KR102457454B1 - Release coating composition - Google Patents

Abstract

The present disclosure relates to a release coating composition. When the release coating composition according to one aspect of the present disclosure is manufactured as a release film, a wide range of peel strength can be realized and superior stability over time compared to a conventional silicone-based release film can be exhibited. The present invention includes a melamine component, a polymer component, and an acid catalyst.

Description

Release coating composition {RELEASE COATING COMPOSITION}

The present disclosure relates to water-based release coating compositions.

The release film is usually used as a protective film for protecting the pressure-sensitive adhesive component from foreign substances or unwanted adherends in the atmosphere by having a pressure-sensitive adhesive film attached thereto, and generally takes a structure in which a release layer is formed on a polyester base film.

In particular, the release film is used as a carrier film for thinly and uniformly coating the ceramic slurry in the green sheet constituting the MLCC (Multi-Layer Ceramic Capacitor, MLCC). MLCC is a type of capacitor used for accumulating electricity or stabilizing current. It is widely used in portable electronic devices due to its small size and large capacitance. are doing These MLCCs are completed by alternately stacking tens or hundreds of layers of green sheets and internal metal electrodes and then connecting external electrodes, and the size varies from less than 1 mm to several nm.

The green sheet used in MLCC is formed by uniformly coating a ceramic slurry on a carrier film, which is a support, and then firing it. A stretched polyester film is used as a base material, and a release film having a silicone polymer release layer coated on one surface thereof is used.

According to the recent trend of miniaturization and high capacity of MLCCs, it is required to make the thickness of the green sheet thinner and to laminate the ceramic slurry in more layers. The problem of being detached from the film may occur. Conversely, if the peeling force of the release film is too high, cracks, fractures, etc. may occur in the green sheet when the release film is removed from the ceramic green sheet. Therefore, the release film used for MLCC is particularly required to have properties that can be peeled off by a suitable peeling force.

In addition, if the organic solvent used in the preparation of the ceramic slurry does not sufficiently volatilize and remains in the release layer, stains such as orange peel occur on the surface of the green sheet. It occurred when it remained in the release layer, so improvement was required. Since preventing the green sheet defects as described above in advance is connected to the improvement of the reliability of the MLCC, it can be said that the function of the release film is very important in the manufacture of the MLCC.

The present disclosure provides techniques for release coating compositions. Specifically, the release coating composition may be used in the manufacture of a release film.

An object of the present disclosure is to provide a release coating composition that can implement a peel force in a variety of ranges.

In one aspect, the present disclosure may provide a release coating composition.

In one aspect, the release coating composition may be a water-based release coating composition.

In one aspect, the release coating composition comprises a melamine component, which is a melamine compound of Formula 1, an oligomer thereof, a polymer thereof, or a combination thereof; a polymer component containing a polar functional group and having a weight average molecular weight of 3,000 to 30,000; and an acid catalyst.

[Formula 1]

(Wherein, X represents a hydrogen atom, -CH ₂ OH, or -CH ₂ -OR, and may be the same or different, respectively. R represents an alkyl group having 1 to 8 carbon atoms, and may be the same or different from each other. at least one X is -CH ₂ -O-CH ₃ )

In one aspect, the total acid value in the melamine component may be 390 to 780 mgKOH / g.

In one aspect, the polymer component is at least one selected from the group consisting of polyester, polyurethane, polyvinyl resin, polyethylene terephthalate, polyethylene terephthalate, acrylate, methacrylate, combinations thereof, and copolymers thereof. can

In one aspect, the polymer component is a polyethylene terephthalate copolymer,

The polyethylene terephthalate copolymer is terephthalic acid; ethylene glycol; and at least one of isophthalic acid, diethylene glycol, mono propylene glycol, and cyclohexylene dimethanol; may be a copolymer comprising.

In one aspect, the polar functional group may be one or more selected from the group consisting of a hydroxyl group, a carboxy group, an amino group, an amine group, a carbonyl group, an acryl group, an acryloyl group, a nitrile group, a vinyl group, a halogen group, a urethane group, and an ester group.

In one aspect, the polymer component may contain two or more different polar functional groups.

In one aspect, the acid catalyst is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid oxalic acid, acetic acid, formic acid, methanesulfonic acid, trifluoromethanesulfonic acid, isoprenesulfonic acid, camphorsulfonic acid, hexanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, decanesulfonic acid, hexadecanesulfonic acid , dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, paratoluenesulfonic 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, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxypolyethylene glycol acid phosphate, bisphenol A acid phosphate , dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di2-ethylhexyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, It may be at least one selected from the group consisting of diphenyl acid phosphate, bisnonylphenyl acid phosphate sulfonium salt, benzothiazolium salt, ammonium salt, and phosphonium salt.

In one aspect, the weight ratio of the melamine component and the acid catalyst in the release coating composition may be 100:5 to 100:30, 100:10 to 100:20, or 100:10 to 100:15.

In one aspect, the release coating composition may comprise 0.2 to 1.0% by weight of the melamine component based on the total weight of the total composition or 0.01 to 5% by weight of the polymer component based on the total weight of the total composition.

In one aspect, the weight ratio of the melamine component and the polymer component in the release coating composition may be 100:3 to 100:70 based on the solid content.

In one aspect, 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.

In one aspect, the antistatic agent may be at least one selected from the group consisting of PEDOT, PEDOT:PSS, polyaniline, polypyrrole, quaternary ammonium salts, sulfonates, and phosphates.

In one aspect, the pH adjusting agent may be at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide and aqueous ammonia.

In one aspect, the surfactant may be a cationic surfactant, an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, a silicone surfactant, a modified silicone surfactant, a fluorine surfactant, or a combination thereof.

In one aspect, the antifouling agent may be at least one selected from the group consisting of fluorine, fluorine-containing silane-based compounds, fluorine-containing organic compounds, and self-emulsifying silicones.

In one aspect, the antifouling agent is a self-emulsifying silicone, and the self-emulsifying silicone may be a silicone monomer including a hydroxyl group.

In one aspect, the release coating composition comprises 0.1 to 30% by weight of an antistatic agent, 0.01 to 0.3% by weight of a pH adjusting agent, 0.05 to 0.2% by weight of a surfactant, or 0.1 to 0.3% by weight, based on the total weight of the total composition may contain antifouling agents.

In one aspect, the release coating composition may further include an oxazoline-based curing agent.

In one aspect, the release coating composition includes water or a combination of water and an organic solvent, and the combination ratio of water and organic solvent is 50:50 or more, 60:40 or more, 70:30 or more, and the weight ratio of water:organic solvent is 50:50 or more. , 80:20 or more, 90:10 or more, 95:5 or more, or 99:1 or more.

