.
이형 코팅 조성물 중 멜라민 수지는 이형층의 주성분이며 이형층에 높은 탄성계수를 갖게 함으로써 이형필름의 블로킹 현상을 억제하고 권취 공정이 원활하게 이루어질 수 있도록 한다. Among the release coating compositions, melamine resin is the main component of the release layer, and by giving the release layer a high modulus of elasticity, it suppresses the blocking phenomenon of the release film and makes the winding process smooth.
이러한 멜라민 수지는 둘 이상의 알콕시 또는 알콕시알킬기를 갖는 멜라민 수지를 포함하는 것이 바람직하다. 멜라민 수지에서 알콕시 또는 알콕시알킬기의 수가 하나 혹은 없는 경우 수지의 경화가 이루어지지 않아 이형층을 구성할 수 없다. 보다 바람직하게는 메톡시기, 메톡시메틸기 및 부톡시메틸기 중 둘 이상을 포함하는 것이 바람직하다. 부톡시메틸기보다 긴 사슬의 알콕시알킬기를 갖는 멜라민의 경우 멜라민 수지의 경화에 높은 열량을 필요로 하므로 경화 공정 중 기재가 주름 등의 열변형이 발생하는 문제가 있다. It is preferable that the melamine resin includes a melamine resin having two or more alkoxy or alkoxyalkyl groups. If the number of alkoxy or alkoxyalkyl groups in the melamine resin is one or not, the resin is not cured and the release layer cannot be formed. More preferably, it is preferable to include at least two of a methoxy group, a methoxymethyl group and a butoxymethyl group. In the case of melamine having an alkoxyalkyl group having a longer chain than a butoxymethyl group, since a high amount of heat is required for curing the melamine resin, there is a problem that the substrate undergoes thermal deformation such as wrinkles during the curing process.
이형 코팅 조성물 중 폴리디메틸실록산과 폴리에테르 공중합체 수지는 이형필름이 우수한 박리성을 갖도록 하며, 주성분인 멜라민 수지와 단단하게 결합하여 우수한 내구성을 갖는 기능을 한다.Among the release coating compositions, the polydimethylsiloxane and polyether copolymer resin makes the release film have excellent releasability, and has a function of having excellent durability by tightly bonding with the melamine resin, which is the main component.
이러한 폴리디메틸실록산과 폴리에테르 공중합체 수지는 멜라민 수지와 결합을 위해 양 말단에 하이드록시기를 갖는 것이 바람직하다. 공중합체 골격 중 폴리에테르 단위는 폴리에틸렌글리콜 또는 폴리프로필렌글리콜 중 적어도 하나를 포함하는 것이 바람직하다. 공중합체를 구성하는 폴리에테르 수지의 사슬 길이가 폴리프로필렌글리콜보다 길 경우 멜라민 수지와의 상용성이 떨어지는 동시에 경화에 높은 열량을 필요로 하므로 경화공정 중 기재가 주름 등의 열변형이 발생하는 문제가 있다.It is preferable that the polydimethylsiloxane and polyether copolymer resin have hydroxyl groups at both ends for bonding with the melamine resin. It is preferable that the polyether unit in the copolymer skeleton contains at least one of polyethylene glycol and polypropylene glycol. If the chain length of the polyether resin constituting the copolymer is longer than that of polypropylene glycol, the compatibility with the melamine resin is lowered, and a high amount of heat is required for curing.Therefore, the substrate undergoes thermal deformation such as wrinkles during curing. have.
이형코팅 조성물 중 폴리에틸렌글리콜은 본 발명의 가장 큰 기술적 특징으로, 이를 첨가함으로써 이형층의 열수축이 현저히 줄어들게 하고 고온에서 장시간의 열처리에도 컬이 발생하지 않는 이형필름을 제조할 수 있다.Among the release coating compositions, polyethylene glycol is the greatest technical feature of the present invention. By adding it, the heat shrinkage of the release layer is significantly reduced, and a release film that does not cause curls even after a long heat treatment at high temperature can be prepared.
이러한 폴리에틸렌글리콜에는 특별한 제약은 없으나 비교적 점도가 낮고 반응이 빠르며 경제성이 있는 분자량 400 내외의 하이드록시기를 갖는 폴리에틸렌글리콜을 사용하는 것이 바람직하다. Although there is no particular restriction on the polyethylene glycol, it is preferable to use a polyethylene glycol having a hydroxy group having a molecular weight of 400 or less, which is relatively low in viscosity, quick reaction, and economical.
일 실시예에서, 멜라민 수지, 폴리디메틸실록산과 폴리에테르의 공중합체 수지 및 폴리에틸렌글리콜의 함량비(중량비)는 1.0 : 0.01~0.10 : 0.1~1.0인 것이 바람직하다. In one embodiment, the content ratio (weight ratio) of a melamine resin, a copolymer resin of polydimethylsiloxane and polyether, and polyethylene glycol is preferably 1.0: 0.01 to 0.10: 0.1 to 1.0.
폴리디메틸실록산과 폴리에테르 공중합체 수지의 함량이 위 바람직한 범위 미만이면 이형 필름의 이형성이 부족하여 세라믹시트 박리가 원활하지 않은 문제가 있고, 위 바람직한 범위를 초과할 경우 이형 필름 사용 중 이형층을 구성하는 수지 중 일부가 세라믹시트로 전사되는 문제가 있다. If the content of the polydimethylsiloxane and polyether copolymer resin is less than the above preferable range, there is a problem that the release of the release film is insufficient and the ceramic sheet is not peeled smoothly. If it exceeds the above preferable range, the release layer is formed while using the release film. There is a problem that some of the resins are transferred to the ceramic sheet.
또한 폴리에틸렌글리콜의 함량이 위 바람직한 범위 미만인 경우 이형층의 열수축을 완화하는 작용이 부족하여 상온 및 고온에서 컬이 발생하는 문제가 있으며, 위 바람직한 범위를 초과할 경우 이형층의 경화도가 부족해지거나 탄성이 부족하여 이형 필름 권취 공정 중 블로킹이 발생하게 된다.In addition, when the content of polyethylene glycol is less than the above preferable range, there is a problem that curling occurs at room temperature and high temperature due to insufficient function to alleviate the heat shrinkage of the release layer.If the content exceeds the above preferable range, the hardening degree of the release layer is insufficient or elasticity is poor. As a result, blocking occurs during the release film winding process.