In one aspect, the melamine component and the polymer component containing a polar functional group may form a crosslinked network structure with each other after curing.

In one aspect, the weight average molecular weight of the polymer component is 5,000 to 30,000, 8,000 to 30,000, 10,000 to 30,000, 10,500 to 30,000, 10,500 to 20,000, 11,000 to 15,000, 11,000 to 14,000, 11,000 to 13,000, or 11,000 to 12,000 days can

In one aspect, the release coating composition may be used for manufacturing a release film for a ceramic green sheet manufacturing process.

The release coating composition according to an aspect of the present disclosure can implement a wide range of peel force and exhibit excellent stability over time when manufactured as a release film, and this effect is more excellent when compared to a silicone-based release coating composition.

FIG. 1A is a diagram illustrating a method of testing the ship-ri of a release film, and FIG. 1B is a photograph illustrating the results of testing a ship-ri of the release film.
2 is a graph showing the FT-IR spectrum measurement result of the release film.

Various aspects or embodiments described in this document are exemplified for the purpose of clearly explaining the technical spirit of the present disclosure, and are not intended to be limited thereto. The technical spirit of the present disclosure includes various modifications, equivalents, and alternatives of each aspect or embodiment described in this document, and aspects or embodiments selectively combined from all or part of each aspect or embodiment includes In addition, the scope of the rights of the technical idea of the present disclosure is not limited to the various aspects or embodiments presented below or specific descriptions thereof.

Terms used in this document, including technical or scientific terms, may have the meanings commonly understood by those of ordinary skill in the art to which this disclosure belongs, unless otherwise defined.

1. Base film

In one aspect of the present disclosure, the base film constituting the release film may use a known film widely used in the conventional release film field, but is not limited thereto.

In one aspect, 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. Specifically, the polyester-based polymer is a polyethylene terephthalate polymer, a polybutylene terephthalate polymer, a polyethylene naphthalate polymer, a polyphenylene sulfide polymer, a polyether ether ketone polymer, a polyphthalamide polymer, a polyimide polymer, a polysulfone polymer, It may be a polyethersulfone polymer, a polyetherimide polymer, or a combination thereof, but is not limited thereto.

In one aspect, the polyester-based polymer may be a polyester obtained from a condensation reaction of an aromatic dicarboxylic acid and an aliphatic glycol. In one aspect, the aromatic dicarboxylic acid is isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid (eg, P-oxybenzoic acid, etc.), or It may be a combination thereof, but is not limited thereto. In one aspect, 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.

In one aspect, as the polyester-based 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 And in consideration of mechanical strength and economic feasibility, it may be preferable to use polyethylene terephthalate. In one aspect, it may be preferable to use a biaxially stretched polyethylene terephthalate film as the base film.

In one aspect, the base film may have a thickness of 10 to 200㎛, but is not limited thereto.

In one aspect, the release coating composition may be applied to at least one surface of the base film to form a release layer.

2. Melamine component

The release coating composition according to an aspect of the present disclosure uses a melamine component as a main chain component constituting a release layer after curing, and when a melamine component is used, a hard release layer coating film can be obtained due to a high crosslinking density, and a silicone-based release coating Levels of cure beyond the composition can be achieved. This is because, in the release film for the ceramic green sheet manufacturing process for manufacturing MLCC, it is effective to harden the release layer coating in order to control the peeling force to a desired level.

In one aspect, the melamine component is not particularly limited, but is generally prepared by the reaction of melamine and formaldehyde, and the methylolated melamine thus produced is reacted with an alcohol having an appropriate carbon number under acid catalytic conditions to an alkyl etherified melamine compound can be obtained.

In one aspect, the melamine component may refer to a melamine compound having the structure of Formula 1 below, an oligomer thereof, a polymer thereof, and/or a combination thereof.

[Formula 1]

Here, X represents a hydrogen atom, —CH ₂ OH, or —CH ₂ —OR, and may be the same or different from each other. R represents an alkyl group having 1 to 8 carbon atoms, and may be the same or different from each other. Also, at least one X may be -CH ₂ -O-CH ₃ .

In one aspect, all of X may be —CH ₂ —O—CH ₃ , and the melamine compound may be a full ether methylated melamine, melamine oligomer and/or melamine polymer.

In one aspect, a variety of commercially available and widely used products can be used as a melamine component, for example, Cymel 300, Cymel 301, Cymel 303LF, Cymel 350, or Cymel 370N (or above, allnes). products) can be used, but are not limited now. Commercially available products may be used alone or in combination of two or more.

In one aspect, the content of the melamine component may be about 0.2 to about 1.0 wt%, based on the total weight of the total composition, specifically about 0.2 to about 0.8 wt%, about 0.3 to about 0.7 wt%, about 0.4 to about 0.4 wt% about 0.6% by weight, or about 0.5 to about 0.6% by weight. When the melamine component is used excessively less than the 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 the curing of the melamine component is not performed properly, the stability over time of the release film may decrease. Therefore, the content of the melamine component preferably satisfies the content ratio with the acid catalyst to be mentioned below.

In one aspect, the total acid value in the melamine component 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 higher, 650 KOH/g or higher, 700 KOH/g or higher, or 750 KOH/g or higher, or 730 KOH/g or lower, 680 KOH/g or lower, 630 KOH/g or lower, 580 KOH/g or lower, 530 KOH/g or lower g or less, 480 KOH/g or less, or 430 KOH/g or less, but is not limited thereto.

3. Polymer component

In one aspect of the present disclosure, the polymer component may be used as a binder or peel force modifier in the release coating composition. Since the melamine component has a low molecular weight of the monomer, it forms a dense crosslinked structure after curing and has a high crosslinking density. A polymer having a long chain structure is bound to the polymer, so that hardness is released and the softness of the release layer can be increased. As the softness increases, the peeling force of the release film also increases, and the present disclosure exhibits an effect of achieving a wide range of peeling force, particularly, a wide range of green sheet peeling strength due to the combination of a melamine component and a polymer component.

The melamine compound may have up to a total of 6 functional groups. The polymer component bonds between the melamine components to prevent the melamine components from bonding to each other, and can form a loose cross-linked network structure due to the long chain structure. It can increase performance and increase stability over time.

Generally, in a silicone-based release film, a silicone polymer component is added to increase peeling force, but when the content of the silicone polymer component exceeds 50% by weight based on the total weight of the composition, a serious problem occurs in stability over time. 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. Unlike the conventional silicone-based release film, in the release coating composition of the present disclosure, as described above, since the melamine component and the polymer component become a copolymer and form a crosslinked network structure, functional groups exhibiting release property are not impregnated from the surface of the release layer to the inside. It can be maintained continuously, and thus excellent stability with time can be exhibited.

In one aspect, the polymer component is not limited as long as it is a polymer having a long chain structure and is capable of binding with the melamine component to form a crosslinked network structure and imparting softness. For example, the polymer component may be at least one selected from the group consisting of polyester, polyurethane, polyvinyl resin, polyethylene terephthalate, polyethylene terephthalate, acrylate, methacrylate, combinations thereof, and copolymers thereof. Not limited. Here, the copolymer of polyethylene terephthalate (co-PET) is not limited as long as it is a copolymer having polyethylene terephthalate as a main repeating unit, but for example, terephthalic acid; ethylene glycol; and at least one of isophthalic acid, diethylene glycol, mono propylene glycol, and cyclohexylene dimethanol; may be a copolymer comprising.

In one aspect, the polymer component may contain a polar functional group, and may contain two or more different polar functional groups.

In one aspect, the polar functional group is not limited as long as it can react with a functional group present in the melamine component to form a crosslink. For example, the polar functional group may be one or more selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, an amine group, a carbonyl group, an acryl group, an acryloyl group, a nitrile group, a vinyl group, a halogen group, a urethane group, and an ester group. Not limited.

In one embodiment, the polymer component has a weight average molecular weight of about 3,000 to about 30,000, about 5,000 to about 30,000, about 8,000 to about 30,000, about 10,000 to about 30,000, about 10,500 to about 30,000, about 10,500 to about 20,000, about 11,000 to about 15,000, from about 11,000 to about 14,000, from about 11,000 to about 13,000, or from about 11,000 to about 12,000. As the weight average molecular weight of the polymer component increases, the softness of the release layer after curing may increase.

In one embodiment, the content of the polymer component is 0.01 to 5% by weight, 0.1 to 4% by weight, 1 to 3.5% by weight, 1.5 to 3% by weight, or 2 to 3% by weight based on the total weight of the total composition. can When the polymer component is used in excess beyond the above maximum value, the melamine component is not sufficiently cured and the uncured polymer component or melamine component rises to the surface of the release layer, so that the rub-off properties of the release film (that is, the release layer) adhesion or adhesion to the base film) may be poor. When an excessively small amount of the polymer component is used below the minimum value, a cross-linked network structure by the curing reaction may not be properly formed, and desired peel strength or stability with time may not be achieved.

4. Acid catalyst

In one aspect, the acid catalyst is not limited as long as it is known to catalyze the crosslinking reaction of the melamine component or the crosslinking reaction of the melamine component and the polymer component, and they may be appropriately selected and used. For example, the acid catalyst is an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid; oxalic acid, acetic acid, formic acid, methanesulfonic acid, trifluoromethanesulfonic acid, isoprenesulfonic acid, camphorsulfonic acid, hexanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, decanesulfonic acid , hexadecanesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, paratoluenesulfonic 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, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxypolyethylene glycol acid phosphate, Bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di2-ethylhexyl acid phosphate, dilauryl acid phosphate, distea Organic acids such as reel acid phosphate, diphenyl acid phosphate, and bisnonylphenyl acid phosphate; and thermal acid generators such as sulfonium salts, benzothiazolium salts, ammonium salts and phosphonium salts, but are not limited thereto. The acid catalyst component may be used alone or in combination of two or more.

In one aspect, the weight ratio of the melamine component and the acid catalyst may be 100:5 to 100:30, 100:10 to 100:20, or 100:10 to 100:15, which is present between the upper and lower limits described above. It may be a weight ratio. When the content of the acid catalyst is used excessively less than the minimum value of the weight ratio, the curing reaction does not occur properly, and when it is used in excess of the maximum value, overcuring occurs, and in both cases, the stability over time may be deteriorated. Therefore, in order to achieve excellent stability over time, it is preferable that the weight ratio of the melamine component and the acid catalyst satisfies the above range.

5. Solvent

In one aspect, the release coating composition may be a water-based release coating composition. In one aspect, the aqueous system may mean an aqueous solution or an aqueous dispersion, and may mean that the solvent component of the composition is water alone or a combination of water and an organic solvent described below.

In one aspect, since the water-based release coating composition is a water-based base, when the release layer is formed, the emission of volatile organic compounds (VOC) can be fundamentally reduced and eco-friendly requirements can be satisfied. In addition, it can be easily used by mixing with water-based additives such as water-based antistatic agents, and has the advantage of implementing both antistatic properties and releasability of a release film with a one-component crude liquid.

In one aspect, 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 the water and the organic solvent is water: the weight ratio of the organic solvent is 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 99:1 or greater.

In one aspect, the organic solvent may be a known organic solvent widely used in the field of release films, and is not particularly limited as long as it has good compatibility with water. For example, the organic solvent is 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.

6. Other Ingredients

In one aspect, 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 of the release layer to be achieved (eg, the frame). .

(1) Antistatic agent and conductivity improver

In one aspect of the present disclosure, the antistatic agent may exhibit an effect of not only imparting an antistatic ability to the release layer, but also preventing adsorption of foreign substances. In the ceramic green sheet manufacturing process, there is a process of cutting and cutting the ceramic green sheet. In this case, since the ceramic green sheet is in the form of agglomerated beads such as particle grains, the bead dropout phenomenon occurs in the process of cutting the green sheet. Therefore, the antistatic ability can prevent the bead from falling off due to static electricity in the process of cutting the release film together with the ceramic green sheet, thereby contributing to the fairness of manufacturing the ceramic green sheet.

In one aspect, the antistatic agent may be a known antistatic agent widely used in the field of release films, and is not particularly limited. For example, 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.

In one aspect, 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%), wherein the antistatic agent The content of the aqueous solution containing It may be a content present in between. When the content of the antistatic agent exceeds the maximum value and is used in excess, it may cause defects in the appearance of the release layer, which may appear as blue spots.

In one aspect, the antistatic agent may be included in the above content to impart a surface resistance of about 10^4 to 10^10 ohm/sq to the release layer.

In one aspect, the release coating composition may further include a conductivity enhancer to achieve a desired level of surface resistance, ie, antistatic ability. Such a conductivity improver may serve to assist the performance of the antistatic agent, and when the conductivity enhancer is used, a desired level of surface resistance of the release layer may be achieved even if a smaller amount of the antistatic agent is used.

In one aspect, 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 total composition. weight percent, about 1.5 to 6 weight percent, about 2 to 6 weight percent, about 2.5 to 6 weight percent, about 3 to 6 weight percent, about 4 to 6 weight percent. When the content of the conductivity improver exceeds the above maximum value and is used in excess, curing of the release layer may be prevented, the appearance and rub-off properties of the release layer may not be achieved at desired levels, and the content of the conductivity enhancer may be lower than the minimum value If it is used too little or less, the effect may be insignificant.