일 실시예에서 이형층을 구성하는 이형 코팅 조성물은 위 성분들 외에 산촉매를 포함할 수 있다.In one embodiment, the release coating composition constituting the release layer may include an acid catalyst in addition to the above components.
산촉매는 특별한 제약은 없으며 멜라민 수지와의 상용성이 좋고 경화를 촉진할 수 있는 파라톨루엔설폰산과 같은 상용의 제품을 사용할 수 있다. 산촉매는 멜라민 수지 100중량부에 대하여 0.1 내지 10중량부 함유하는 것이 바람직하다. 산촉매의 함량이 0.1중량부 미만일 경우 이형층 경화에 높은 열량을 필요로 하므로 경화공정 기재의 열변형을 유발할 수 있으며 10중량부를 초과할 경우 이형코팅 조성물의 포트 라이프(pot life)가 짧아 코팅 전에 경화가 일어나는 문제가 있다.There is no specific restriction on the acid catalyst, and a commercial product such as paratoluenesulfonic acid that has good compatibility with melamine resin and can accelerate curing can be used. The acid catalyst is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the melamine resin. If the content of the acid catalyst is less than 0.1 parts by weight, it requires a high amount of heat to cure the release layer, so it may cause thermal deformation of the curing process substrate. If it exceeds 10 parts by weight, the pot life of the release coating composition is short and it is cured before coating. There is a problem that happens.
일 실시예에서 이형층을 구성하는 이형 코팅 조성물은 위 성분들 외에 유기용제를 포함할 수 있다.In one embodiment, the release coating composition constituting the release layer may include an organic solvent in addition to the above components.
유기용제는 멜라민 수지와 상용성이 있는 것이라면 어느 것이든 무방하며 아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 사이클로헥사논,톨루엔, 자일렌, 메탄올, 에탄올, 부탄올, 이소프로필알콜, 이소부틸알콜, 에틸에세테이트, 부틸아세테이트, 프로필 아세테이트, 이소프로필아세테이트, 헥산, 헵탄, 옥탄, 이소옥탄 중에서 하나 또는 둘 이상을 혼합하여 사용할 수 있다.Any organic solvent that is compatible with melamine resin can be used. Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, methanol, ethanol, butanol, isopropyl alcohol, isobutyl alcohol, One or two or more of ethyl acetate, butyl acetate, propyl acetate, isopropyl acetate, hexane, heptane, octane, and isooctane may be used in combination.
일 실시예에서, 이형코팅 조성물은 코팅 공정에 적합하게끔 전체 고형분 및 점도를 적당히 조절하여 구성하며, 그라비아 코팅을 활용할 경우 1 ~ 10%의 고형분 및 50cps 이하의 점도를 갖는 것이 바람직하다.In one embodiment, the release coating composition is configured by appropriately adjusting the total solid content and viscosity to be suitable for the coating process, and when using a gravure coating, it is preferable to have a solid content of 1 to 10% and a viscosity of 50 cps or less.
또한 이형 코팅 조성물을 코팅하는 방법에는 특별한 제한이 있는 것은 아니며, 바 코팅, 그라비아 코팅, 다이코팅, 콤마코팅 등을 활용할 수 있다.In addition, there is no particular limitation on the method of coating the release coating composition, and bar coating, gravure coating, die coating, comma coating, etc. may be used.
이형코팅 조성물 코팅 후 건조 및 경화를 위해서는 열풍건조기를 적용하는 것이 바람직하며, 140℃의 온도로 30초간 가열함으로써 경화된 이형 필름을 얻을 수 있다.After coating the release coating composition, it is preferable to apply a hot air dryer for drying and curing, and a cured release film can be obtained by heating at a temperature of 140° C. for 30 seconds.
또한 건조 및 경화가 완료된 후의 이형층의 두께는 기재의 십점평균조도(SRz)의 0.5 내지 3.0배인 것이 바람직하다. 이와 같은 두께의 이형층은 기재의 돌출부를 덮어 평탄한 표층을 갖게 됨으로써 종래의 이형필름 대비 이형층의 표면조도가 낮게 형성된다. 건조 후 이형층의 두께는 이형 필름을 제조한 후 단면을 주사전자현미경으로 관찰하여 측정된 코팅 두께이다. In addition, the thickness of the release layer after drying and curing is completed is preferably 0.5 to 3.0 times the ten point average roughness (SRz) of the substrate. The release layer of such a thickness has a flat surface layer covering the protrusion of the substrate, so that the surface roughness of the release layer is lower than that of the conventional release film. The thickness of the release layer after drying is the coating thickness measured by observing the cross section with a scanning electron microscope after preparing the release film.
이형층의 두께가 위 바람직한 범위 미만인 경우 이형코팅을 통한 표면조도 감소 효과가 미미하여 사용 시 세라믹시트의 핀홀 불량을 유발하게 되며, 이형층의 두께가 위 바람직한 범위를 초과하는 경우 이형 필름 권취 공정에서 블로킹이 발생하게 된다.If the thickness of the release layer is less than the above preferable range, the effect of reducing the surface roughness through the release coating is insignificant, causing pinhole defects in the ceramic sheet when used.If the thickness of the release layer exceeds the above preferable range, blocking in the release film winding process Will occur.
또한 이형층 표면의 십점평균조도(F_SRz)는 기재의 이형코팅층 반대측 표면의 십점평균조도(B_SRz)와의 관계가 하기 수학식 1을 만족하는 것이 바람직하다. In addition, it is preferable that the relationship between the ten point average roughness (F_SRz) of the surface of the release layer and the ten point average roughness (B_SRz) of the surface opposite to the release coating layer of the base material satisfies the following equation.