In one aspect, the conductivity enhancer may be a known conductivity enhancer widely used in the conventional release film field, and is not particularly limited. For example, 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.

(2) pH adjusting agent

In one aspect of the present disclosure, the pH adjusting agent may adjust the pH of the entire composition to a desired level. The release coating composition may contain an antistatic agent exhibiting acidity, and when the composition becomes acidic, neutral or basic components such as surfactants or polymer components may not function properly, so pH adjustment is required in this case. If the pH of the entire release coating composition is not adjusted, the stability of the composition itself may rapidly deteriorate over time, and the transfer of the release layer may deteriorate depending on the elapsed time after the composition is prepared. For example, when a release coating composition is prepared and immediately applied to a base film to form a release layer, a good appearance is obtained. phenomenon may occur.

In one aspect, the pH adjusting agent may be a well-known pH adjusting agent widely known in the field of release films, but is not particularly limited. For example, the pH adjusting agent may be one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide and aqueous ammonia, but is not limited thereto. The pH adjusting agent may be a basic pH adjusting agent.

In one aspect, the content of the pH adjusting agent 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 total composition, and is between the upper limit value or the lower limit value described above. It may be an amount that When the pH adjusting agent is used in excess beyond the above maximum value, curing of the release layer may be hindered.

(3) surfactant

In one aspect of the present disclosure, the surfactant may improve the wetting property of the release coating composition or the spreadability of the base film, and improve the compatibility between the melamine component and the polymer component. In one aspect, when water is used as the sole solvent in the aqueous release coating composition, two or more different surfactants may be used.

In one aspect, the surfactant may be a component capable of lowering the surface tension as a well-known surfactant widely known in the field of release films, and is not particularly limited. For example, the surfactant may be a cationic surfactant, an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, a silicone surfactant, a modified silicone surfactant, a fluorine surfactant, or a combination thereof. Not limited.

In one aspect, the cationic surfactant may be, for example, an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, or an alkylbenzyldimethylammonium salt, but is not limited thereto.

In one aspect, the anionic surfactant may be, for example, a fatty acid salt, an alkylbenzenesulfonate, an alkylsulfonate, an alkylethersulfonic acid ester salt, an alkylpolyoxyethylenesulfonate, or a monoalkylphosphate, but is limited thereto. it doesn't happen

In one aspect, the amphoteric surfactant may be, for example, an alkyldimethylamine oxide, or an alkylcarboxybetaine, but is not limited thereto.

In one aspect, the nonionic surfactant is, 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.

In one aspect, the silicone-based surfactant may be, for example, polyether-modified silicone, or polyglycerin-modified silicone, but is not limited thereto. The structure of these modified silicones is classified into side chain modified type, both ends modified type (ABA type), single end modified type (AB type), both ends side chain modified type, straight chain block type (ABn type), branched type, etc. However, modified silicon of any of these structures may be used.

In one aspect, 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 total composition, and is between the upper limit value or the lower limit value described above. It may be an amount that

(4) antifouling agent

In one aspect of the present disclosure, the antifouling agent may control the surface energy of the release layer and impart antifouling properties. When the difference in surface energy between the base film and the release layer is small, wettability and peelability of the release layer with respect to the base film may be reduced, but the antifouling agent lowers the surface energy of the release layer to prevent it. In addition, since the melamine component included in the release coating composition of the present disclosure has little slip property (slip property), the antifouling agent may impart slip property to the release layer.

In one aspect, the antifouling agent may be at least one selected from the group consisting of fluorine, a fluorine-containing silane-based compound, a fluorine-containing organic compound, and self-emulsifying silicone, but is not limited thereto. In one aspect, the self-emulsifying silicone may be a silicone monomer including one or more hydroxyl groups, but is not limited thereto.

In one aspect, 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 total composition, and is between the upper limit value or the lower limit value described above. It may be the amount of If the antifouling agent is used excessively less than the minimum value, a problem may occur that stain marks remain when the release film is peeled off, and the green sheet slurry particles may remain in the release layer after the release film is peeled from the green sheet. have.

(5) Oxazoline-based curing agent

In one aspect of the present disclosure, the oxazoline-based curing agent can induce a curing reaction of a polar functional group of a polymer component, for example, a carboxyl group, an aromatic thiol group or a phenol group, so that the release film has Rub-off properties or content It can improve sanity. Specifically, the polar functional group present in the polymer component has curing priority over curing between the hydroxyl groups involved in bonding between the melamine component or between the hydroxyl groups of the melamine component and the silicone component (eg, self-emulsifying silicone) included in the release coating composition. may be low and thus the polar functionality of the polymer component may not fully participate in the curing reaction. In this case, since the polymer component including the polar functional group exists with a weak bonding force of about van der Waals force on the cured structure composed of melamine-melamine or melamine-silicon, a problem in that the solvent resistance of the release layer is weakened may appear. When an oxazoline-based curing agent is used, a polar functional group can participate in the curing reaction, and thus a cross-linked product between the polymer components or a cross-linked product between the polymer component and the melamine component is further formed, improving the rub-off properties or solvent resistance of the release film. can do it

In one aspect, the oxazoline-based curing agent may be a compound or polymer containing an oxazoline group, and any known component widely used in the field of release films may be used without particular limitation. Examples of the oxazoline group-containing monomer that can be used for preparing the oxazoline-based curing agent include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5- Methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, or these It may be a combination of, but is not limited to. As other monomers usable for the preparation of the oxazoline-based curing agent, any monomer capable of forming a copolymer with the oxazoline group-containing monomer described above can be used without limitation, for example, alkyl (meth)acrylate, acrylic acid, methacrylic acid, ethylene, propylene, vinyl chloride, or styrene, but is not limited thereto.

In one aspect, commercially available oxazoline-based curing agents include Nippon Shokubai's product names WS-300, WS-500, WS-700, K-2010E, K2020E, K2030E, or RPS-1005. It is not limited.

7. Physical properties of the release film

In one aspect of the present disclosure, the release film may be prepared by applying a release coating composition to at least one surface of the base film to form a release layer, and the release film thus prepared may have the following physical properties. The following physical properties may be measured by the method described in Experimental Examples.

In one aspect, the release layer constituting the release film may satisfy the following formula (1).

Formula (1)

0.5 ≤ P _b /P _a ≤ 10.0

P _a : In the FT-IR spectrum, the maximum absorption peak intensity in the region having a wave number of 1450 cm ^-1 or more and less than 1650 cm ^-1

P _b : In the FT-IR spectrum, the maximum absorption peak intensity in the region having a wave number of 1650 cm ^-1 or more and 1850 cm ^-1 or less

The FT-IR spectrum of the release layer may be measured by the method described in Experimental Example 8.