(수학식 1)(Equation 1)
0.25 < (F_SRz/B_SRz) < 0.900.25 <(F_SRz/B_SRz) <0.90
일 실시예에서, 이형 필름의 잔류접찹률은 90% 이상인 것이 바람직하며, 이형 필름의 잔류접착률이 90% 미만이면 이형 필름 사용 중 이형코팅층의 일부 성분이 세라믹시트로 전사됨에 따라 MLCC의 쇼트 불량을 야기할 수 있다.In one embodiment, it is preferable that the residual adhesion rate of the release film is 90% or more, and if the residual adhesion rate of the release film is less than 90%, short circuit failure of the MLCC occurs as some components of the release coating layer are transferred to the ceramic sheet during the use of the release film. Can cause.
일 실시예에서, 이형 필름은 상온 컬(Curl) 발생량이 0 내지 1mm 이고, 고온 컬(curl) 발생량이 0 내지 1mm인 것이 바람직하다. 이형 필름에서 컬이 발생량이 위 범위보다 초과할 경우 이형 필름에 세라믹시트를 성형 및 적층하는 공정에서 세라믹시트의 적층 불량이나 들뜸 현상이 발생하는 문제가 있다.In one embodiment, it is preferable that the release film has a room temperature curl of 0 to 1 mm, and a high temperature curl of 0 to 1 mm. When the amount of curling in the release film exceeds the above range, there is a problem that lamination of the ceramic sheet is defective or lifted in the process of forming and laminating the ceramic sheet on the release film.
따라서 본 발명에 의하면 이형층이 기재의 표면 거칠기를 완화하는 기능을 가짐으로써 종래 대비 표면조도가 낮은 이형 필름을 제공할 수 있고, 또한 이형층의 열수축이 적어 고온으로 가열 시에도 컬(curl)이 발생하지 않는 이형 필름을 제공할 수 있다.Therefore, according to the present invention, since the release layer has the function of alleviating the surface roughness of the substrate, it is possible to provide a release film having a lower surface roughness compared to the prior art. Also, the heat shrinkage of the release layer is small, so that curls are prevented even when heated at high temperatures A release film that does not occur can be provided.
특히, 본 발명에 따른 이형 필름은 적층세라믹커패시터(MLCC) 제조공정 중 세라믹시트 성형을 위한 캐리어필름 용도에 적합할 수 있으며, 핀홀 및 사행 등의 공정 불량을 개선하는데 기여할 수 있으며, 보다 낮은 두께의 세라믹시트 생산이 가능케 함에 따라 MLCC의 물성 향상에 크게 기여할 수 있다.In particular, the release film according to the present invention may be suitable for use as a carrier film for forming a ceramic sheet during the manufacturing process of a multilayer ceramic capacitor (MLCC), and may contribute to improving process defects such as pinholes and meandering, and have a lower thickness. As ceramic sheet production becomes possible, it can greatly contribute to improving the physical properties of MLCC.
이하, 실시예와 비교예를 통하여 본 발명을 보다 상세히 설명하고자 한다. 본 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것이며, 본 발명의 범위가 이들 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples and comparative examples. These examples are for explaining the present invention in more detail, and the scope of the present invention is not limited by these examples.
[실시예 1~9 및 비교예 1~7][Examples 1 to 9 and Comparative Examples 1 to 7]
1. 기재필름1. Base film
기재필름으로서 심점평균조도(SRz)가 각각 130nm, 400nm, 900nm인 폴리에틸렌테레프탈레이트 필름(제조사: 도레이첨단소재, 제품명: EXCEL)을 사용하였으며, 표 1과 같이 각각의 실시예 및 비교예에 구분하여 적용하였다. 그리고 기재필름 양면의 표면조도는 동일하다.A polyethylene terephthalate film (manufacturer: Toray Advanced Materials, product name: EXCEL) having a core point average roughness (SRz) of 130 nm, 400 nm, and 900 nm, respectively, was used as the base film, and as shown in Table 1, each Example and Comparative Example were divided into Applied. And the surface roughness of both sides of the base film is the same.
2. 이형 코팅 조성물2. Release coating composition
(a) 멜라민 수지로서 메톡시기 및 메톡시메틸 작용기를 갖는 멜라민 수지 (제조사: Cytec, 제품명: Cymel-325)(a) Melamine resin having a methoxy group and a methoxymethyl functional group as a melamine resin (manufacturer: Cytec, product name: Cymel-325)
(b) 폴리디메틸실록산과 폴리에테르 공중합체 수지로서 양 말단에 하이드록시기를 갖고 폴리에틸렌글리콜 및 폴리프로필렌글리콜 반복단위를 갖는 공중합체 수지 (제조사: DOW, 제품명: OFX-3667)(b) Polydimethylsiloxane and polyether copolymer resin, which has hydroxyl groups at both ends and repeating units of polyethylene glycol and polypropylene glycol (manufacturer: DOW, product name: OFX-3667)
(c) 양 말단에 하이드록시기를 갖는 분자량 400의 폴리에틸렌글리콜 수지 (제조사: Sigma Aldrich, 제품명: PEG-400)(c) Polyethylene glycol resin having a molecular weight of 400 having hydroxyl groups at both ends (manufacturer: Sigma Aldrich, product name: PEG-400)
(d) 40중량%의 파라톨루엔설폰산과 잔량의 유기용제로 구성된 산촉매 (제조사: Allnex, 제품명: Cycat-4040)(d) an acid catalyst composed of 40% by weight of paratoluenesulfonic acid and the balance of organic solvent (manufacturer: Allnex, product name: Cycat-4040)
(e) 메틸에틸케톤과 사이클로헥사논을 1:1로 혼합한 유기용제(e) An organic solvent in which methyl ethyl ketone and cyclohexanone are mixed 1:1
위 (a) 내지 (e) 성분을 하기 표 1의 실시예 및 비교예와 같이 각각 중량비로 혼합함으로써 이형코팅 조성물을 제조하였다.A release coating composition was prepared by mixing the components (a) to (e) at a weight ratio, respectively, as in the Examples and Comparative Examples of Table 1 below.