The P _b /P _a value is not particularly limited as long as it satisfies the above range, but for example, 0.55 or more, or 0.6 or more, 9.95 or less, or 9.9 or less, or 9.85 or less, or 9.8 or less, or 9.75 or less. or less, or 9.7 or less, or 9.65 or less, or 9.6 or less.

The P _a is a peak due to the polar functional group included in the polymer component, the P _b is a peak due to NCN bending in the melamine component, and the P _b /P _a value satisfies the above-described range. Through the inclusion of the polymer component and melamine, the release film can achieve excellent stability over time and at the same time achieve a wide range of green sheet peel strength. In addition, the release film can achieve excellent residual adhesion and stability over time while increasing the peeling force of the green sheet. Out of the above range, when the P _b /P _a value exceeds 10.0, the content of a polymer component (eg, co-PET) including a polar functional group is too high, and a residue remains when the green sheet is peeled off and complete transfer can become difficult

In one aspect, the release film may exhibit a tape immediate peel force of 30 to 50 gf/in, and may exhibit a peel force of a value that exists between the upper and lower limits described above, for example, 32 gf/in or higher, 34 gf/in or higher, 36 gf/in or higher, 38 gf/in or higher, 40 gf/in or higher, 42 gf/in or higher, 44 gf/in or higher, 46 gf/in or higher, or 48 gf or higher /in or more, 48 gf/in or less, 46 gf/in or less, 44 gf/in or less, 42 gf/in or less, 40 gf/in or less, 38 gf/in or less, 36 gf/in or less, 34 gf/in or less in or less, or 32 gf/in or less.

In one aspect, the release film may exhibit a peel strength of 200 to 250 gf/in of tape at room temperature per day, and may indicate a peel strength of a value existing between the upper and lower limits described above, for example, , 210 gf/in or greater, 220 gf/in or greater, 230 gf/in or greater, or 240 gf/in or greater, or 240 gf/in or greater, 230 gf/in or less, 220 gf/in or less, or 210 gf/in or less can This release film satisfies the peel strength of the jungbak release film or ultra jungbak release film, and can be used in a variety of fields that require it.

In one aspect, the release film exhibits a green sheet peeling force of 1 to 100 gf/in, 4 to 98 gf/in, 10-70 gf/in, 20 to 60 gf/in, or 20 to 50 gf/in. It may be one, and may represent the peel force of a numerical value that exists between the upper and lower limit values described above. The peel force of the green sheet may be measured by the method described in Experimental Example 1, and may represent the peel force of a green sheet having a thickness of 3 μm. In one aspect, the release film exhibits a wide green sheet peeling force, and this range corresponds to physical properties that cannot be achieved from a conventional silicone release film. In particular, in order to achieve a peel force of at least 4 gf/in for a green sheet having a thickness of 3 μm, in the silicone release film, a large amount of a silicone resin must be added to increase the peel force, and the content of the silicone resin is the total amount of the release coating composition. If it exceeds 50% by weight based on the weight, a serious problem may occur in stability over time, as described above. Therefore, the release film according to an aspect of the present disclosure or the release coating composition used for preparing the release film exhibits excellent stability over time, and can implement a wide range of green sheet peeling force by combining a melamine component and a polymer component, so it is very It has the advantage that it can be used in a wide range of industrial fields.

Therefore, the release film according to one aspect of the present disclosure has the advantage of being able to implement various green sheet peel force grades and at the same time realize a certain range of medium peel strength based on the immediate peeling force of the tape or the peeling force of the tape at room temperature for one day. , thus, a single release film can be used as a release film for the manufacture of green sheets for various purposes, and can be used in industrial fields that require peeling force of jungbak-ri based on tape peeling force, so it can be used for various purposes.

In one aspect, the release film is 0.9 or more, 0.91 or more, 0.92 or more, 0.93 or more, 0.94 or more, 0.95 or more, 0.96 or more, 0.97 or more, or 0.98 or more, or 1.2 or less, 1.18 or less, 1.16 or less, 1.14 or less, 1.12 or more. or less, 1.10 or less, 1.08 or less, 1.06 or less, 1.04 or less, or 1.08 or less, which may represent an RF ₉₀ /RF ₁ value, and represents an RF ₉₀ /RF ₁ value of a numerical value existing between the upper and lower limit values described above it could be Here, RF ₁ and RF ₉₀ denotes the release film to the green sheet, measured after storing the release film to which the green sheet is attached for 24 hours (1 day) and 90 days at room temperature of 23° C. and humidity of 50%, respectively. means power. The RF ₉₀ /RF ₁ value may be measured by the method described in Experimental Example 1, and may represent stability over time for a green sheet having a thickness of 3 μm through the change rate of the peel force of the green sheet after 90 days. In one aspect, the release film exhibits excellent stability over time, and this range corresponds to physical properties that cannot be achieved from a conventional silicone release film. Therefore, the release film according to an aspect of the present disclosure or the release coating composition used for preparing the release film exhibits excellent stability over time, and can implement a wide range of green sheet peeling force by combining a melamine component and a polymer component, so it is very It has the advantage that it can be used in a wide range of industrial fields.

In one aspect, the release film may have a silicon content of about 0.001 to about 0.015 g/m ² in the release layer measured using an X-ray fluorescence analyzer.

In one aspect, 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. In general, in a process of peeling a release film, an adhesive such as a pressure sensitive adhesive (PSA) or an optically clear adhesive (OCA) is attached on the release film, and then the release film is peeled off. However, in the process of peeling the release film in this way, an uncured component present in the release layer of the release film is transferred, which may cause a problem of disturbing 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 an advantage that it can be used in fields requiring high standards.

In one aspect, the release film may have a surface energy of about 21 to about 30 dyne/cm or about 25 to about 27 dyne/cm of the release layer, and a surface energy value of a numerical value existing between the upper and lower limits described above. may indicate The surface energy of the release layer may be measured by the method described in Experimental Example 5.

In one aspect, 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.

8. Manufacturing method of release film

In one aspect of the present disclosure, the method of manufacturing the release film is not particularly limited as long as the release layer is formed using the release coating composition. For example, it is possible to apply a release coating composition to at least one side of a base film, and heat and dry it to cure a melamine component and a polymer component contained in the release coating composition to form a release layer, thereby obtaining a release film do.

In one aspect, the method of applying the release coating composition may be a known method widely used in the field of release film, for example, gravure coating method, bar coating method, spray coating method, spin coating method, knife coating There may be a method, a roll coating method, a die coating method, an in-line coating method, an off-line coating method, etc., but is not limited thereto.

In one aspect, the applied release coating composition may be thermally cured by heating and drying, wherein 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. In one aspect, 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.