3. 이형 코팅 및 경화3. Release coating and curing
위에서 제조된 이형 코팅 조성물을 기재필름의 일면에 메이어바(cheminstruments사제, #5 mesh)로 코팅한 후 열풍건조기를 이용하여 150℃의 조건에서 30초간 가열 경화시킴으로써 실시예 1~9 및 비교예 1~7의 건조 후 이형층 두께를 갖는 이형 필름을 각각 제조하였다. Examples 1 to 9 and Comparative Example 1 by coating the release coating composition prepared above with a Mayer bar (manufactured by Cheminstruments, #5 mesh) on one side of the base film and then curing by heating at 150°C for 30 seconds using a hot air dryer. After drying of ~7, a release film having a release layer thickness was prepared, respectively.
구분division | 기재필름Base film | 이형코팅 조성물(g)Release coating composition (g) | 이형층 두께(nm)Release layer thickness (nm) | ||||
SRz(nm)SRz(nm) | aa | bb | cc | dd | ee | ||
실시예 1Example 1 | 130130 | 6.06.0 | 0.10.1 | 3.03.0 | 0.60.6 | 100100 | 279279 |
실시예 2Example 2 | 130130 | 6.06.0 | 0.30.3 | 3.03.0 | 0.60.6 | 100100 | 282282 |
실시예 3Example 3 | 130130 | 6.06.0 | 0.50.5 | 3.03.0 | 0.60.6 | 100100 | 282282 |
실시예 4Example 4 | 130130 | 6.06.0 | 0.30.3 | 1.01.0 | 0.60.6 | 100100 | 278278 |
실시예 5Example 5 | 130130 | 6.06.0 | 0.30.3 | 5.05.0 | 0.60.6 | 100100 | 281281 |
실시예 6Example 6 | 130130 | 1.81.8 | 0.090.09 | 0.90.9 | 0.180.18 | 100100 | 8080 |
실시예 7Example 7 | 130130 | 3.03.0 | 0.150.15 | 1.51.5 | 0.30.3 | 100100 | 142142 |
실시예 8Example 8 | 130130 | 7.87.8 | 0.390.39 | 3.93.9 | 0.780.78 | 100100 | 358358 |
실시예 9Example 9 | 400400 | 7.87.8 | 0.390.39 | 3.93.9 | 0.780.78 | 100100 | 358358 |
비교예 1Comparative Example 1 | 130130 | 6.06.0 | 0.050.05 | 3.03.0 | 0.60.6 | 100100 | 271271 |
비교예 2Comparative Example 2 | 130130 | 6.06.0 | 0.70.7 | 3.03.0 | 0.60.6 | 100100 | 275275 |
비교예 3Comparative Example 3 | 130130 | 6.06.0 | 0.30.3 | 0.50.5 | 0.60.6 | 100100 | 271271 |
비교예 4Comparative Example 4 | 130130 | 6.06.0 | 0.30.3 | 7.07.0 | 0.60.6 | 100100 | 280280 |
비교예 5Comparative Example 5 | 130130 | 1.21.2 | 0.060.06 | 0.60.6 | 0.120.12 | 100100 | 5555 |
비교예 6Comparative Example 6 | 130130 | 9.09.0 | 0.450.45 | 4.54.5 | 0.90.9 | 100100 | 481481 |
비교예 7Comparative Example 7 | 900900 | 12.012.0 | 0.60.6 | 6.06.0 | 1.21.2 | 100100 | 555555 |
a: 멜라민 수지, b: 폴리디메틸실록산과 폴리에테르 공중합체 수지, c: 폴리에틸렌글리콜, d: 40중량%의 파라톨루엔설폰산과 잔량의 유기용제로 구성된 산촉매, e: 유기용제 (메틸에틸케톤 및 사이클로헥사논 1 : 1 혼합액)a: melamine resin, b: polydimethylsiloxane and polyether copolymer resin, c: polyethylene glycol, d: acid catalyst composed of 40% by weight of paratoluenesulfonic acid and remaining amount of organic solvent, e: organic solvent (methylethylketone and cyclo Hexanone 1:1 mixture) |
상기 실시예 1 내지 9 및 비교예 1 내지 7에 따른 이형 필름을 사용하여 다음과 같은 실험예를 통해 물성을 측정하고 그 결과를 다음 표 2에 나타내었다.Physical properties were measured through the following experimental examples using the release films according to Examples 1 to 9 and Comparative Examples 1 to 7, and the results are shown in Table 2 below.
[[
실험예Experimental example
]]
1. 표면조도 측정1. Surface roughness measurement
실시예 및 비교예에서 제조된 이형 필름으로부터 접촉식 3차원 표면조도 측정기(KOSAKA 사 SE3300 제품, 컷오프 0.25)를 사용하여 십점평균조도인 SRz를 측정하였다. 이형층 표면(F_SRz) 및 이형층 반대면(B_SRz)을 각각 측정하여 비교하였다.SRz, which is a ten point average roughness, was measured from the release films prepared in Examples and Comparative Examples using a contact type three-dimensional surface roughness meter (KOSAKA SE3300, cutoff 0.25). The surface of the release layer (F_SRz) and the opposite surface of the release layer (B_SRz) were measured and compared.
2. 블로킹성 평가2. Blocking evaluation
실시예 및 비교예에서 제조된 각각의 이형 필름을 각각의 기재필름에 이형층이 기재필름면과 접하도록 겹쳐놓은 후 100gf/㎠의 하중 하에서 24시간 방치한 후의 블로킹 현상의 유무를 평가하였다. 겹쳐진 이형 필름을 형광등 하에서 육안으로 관찰하여 블로킹으로 인한 자국이 관찰되지 않는 경우는 '양호', 블로킹 자국이 관찰되는 경우는 '불량'으로 판정하였다.Each release film prepared in Examples and Comparative Examples was stacked on each base film so that the release layer was in contact with the base film surface, and the presence or absence of blocking was evaluated after leaving for 24 hours under a load of 100 gf/cm 2. The superimposed release film was visually observed under a fluorescent lamp, and it was judged as'good' when no marks due to blocking were observed, and'defective' when blocking marks were observed.
3. 세라믹시트의 핀홀 불량 평가 및 박리력 측정3. Evaluation of pinhole defect of ceramic sheet and measurement of peel force
평균입경 0.2㎛의 티탄산바륨 입자 100g, 폴리비닐부티랄 10g, 톨루엔 8g 및 부탄올 2g을 혼합한 후 상온에서 12시간 교반한 다음 500rpm에서 24시간 볼밀처리하여 세라믹 슬러리를 제조하다. 이를 실시예 및 비교예에 따른 이형 필름의 이형층에 어플리케이터를 이용하여 일정 두께로 코팅한 후 80℃ 온도에서 5분간 열풍 건조함으로써 평균 두께 1㎛의 이형 필름을 제조하였다. 이후 간섭계 현미경으로 1 mm2의 면적을 10회 관측하였으며, 1㎛를 초과하는 핀홀의 수가 단위면적(mm2)당 평균 1 개 이상이면 '불량'으로 판정하고 그 이외에는 '양호'로 판정하였다.After mixing 100 g of barium titanate particles having an average particle diameter of 0.2 μm, 10 g of polyvinyl butyral, 8 g of toluene, and 2 g of butanol, stirring at room temperature for 12 hours and then ball milling at 500 rpm for 24 hours to prepare a ceramic slurry. This was coated on the release layer of the release film according to Examples and Comparative Examples to a predetermined thickness using an applicator and then hot air dried at 80° C. for 5 minutes to prepare a release film having an average thickness of 1 μm. Thereafter, an area of 1 mm 2 was observed 10 times with an interferometric microscope, and if the number of pinholes exceeding 1 μm on average was more than 1 per unit area (mm 2 ), it was judged as'poor' and other than that, it was judged as'good'.
또한 점착테이프(제조사: Nitto, 제품명: 31B)를 세라믹시트 면에 붙이고 이를 180°각도, 10mpm 속도로 박리시킬 때의 박리력을 측정하였다. 박리력 측정에는 cheminstrument사의 AR-1000기기를 사용하였다. In addition, an adhesive tape (manufacturer: Nitto, product name: 31B) was attached to the surface of the ceramic sheet and the peeling force was measured when peeling it at a 180° angle and a 10 mpm speed. An AR-1000 device manufactured by cheminstrument was used to measure the peel force.
4. 컬 (상온) 측정4. Curl (room temperature) measurement
실시예 및 비교예에 따른 이형 필름을 한 변의 길이가 10센티미티인 정사각형으로 재단한 후, 편평한 유리판 위에 이형층이 위로 오도록 놓고 컬을 측정하였다. 유리판으로부터 가장 높이 올라온 부분의 높이를 자로 측정한 후 표기하였다.The release films according to Examples and Comparative Examples were cut into a square having a side length of 10 cm, and then the release layer was placed on a flat glass plate with the release layer on top, and curls were measured. The height of the part raised the highest from the glass plate was measured with a ruler and marked.
5. 컬 (고온) 측정5. Curl (high temperature) measurement
실시예 및 비교예에 따른 이형 필름을 열풍건조기를 이용하여 150℃ 온도에서 30분간 가열한 후 상온 컬과 동일한 방법으로 컬을 측정하였다.The release films according to Examples and Comparative Examples were heated at 150° C. for 30 minutes using a hot air dryer, and then curl was measured in the same manner as for room temperature curl.
6. 잔류접착률 측정6. Measurement of residual adhesion rate
(1) 샘플 박리력 측정 (1) Sample peel force measurement
실시예 및 비교예에 따른 이형 필름에 표준점착테이프 (TESA7475)를 2kg 롤러로 1회 왕복하여 문질러 부착하였다. 부착되었던 테이프를 박리한 후 이형코팅을 실시하지 않은 기재필름에 부착한 후 다시 박리할 때의 박리력을 측정하였다. A standard adhesive tape (TESA7475) was rubbed and attached to the release films according to Examples and Comparative Examples by reciprocating once with a 2 kg roller. After peeling the attached tape, the peeling force was measured when peeling again after attaching to the base film not subjected to release coating.
이때, 박리력은 0.3mpm, 180°각도로 박리 시의 박리력을 측정하였으며, 측정기는 Cheminstrument사의 AR-1000 제품을 사용하였다.At this time, the peeling force was measured at 0.3mpm, 180° angle, and the peeling force at the time of peeling was measured, and the measuring instrument was an AR-1000 product of Cheminstrument.
(2) 기준 박리력 측정(2) Measurement of standard peel force
이형코팅을 실시하지 않은 기재필름에 표준점착테이프 (TESA7475)를 2kg 롤러로 1회 왕복하여 문질러 부착하였다. 이를 박리할 때의 박리력을 측정하였다.A standard adhesive tape (TESA7475) was rubbed and adhered to the base film not subjected to release coating by reciprocating once with a 2 kg roller. The peeling force when peeling this was measured.
(3) 잔류접착률 측정(3) Measurement of residual adhesion rate
[샘플 박리력]/[기준 박리력]*100% 의 수식으로 잔류접착률을 계산하였다.The residual adhesion rate was calculated by the formula of [Sample peel force]/[Standard peel force]*100%.