In one aspect, after heat drying of the release coating composition, a post curing process may be included for curing the uncured component. For example, the post-curing process may be to make a roll (roll) form by winding a release film prepared by heat drying, and then to process at 40 ° C. to 60 ° C. for 1 to 5 days. The treatment temperature may be from 40°C to 60°C, from 45°C to 55°C, from 47°C to 53°C, from 49°C to 53°C, from 50°C to 53°C, or from 50°C to 51°C, and the treatment time is from 1 day to 5 days. days, 1.5 days to 4.5 days, 2 days to 4 days, 2.5 days to 3.5 days, or 3 days to 3.5 days. When the post-curing process is performed, the stability over time may be improved in the physical properties of the release film (eg, peel force, residual adhesion, or rub-off characteristics).

In one aspect, the release layer of the release film may be formed in a dry thickness of 0.01 to 2㎛, or 50 nm to 500 nm.

The present disclosure will become clearer through the aforementioned aspects and experimental examples or examples to be described later. Hereinafter, it will be described in detail so that those skilled in the art can easily understand and implement through the embodiments described with reference to the accompanying table of the present disclosure. However, these experimental examples or examples are for illustrative purposes of the present disclosure, and the scope of the present disclosure is not limited to these experimental examples or examples.

[Example]

1. Preparation of release coating composition

A release coating composition was prepared by mixing the following ingredients. However, the content of the co-PET compound corresponding to the polymer component was prepared in different amounts based on 100 parts by weight of the melamine component according to Table 1.

- Melamine component (manufacturer: Allnex, product name: CYMEL® 303 LF Resin) 0.5 wt%

- Polymer component (co-PET compound; 25% by weight of a compound prepared by mixing 52% by weight of terephthalic acid, 45% by weight of ethylene glycol, and 3% by weight of isophthalic acid, based on solid content, 70% by weight of water and 5% by weight % of isopropyl alcohol added in the form of a crude solution)

- Melamine catalyst (manufacturer: Allnex, product name: Cymel® 4040 Catalyst) 0.06 wt%

- PEDOT aqueous solution (manufacturer: Heraeus, product name: Clevios PT2) 20% by weight

- 9% ammonia water (Manufacturer: Duksan Pharmaceutical Co., Ltd.) 0.05 wt%

- Surfactant (manufacturer: BYK, product name: BYK348) 0.01 wt%

- Antifouling agent (Manufacturer: Silicon DNA, Product name: SD3667) 0.2 wt%

- Remaining amount of distilled water

2. Preparation of release film

The release coating composition thus prepared is applied on at least one side of a polyethylene terephthalate base film having a thickness of 50 μm (manufacturer: Toray Advanced Materials, product name: XD500) using a bar coater, and then in a hot air dryer at 150° C. for 30 seconds. After curing by heating and drying, a release film having a release layer formed on the substrate was prepared.

[Comparative example]

1. Preparation of release coating composition

A release coating composition was prepared in the same manner as in Examples, except for the polymer component (co-PET compound) in Comparative Example 1, and in Comparative Examples 2 to 5, the conventional controlled release additive (CRA) instead of the polymer component. ) (Shin-Etsu Corporation, product name: X-62-185) was added in an amount of 50%, 20%, 40%, and 60%, respectively, based on the melamine component.

2. Preparation of release film

A release film with a release layer was prepared by using the release coating composition of the comparative example in the same manner as in the above example.

[Experimental Example 1] Green sheet peel force measurement and stability over time measurement

50 parts by mass of barium titanate (BaTiO3; manufactured by Sakai Chemical Industries, Ltd., product name: BT-03), 5 parts by mass of polyvinyl butyral (made by Sekisui Chemical Industries, product name: S-Rec B·KBM-2), and dioctyl phthalate ( 69 parts by mass of toluene and 46 parts by mass of ethanol were added to 2 parts by mass of Kanto Chemical, product name: dioctyl cica phthalate 1st class), and mixed and dispersed with a ball mill to prepare a ceramic slurry.

The ceramic slurry was uniformly applied to the release film stored at room temperature for 48 hours after preparation in Examples and Comparative Examples using an applicator on the surface of the release layer. Then, it dried at 80 degreeC with a dryer for 1 minute. Finally, a ceramic green sheet having a thickness of 3 μm was obtained on the release film, and a release film to which the ceramic green sheet was attached was prepared.

The release film to which the ceramic green sheet was attached was stored for 24 hours and 90 days at room temperature of 23°C and humidity of 50%. Then, on the ceramic green sheet, an acrylic adhesive tape (manufactured by Nitto Denko, trade name: 31B tape) was adhered to the side opposite to the release film, and cut to a width of 25 mm in that state, which was used as a measurement sample.

After fixing the adhesive tape side of the measurement sample to a flat plate, the release film was peeled from the ceramic green sheet at a peeling angle of 90° and a peeling rate of 500 mm/min using a tensile tester (AR-1000 device by ChemInstrument), Peel force (gf/25mm) was measured. Table 1 shows the average value of the results of 5 measurements.

In addition, the ratio (RF ₉₀ /RF ₁ ) of the peel force (RF ₉₀ ) after storage for 90 days to the peel force (RF ₁ ) after storage for 24 hours was measured, indicating stability over time.

[Experimental Example 2] Tape peel force measurement

Using the TESA7475 tape (manufactured by TESA, Germany), which is a standard tape widely used in the technical field of the present disclosure, the release coating composition prepared in the above Examples and Comparative Examples was applied to evaluate the peel strength of the release film prepared.

A TESA7475 tape, which is a standard tape, was attached to the release coating surface of the release layer with a 2 kg roller, and the peel force at the time of peeling was measured after 20 minutes at room temperature or 24 hours at room temperature. Peel force measurement was measured 5 times at a peeling angle of 180° and a peeling rate of 12 in/min using an AR-1000 device from ChemInstrument, and the average value was obtained.

[Experimental Example 3] Silicon content measurement

An X-ray fluorescence analyzer (XRF) (manufactured by OXFORD, product name: LAB X-3500) was used to measure the silicone content in the release layer of the release films prepared in Examples and Comparative Examples.

[Experimental Example 4] Measurement of residual adhesion rate

After storing the sample for measurement of the release film prepared in the above Examples and Comparative Examples at 25° C. and 65% RH for 24 hours, attach the Nitto31B tape, a standard tape, to the release coating surface, and then apply the sample at room temperature to 20 g/cm ² of It was pressed under load for 24 hours. After the tape adhered to the release coating surface was collected without contamination, the surface was adhered to the flat and clean polyethylene terephthalate (PET) film surface, and the adhesive force was measured after reciprocating compression with a 2 kg tape roller once.