F_SRz(nm)F_SRz(nm) | B_SRz(nm)B_SRz(nm) | F_SRz/B_SRzF_SRz/B_SRz | 블로킹blocking | 컬(mm)Curl(mm) | 잔류접착률(%)Residual adhesion rate (%) | 세라믹시트Ceramic sheet | |||
상온Room temperature | 고온High temperature | 핀홀Pinhole | 박리력(gf/in)Peel force (gf/in) | ||||||
실시예 1Example 1 | 6363 | 131131 | 0.480.48 | 양호Good | 00 | 00 | 9696 | 양호Good | 4.44.4 |
실시예 2Example 2 | 6363 | 142142 | 0.440.44 | 양호Good | 00 | 0.20.2 | 9494 | 양호Good | 3.53.5 |
실시예 3Example 3 | 6767 | 126126 | 0.530.53 | 양호Good | 00 | 00 | 9393 | 양호Good | 3.13.1 |
실시예 4Example 4 | 7171 | 119119 | 0.600.60 | 양호Good | 00 | 0.20.2 | 9595 | 양호Good | 3.33.3 |
실시예 5Example 5 | 5959 | 131131 | 0.450.45 | 양호Good | 00 | 00 | 9595 | 양호Good | 3.63.6 |
실시예 6Example 6 | 109109 | 124124 | 0.880.88 | 양호Good | 00 | 00 | 9393 | 양호Good | 4.94.9 |
실시예 7Example 7 | 9191 | 126126 | 0.720.72 | 양호Good | 00 | 00 | 9393 | 양호Good | 4.44.4 |
실시예 8Example 8 | 3333 | 127127 | 0.260.26 | 양호Good | 00 | 0.20.2 | 9393 | 양호Good | 2.22.2 |
실시예 9Example 9 | 109109 | 411411 | 0.270.27 | 양호Good | 00 | 0.40.4 | 9393 | 양호Good | 1.91.9 |
비교예 1Comparative Example 1 | 6565 | 127127 | 0.510.51 | 양호Good | 00 | 0.20.2 | 9797 | 양호Good | 14.114.1 |
비교예 2Comparative Example 2 | 6767 | 119119 | 0.560.56 | 양호Good | 00 | 0.20.2 | 8484 | 양호Good | 2.92.9 |
비교예 3Comparative Example 3 | 6363 | 126126 | 0.500.50 | 양호Good | 2.22.2 | 77 | 9494 | 양호Good | 3.43.4 |
비교예 4Comparative Example 4 | 5959 | 137137 | 0.430.43 | 양호Good | 00 | 0.20.2 | 8383 | 양호Good | 4.24.2 |
비교예 5Comparative Example 5 | 139139 | 141141 | 0.990.99 | 양호Good | 00 | 0.20.2 | 9797 | 불량Bad | 6.16.1 |
비교예 6Comparative Example 6 | 2121 | 119119 | 0.180.18 | 불량Bad | 00 | 0.40.4 | 9393 | 양호Good | 2.82.8 |
비교예 7Comparative Example 7 | 651651 | 931931 | 0.700.70 | 양호Good | 0.20.2 | 0.60.6 | 9292 | 불량Bad | 2.42.4 |
표 2에서 알 수 있듯이, 본 발명에서 제공하는 바람직한 구성을 갖는 이형 코팅 조성물로부터 제조된 실시예 1~9에 따른 이형 필름은 다양한 평가 결과에서 모두 양호한 특성을 보였다. 비교적 높은 두께의 이형 코팅으로 인하여 이형층 표면의 십점평균조도(F_SRz)가 기재 표면의 십점평균조도(B_SRz)에 비해 낮아지는 결과를 보였으며, 이로 인해 세라믹시트 제조 시에도 핀홀 불량이 발생하지 않음을 확인할 수 있다. 또한 비교적 높은 이형층 두께에도 불구하고 상온 및 고온 컬 발생량이 1mm 이하로 바람직한 범위를 가짐을 확인할 수 있다.As can be seen from Table 2, the release films according to Examples 1 to 9 prepared from the release coating composition having a preferred configuration provided by the present invention showed good properties in various evaluation results. Due to the relatively high thickness of the release coating, the ten point average roughness (F_SRz) of the surface of the release layer was lowered compared to the ten point average roughness (B_SRz) of the surface of the substrate, and as a result, pinhole defects did not occur even when manufacturing the ceramic sheet. can confirm. In addition, despite the relatively high thickness of the release layer, it can be seen that the amount of curling at room temperature and high temperature has a preferable range of 1 mm or less.
또한 이형 코팅 조성물의 구성에 있어서 (b) 폴리디메틸실록산과 폴리에테르 공중합체 수지의 함량은 잔류접착률과 세라믹시트의 박리력에 영향을 미친다. MLCC 업계에 있어 이형 필름의 잔류접착률은 통상 90% 이상인 것이 바람직하며 90% 미만인 경우 MLCC 제조 후 쇼트(short)불량을 야기할 수 있는 것으로 알려져 있다. 또한 세라믹시트 박리 시의 박리력은 통상 5gf/in인 것이 바람직하며 이를 초과할 경우 MLCC 제조 공정 중 세라믹시트를 박리하는 과정에서 세라믹시트가 일부 박리되지 않고 찢어지거나 주름이 혼입되는 적측불량이 야기될 수 있다. 본 발명에서 제공하는 바람직한 구성을 갖는 이형 코팅 조성물로부터 제조된 실시예 1~9에 따른 이형 필름은 잔류접착률 및 세라믹시트 박리력에서 모두 바람직한 범위의 값을 보임을 확인할 수 있다. In addition, in the constitution of the release coating composition, the content of (b) polydimethylsiloxane and polyether copolymer resin affects the residual adhesion rate and the peeling force of the ceramic sheet. In the MLCC industry, it is preferable that the residual adhesion rate of the release film is usually 90% or more, and if it is less than 90%, it is known that short failure may occur after MLCC production. In addition, it is preferable that the peeling force when peeling the ceramic sheet is usually 5gf/in.If this is exceeded, the ceramic sheet is not partially peeled off during the peeling of the ceramic sheet during the MLCC manufacturing process, and tearing or wrinkles are mixed. I can. It can be seen that the release films according to Examples 1 to 9 prepared from the release coating composition having a preferred configuration provided by the present invention show values in a preferable range in both the residual adhesion rate and the ceramic sheet peeling force.
반면, 폴리디메틸실록산과 폴리에테르 공중합체 수지의 함량이 본 발명에서 제공하는 바람직한 범위 미만인 비교예 1의 경우 세라믹시트 박리력이 14.1gf/in로 매우 높게 형성되었으며, 바람직한 범위를 초과하는 비교예 2의 경우 잔류접착률이 84%로 바람직한 범위에 미달하였다.On the other hand, in the case of Comparative Example 1 in which the content of the polydimethylsiloxane and the polyether copolymer resin was less than the preferred range provided by the present invention, the peeling force of the ceramic sheet was formed very high as 14.1 gf/in, and Comparative Example 2 exceeding the preferred range. In the case of, the residual adhesion rate was 84%, which was less than the preferred range.
또한 이형코팅 조성물의 구성에 있어서 (c) 폴리에틸렌글리콜은 상온 및 고온 컬을 낮추는 작용을 하는데 본 발명에서 제공하는 바람직한 함량을 갖는 실시예 1~9와는 달리 비교예 3의 경우 폴리에틸렌글리콜의 함량이 부족하여 상온 및 고온 컬이 심하게 발생함을 확인할 수 있다. 또한 비교예 4의 경우 폴리에틸렌글리콜의 함량이 (a) 멜라민수지의 함량에 비해 높아 이형층의 경화가 충분히 일어나지 않음에 따라 잔류접착률이 바람직한 범위에 미달하는 결과를 보인다.In addition, in the composition of the release coating composition, (c) polyethylene glycol has a function of lowering room temperature and high temperature curl, but unlike Examples 1 to 9 having a preferable content provided in the present invention, Comparative Example 3 lacks the content of polyethylene glycol. As a result, it can be confirmed that curls at room temperature and high temperature are severely generated. In addition, in the case of Comparative Example 4, the content of the polyethylene glycol (a) is higher than the content of the melamine resin, so that the release layer is not sufficiently cured, and thus the residual adhesion rate is less than the preferred range.
또한 기재필름의 십점평균표면조도(B_SRz)와 이형 코팅층의 두께에 있어서는 그 상관관계가 본 발명에서 제공하는 바람직한 범위 내에 있는 실시예 1~9의 경우 이형 코팅층 표면의 십점평균조도(F_SRz)가 110nm 이하로 극히 낮게 형성됨에 따라 세라믹시트의 핀홀 불량이 발생하지 않음을 확인할 수 있다.In addition, in the case of Examples 1 to 9 in which the correlation between the base film's ten point average surface roughness (B_SRz) and the release coating layer thickness is within the preferred range provided by the present invention, the ten point average roughness (F_SRz) of the release coating layer surface is 110 nm. It can be seen that the pinhole defect of the ceramic sheet does not occur as it is formed extremely low below.
반면 수학식 1의 범위를 초과하는 비교예 5의 이형 필름은 B_SRz에 비해 이형 코팅층의 두께가 얇아 이형층의 F_SRz가 139nm로 높은 값을 보임에 따라 세라믹시트의 핀홀 불량을 야기함을 확인할 수 있다. 또한 수학식 1의 범위 미만인 비교예 6의 이형 필름은 B_SRz에 비해 이형 코팅층의 두께가 두꺼워 이형 필름 권취 공정에서 블로킹이 발생함을 알 수 있다. On the other hand, in the release film of Comparative Example 5 exceeding the range of Equation 1, the thickness of the release coating layer was thinner than that of B_SRz, and as the F_SRz of the release layer showed a high value of 139 nm, it could be confirmed that pinhole defects in the ceramic sheet were caused . In addition, it can be seen that the release film of Comparative Example 6, which is less than the range of Equation 1, has a thicker release coating layer than B_SRz, and thus blocking occurs in the release film winding process.
또한 비교예 7의 이형 필름의 경우 B_SRz와 이형 코팅층 두께와의 관계는 본 발명에서 제안하는 바람직한 범위 내에 있으나, 기재의 B_SRz 자체가 본 발명의 바람직한 범위인 500nm를 초과함에 따라 이형코팅 후에도 651nm의 높은 F_SRz를 보여 세라믹시트의 핀홀 불량을 유발함을 알 수 있다.In addition, in the case of the release film of Comparative Example 7, the relationship between B_SRz and the release coating layer thickness is within the preferred range suggested by the present invention, but as the B_SRz of the substrate itself exceeds 500nm, which is the preferred range of the present invention, a high of 651nm even after release coating. It can be seen that F_SRz is shown to cause a pinhole defect in the ceramic sheet.
상술한 바와 같이, 본 발명에서 제공하는 특수한 구성의 이형 코팅 조성물로부터 이형필름을 제조하는 경우 기재에 비해 낮은 이형층 표면조도를 갖는 이형필름을 한 차례의 코팅 공정만으로 얻을 수 있으며, 종래의 기술과는 다르게 블로킹 및 컬 현상에서 자유로운 이형 필름을 얻을 수 있다. As described above, in the case of manufacturing a release film from a release coating composition having a special configuration provided by the present invention, a release film having a lower surface roughness of the release layer compared to the substrate can be obtained with only one coating process. Differently, it is possible to obtain a release film free from blocking and curling.
특히, 본 발명에 따른 이형 필름은 MLCC제조 공정에 적합하며, 보다 낮은 두께의 세라믹시트를 핀홀 불량이나 적층 불량 없이 제조하는데 기여할 수 있다. 또한 MLCC에 있어 세라믹시트의 두께는 제품의 용량 및 크기와 직결되므로 본 발명에 따른 이형 필름은 공정상의 불량률 개선뿐만 아니라 완제품인 MLCC의 물성을 향상시키는데도 기여할 수 있다. In particular, the release film according to the present invention is suitable for the MLCC manufacturing process, and may contribute to manufacturing a ceramic sheet having a lower thickness without pinhole or lamination defects. In addition, in MLCC, since the thickness of the ceramic sheet is directly related to the capacity and size of the product, the release film according to the present invention can contribute not only to improving the defect rate in the process but also improving the physical properties of the finished product, the MLCC.
본 명세서에서는 본 발명자들이 수행한 다양한 실시예 가운데 몇 개의 예만을 들어 설명하는 것이나 본 발명의 기술적 사상은 이에 한정하거나 제한되지 않고, 당업자에 의해 변형되어 다양하게 실시될 수 있음은 물론이다.In the present specification, only a few examples of various embodiments performed by the present inventors are described, but the technical idea of the present invention is not limited or limited thereto, and it is obvious that it may be modified and variously implemented by those skilled in the art.