For comparison, the Nitto31B tape, which has never been used, was adhered to a PET film with a flat and clean surface, and then reciprocated with a 2 kg tape roller once and the peel force was measured.

Peel force was measured as follows, and the residual adhesion rate was calculated from it by Equation 1.

Measuring instrument: ChemInstrument's AR-1000 instrument

Measurement method: 180° peeling angle, peeling speed 30mm/min

<Equation 1>

Residual adhesion rate (%) = [Peel force of the adhesive tape peeled off after adhering to the surface of the release layer / Peel force of the adhesive tape not in contact with the surface of the release layer] × 100

[Experimental Example 5] Surface energy measurement

After measuring each contact angle by dropping distilled water and methylene iodide (diiodomethane) using a contact angle meter (KRUSS company product name: DSA-100) on the release coating surface of the release film prepared in Examples and Comparative Examples, the measured The surface energy was calculated by substituting the contact angle value into the Owens-Wendt model.

[Experimental Example 6] Rub-off test

By applying force with the thumb, the degree of change in the surface of the release layer after the release layer of the release film prepared in the above Examples and Comparative Examples was reciprocally rubbed 10 times was visually observed. As a result, the rub-off characteristics were evaluated as follows.

◎：　If there is no change after evaluation

○：　When there is no problem in use even though it is pushed slightly

△: 　When the surface of the release layer becomes cloudy

X：　When the release layer is peeled off

The results obtained according to the above experimental example are shown in Table 1 below.

Melamine component: polymer component weight ratio
(based on solid content) Green sheet peel strength
(RF ₁ )
(1 day after manufacture) Green sheet peel strength
(RF ₉₀ )
(90 days after manufacture) stability over time
(RF ₉₀ /RF ₁ ) Tape Instant Peel Force
(gf/in) Tape peel strength at room temperature per day Silicon content (g/m ² ) Residual Adhesion
(%) surface energy
(dyne/cm) Rub-off Comparative Example 1 100:0 2.8 2.9 1.04 40.4 221.1 0.006 96 26.1 ◎ Example 1 100:3 4.6 4.6 1.0 43.9 224.4 0.006 95 26.2 ◎ Example 2 100:6 10.1 10.7 1.06 39.6 212.7 0.005 96 25.9 ◎ Example 3 100:13 24.7 24.4 0.99 43.1 230.4 0.006 95 26.4 ◎ Example 4 100:33 60.2 61.1 1.01 38.7 228.6 0.005 94 26.1 ◎ Example 5 100:66 99.3 98.4 0.99 42.1 220 0.006 95 26.7 ◎ Comparative Example 2 Conventional Additives (50%) 3.3 2.8 0.85 30.2 78.8 0.061 95 19.1 ◎ Comparative Example 3 Conventional Additives (20%) 2.5 2.1 0.84 9.4 34.1 0.033 94 20.2 ◎ Comparative Example 4 Conventional Additives (40%) 3.2 2.4 0.75 24.1 71.9 0.045 91 19.4 ○ Comparative Example 5 Conventional additives (60%) 4.5 3.3 0.73 38.4 124.1 0.058 82 20.1 ○

According to the results in Table 1, the release film obtained using the release coating composition according to an aspect of the present disclosure exhibited excellent stability over time compared to the case of using the comparative example, and at the same time achieved a green sheet peeling force in a variety of ranges. Therefore, it can have an advantage that can be utilized in various industrial fields.

In the case of Comparative Examples 2 to 5, which are release films showing heavy peeling power in the prior art, the peeling force for a green sheet of 3 μm did not exceed 4 gf/in, and even if it exceeds this, stability over time was very poor. This is because, as explained, the content of CRA corresponding to the silicone resin is too excessive. On the other hand, in Examples, it was possible to achieve heavy peeling force that could not be achieved in the past by exceeding 4 gf/in through the combination of the melamine component and the polymer component.

The Example according to an aspect of the present disclosure exhibited a green sheet peel force almost similar to that of the first day after manufacturing even when the peel force was measured on the green sheet 90 days after manufacturing, and exhibited very excellent stability over time, but Comparative Example The peel strength of the green sheet decreased over time and showed relatively poor stability over time. This is because, in the case of Examples, the melamine component and the polymer component form a crosslinked network structure after curing, whereas the comparison does not form such a structure.

In addition, it was confirmed that the Example according to an aspect of the present disclosure exhibits a residual adhesion rate of at least 94% and exhibits excellent rub-off properties.

[Experimental Example 7] Ship-ri test

A folding tester (Flexigo Co., Ltd., Foldy-100-1C) was used in order to simulate and evaluate the degree of vessel clearance of the release film. After fixing the release film to which the ceramic green sheet prepared according to Experimental Example 1 is attached with tape on the fixed plate and the moving plate, repeat 1 to 100 times at a rate of 1.5 times/sec to the degree that the green sheet is separated from the release film were compared and the results are shown in FIG. 1 .

According to FIG. 1b, in the case of Example 2, even if the repetition continues, the ship-breaking hardly occurs, and only the ship-breaking occurs little by little at the end of the 30th repetition. In contrast, in the case of Comparative Example 2, a lifting phenomenon was observed after application, and a significant amount of vessel clearance occurred from the first repetition, and as the repetition progressed, it was confirmed that vessel clearance occurred steadily and the vessel clearance area increased. have.

These results show that the release film prepared using the release coating composition according to an aspect of the present disclosure can implement a relatively high green sheet peeling force compared to the release film exhibiting heavy peeling force in the prior art, and excellent stability over time. it means to have In the case of the conventional release film, higher CRA content can be increased to realize higher green sheet peeling force. However, in the present disclosure, by using a combination of a melamine component and a polymer component, a wide range of green sheet peeling force is realized and excellent stability over time is achieved, so it is much more advantageous for use in the relevant industrial field.

In addition, the release film of the present disclosure exhibits much superior ship-removal properties and stability over time compared to the conventional release film even when the same peeling force is implemented. In particular, as the thickness of the green sheet increases, a higher level of peeling force is required. In the case of a conventional release film, when this peeling force is achieved, the stability over time becomes very poor. In this case, even a small physical impact may cause the release film to float. On the contrary, since the release film of the present disclosure realizes various levels of peeling force of the green sheet and at the same time exhibits excellent stability over time, it can be used for a thick green sheet without the same problems as with the conventional release film.

[Experimental Example 8] FT-IR spectrum measurement

FT-IR spectra of the release layers prepared with the release coating compositions of Example 2 and Comparative Example 1 were measured. Specifically, Bruker's VERTEX70 device was used, and the release coating composition of Examples and Comparative Examples was applied to a glass plate, dried by heating and drying at 150° C. for 30 seconds in a hot air dryer, and then 0.1 g of the coating layer was collected with a ceramic knife. The spectrum was measured by ATR method. The FT-IR spectrum measurement result is shown in FIG. 2 .

According to FIG. 2 , it can be confirmed that the release layer prepared from the release coating composition of the present disclosure, unlike Comparative Example 1, exhibits high absorption peak intensity in a region of 1650 cm ^-1 or more and 1850 cm ^-1 or less. Meanwhile, P _b /P _a values for the release layer prepared from the release coating composition of Examples are shown in Table 2 below.

P _a P _b P _b /P _a Comparative Example 1 0.1 0.03 0.3 Example 1 0.1 0.06 0.6 Example 2 0.1 0.09 0.9 Example 3 0.1 0.18 1.8 Example 4 0.1 0.48 4.8 Example 5 0.1 0.96 9.6

Therefore, the release film prepared using the release coating composition of the present disclosure has the maximum absorption peak intensity in the region of 1450 cm ^-1 or more and less than 1650 cm ^-1 in the region of Pa, 1650 cm ^-1 or more and 1850 cm ^-1 or less. It can be confirmed that the expression of 0.5 ≤ Pb/Pa ≤ 10.0 is satisfied when the maximum absorption peak intensity is Pb. In addition, by satisfying the P _b /P _a value in this range, it can be confirmed that, as shown in Table 1, excellent stability over time is exhibited and green sheet peeling force in various ranges is achieved.

Claims (22)

A melamine component that is a melamine compound of Formula 1, an oligomer thereof, a polymer thereof, or a combination thereof;
a polymer component containing a polar functional group and having a weight average molecular weight of 3,000 to 30,000; and
containing an acid catalyst;
After curing to form a crosslinked network structure consisting of the melamine component and the polymer component,
A water-based release coating composition.
[Formula 1]

(Wherein, X represents a hydrogen atom, -CH ₂ OH, or -CH ₂ -OR, and may be the same or different, respectively. R represents an alkyl group having 1 to 8 carbon atoms, and may be the same or different from each other. at least one X is -CH ₂ -O-CH ₃ ) The method according to claim 1, The total acid value in the melamine component is 390 to 780mgKOH / g,
A water-based release coating composition. According to claim 1,
The polymer component is at least one selected from the group consisting of polyester, polyurethane, polyvinyl resin, polyethylene terephthalate, polyethylene terephthalate, acrylate, methacrylate, combinations thereof, and copolymers thereof,
A water-based release coating composition. According to claim 1,
The polymer component is a polyethylene terephthalate copolymer,
The polyethylene terephthalate copolymer is terephthalic acid; ethylene glycol; and at least one of isophthalic acid, diethylene glycol, mono propylene glycol, and cyclohexylene dimethanol; which is a copolymer comprising
A water-based release coating composition. According to claim 1,
The polar functional group is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, an amine group, a carbonyl group, an acryl group, an acryloyl group, a nitrile group, a vinyl group, a halogen group, a urethane group, and an ester group,
A water-based release coating composition. According to claim 1,
wherein the polymer component contains at least two different polar functional groups,
A water-based release coating composition. According to claim 1,
Acid catalysts are hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid oxalic acid, acetic acid, formic acid, methanesulfonic acid, trifluoromethanesulfonic acid, isoprenesulfonic acid, camphorsulfonic acid, hexanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, decanesulfonic acid, hexadecanesulfonic acid, dinonylnaphthalenesulfonic acid , dinonylnaphthalenedisulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, paratoluenesulfonic acid, melamine zinc iodide (melamine ZnI ₂ ), melamine trisulfonic acid (MTSA), cumenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, no Naphthalenesulfonic 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, Stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di2-ethylhexyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, At least one selected from the group consisting of bisnonylphenyl acid phosphate sulfonium salt, benzothiazolium salt, ammonium salt, and phosphonium salt,
A water-based release coating composition. According to claim 1,
The weight ratio of the melamine component and the acid catalyst is 100:5 to 100:30, 100:10 to 100:20, or 100:10 to 100:15,
A water-based release coating composition. According to claim 1,
0.2 to 1.0% by weight of a melamine component based on the total weight of the total composition or
0.01 to 5% by weight of a polymer component, based on the total weight of the total composition;
A water-based release coating composition. According to claim 1,
The weight ratio of the melamine component and the polymer component is 100:3 to 100:70 on a solids basis,
A water-based release coating composition. According to claim 1,
Further comprising at least one of an antistatic agent, a conductivity improver, a pH adjuster, a surfactant, and an antifouling agent,
A water-based release coating composition. 12. The method of claim 11,
The antistatic agent is at least one selected from the group consisting of PEDOT, PEDOT:PSS, polyaniline, polypyrrole, quaternary ammonium salts, sulfonates, and phosphates,
A water-based release coating composition. 12. The method of claim 11,
The pH adjusting agent is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide and aqueous ammonia,
A water-based release coating composition. 12. The method of claim 11,
Surfactants are cationic surfactants, anionic surfactants, amphoteric surfactants, nonionic surfactants, silicone surfactants, modified silicone surfactants, fluorine surfactants, or a combination thereof,
A water-based release coating composition. 12. The method of claim 11,
The antifouling agent is at least one selected from the group consisting of fluorine, fluorine-containing silane-based compounds, fluorine-containing organic compounds, and self-emulsifying silicones;
A water-based release coating composition. 16. The method of claim 15,
The antifouling agent is a self-emulsifying silicone,
The self-emulsifying silicone is a silicone monomer containing a hydroxyl group,
A water-based release coating composition. 12. The method of claim 11, based on the total weight of the total composition.
0.1 to 30% by weight of an antistatic agent,
0.01 to 0.3% by weight of a pH adjusting agent,
0.05 to 0.2% by weight of a surfactant, or
0.1 to 0.3% by weight of an antifouling agent
A water-based release coating composition. According to claim 1,
Further comprising an oxazoline-based curing agent,
A water-based release coating composition. According to claim 1,
water or a combination of water and an organic solvent;
The water and organic solvent combination ratio is 50:50 or more, 60:40 or more, 70:30 or more, 80:20 or more, 90:10 or more, 95:5 or more, or 99:1 or more by weight of water: organic solvent ,
A water-based release coating composition. According to claim 1,
The weight average molecular weight of the polymer component is 5,000 to 30,000, 8,000 to 30,000, 10,000 to 30,000, 10,500 to 30,000, 10,500 to 20,000, 11,000 to 15,000, 11,000 to 14,000, 11,000 to 13,000, or 11,000 to 12,000,
A water-based release coating composition. The method according to claim 1, which is used for manufacturing a release film for a ceramic green sheet manufacturing process.
A water-based release coating composition. delete

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