Claims (13)
- 기재; materials;상기 기재의 일면에 형성된 이형층;을 포함하며,Includes; a release layer formed on one side of the substrate,상기 이형층은 멜라민 수지, 폴리디메틸실록산과 폴리에테르 공중합체 수지 및 폴리에틸렌글리콜을 포함하는 이형 코팅 조성물로 형성된, 이형 필름.The release layer is formed of a release coating composition comprising a melamine resin, polydimethylsiloxane and polyether copolymer resin, and polyethylene glycol, a release film.
- 제1항에 있어서,The method of claim 1,상기 이형층은 멜라민 수지, 폴리디메틸실록산과 폴리에테르 공중합체 수지 및 폴리에틸렌글리콜의 중량비가 1.0 : 0.01~0.10 : 0.1~1.0인, 이형 필름. The release layer has a weight ratio of melamine resin, polydimethylsiloxane and polyether copolymer resin, and polyethylene glycol is 1.0: 0.01 to 0.10: 0.1 to 1.0, a release film.
- 제1항에 있어서,The method of claim 1,상기 이형 코팅 조성물은 산촉매와 유기 용제를 더 포함하되,The release coating composition further comprises an acid catalyst and an organic solvent,상기 멜라민 수지 100중량부에 대하여 0.1 내지 10중량부의 산촉매를 더 포함하는, 이형 필름.A release film further comprising 0.1 to 10 parts by weight of an acid catalyst based on 100 parts by weight of the melamine resin.
- 제1항에 있어서,The method of claim 1,상기 기재의 십점평균조도(SRz)는 500nm 이하인, 이형 필름.Ten point average roughness (SRz) of the substrate is 500 nm or less, a release film.
- 제1항에 있어서,The method of claim 1,상기 이형층의 건조 후 두께는 상기 기재의 십점평균조도(SRz)의 0.5 내지 3.0배인, 이형 필름.The thickness after drying of the release layer is 0.5 to 3.0 times the ten point average roughness (SRz) of the substrate, a release film.
- 제1항에 있어서,The method of claim 1,상기 멜라민 수지는 둘 이상의 알콕시 또는 알콕시알킬기를 갖는 멜라민 수지를 포함하는, 이형 필름.The melamine resin includes a melamine resin having two or more alkoxy or alkoxyalkyl groups, a release film.
- 제1항에 있어서,The method of claim 1,상기 멜라민 수지는 메톡시기, 메톡시메틸기 및 부톡시메틸기 중 적어도 둘 이상의 작용기를 갖는, 이형 필름.The melamine resin has a functional group of at least two or more of a methoxy group, a methoxymethyl group and a butoxymethyl group, a release film.
- 제1항에 있어서,The method of claim 1,상기 폴리에테르는 폴리에틸렌글리콜 또는 폴리프로필렌글리콜 중 적어도 하나를 포함하는, 이형 필름. The polyether is a release film containing at least one of polyethylene glycol or polypropylene glycol.
- 제1항에 있어서,The method of claim 1,상기 폴리디메틸실록산과 폴리에테르 공중합체 수지는 양 말단에 하이드록시기가 결합되어 있는, 이형 필름. The polydimethylsiloxane and polyether copolymer resin is a release film in which hydroxyl groups are bonded to both ends.
- 제1항에 있어서,The method of claim 1,상기 이형 필름의 잔류접착률은 90% 이상인, 이형 필름.The release film has a residual adhesion rate of 90% or more.
- 제1항에 있어서,The method of claim 1,상기 이형 필름은 상온 컬(Curl) 발생량이 0 내지 1mm 인, 이형 필름. The release film is a room temperature curl (Curl) generation amount of 0 to 1mm, a release film.
- 제1항에 있어서,The method of claim 1,상기 이형 필름은 고온 컬(curl) 발생량이 0 내지 1mm인, 이형 필름.The release film is a high temperature curl (curl) generation amount of 0 to 1mm, a release film.
- 제1항 내지 제12항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 12,상기 이형 필름은 하기 수학식 1을 만족하되, The release film satisfies the following Equation 1,(수학식 1)(Equation 1)0.25 < (F_SRz/B_SRz) < 0.900.25 <(F_SRz/B_SRz) <0.90이고, 여기서 F_SRz는 이형층 표면의 십점평균조도이고, B_SRz는 이형층과 맞닿지 않는 기재의 일면의 십점평균조도인, 이형 필름.Where F_SRz is the ten point average roughness of the surface of the release layer, and B_SRz is the ten point average roughness of one surface of the base material not in contact with the release layer.
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CN115383868B (en) * | 2022-08-24 | 2024-05-10 | 上海泽丰半导体科技有限公司 | LTCC green ceramic tape and manufacturing method thereof |
KR102709726B1 (en) * | 2022-12-06 | 2024-09-25 | 도레이첨단소재 주식회사 | Release film |
CN115716927B (en) * | 2022-12-31 | 2023-12-01 | 浙江洁美电子科技股份有限公司 | Release film for tape casting of patch type laminated inductor and manufacturing method thereof |
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- 2020-06-01 CN CN202080039903.4A patent/CN113924343B/en active Active
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JP2008503639A (en) * | 2005-01-19 | 2008-02-07 | エルジー・ケム・リミテッド | Filter for plasma display panel having excellent removability and plasma display panel including the same |
KR20090005437A (en) * | 2007-07-09 | 2009-01-14 | 도레이새한 주식회사 | Polyester release film and manufacturing method thereof |
KR20120099546A (en) * | 2011-01-28 | 2012-09-11 | 도레이첨단소재 주식회사 | Polyester release film for forming green sheet |
KR20160001308A (en) * | 2014-06-27 | 2016-01-06 | 코오롱인더스트리 주식회사 | Multi layer film having high migration and transparency |
KR20170046089A (en) * | 2015-10-20 | 2017-04-28 | 아라까와 가가꾸 고교 가부시끼가이샤 | Thermosetting release coating agent, release film and release pet film |
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KR102223435B1 (en) | 2021-03-04 |
CN113924343B (en) | 2023-06-09 |
JP7283810B2 (en) | 2023-05-30 |
JP2022534729A (en) | 2022-08-03 |
CN113924343A (en) | 2022-01-11 |
KR20200137357A (en) | 2020-12-09 |
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