WO2024225614A1 - Releasable composition for coating protection - Google Patents
Releasable composition for coating protection Download PDFInfo
- Publication number
- WO2024225614A1 WO2024225614A1 PCT/KR2024/003323 KR2024003323W WO2024225614A1 WO 2024225614 A1 WO2024225614 A1 WO 2024225614A1 KR 2024003323 W KR2024003323 W KR 2024003323W WO 2024225614 A1 WO2024225614 A1 WO 2024225614A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acrylic emulsion
- film
- weight
- composition
- coating
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 239000011248 coating agent Substances 0.000 title claims abstract description 55
- 238000000576 coating method Methods 0.000 title claims abstract description 55
- 239000000839 emulsion Substances 0.000 claims abstract description 145
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 144
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 16
- 229930195729 fatty acid Natural products 0.000 claims abstract description 16
- 239000000194 fatty acid Substances 0.000 claims abstract description 16
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims description 14
- 230000009477 glass transition Effects 0.000 claims description 13
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 239000007798 antifreeze agent Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002356 laser light scattering Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- -1 alkalis Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000008733 trauma Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/18—Homopolymers or copolymers of nitriles
- C09D133/20—Homopolymers or copolymers of acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/008—Temporary coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/022—Emulsions, e.g. oil in water
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Definitions
- the present invention relates to a peelable composition for temporarily protecting a painted surface of an automobile or heavy equipment, etc., and having excellent adhesive strength while being easy to peel.
- Automobiles or heavy equipment, etc. are temporarily stored outdoors or during transportation before being delivered to the final user. There is a high possibility that their painted surfaces may be damaged, stained, discolored, or contaminated by contaminants such as sand, dust, iron, salts, alkalis, acids, soot, insect waste or bodily fluids, sunlight, wind, and other influences. There may also be cases where physical force causes damage to the material.
- peelable coating compositions have been proposed that can be applied to the surface of a car or heavy equipment in advance at the product shipment stage to temporarily protect the surface from contaminants, sunlight, wind and rain, trauma, etc., and can be easily peeled off after a certain period of storage.
- compositions containing alkali-soluble resins as their main components are also being used, but since alkaline detergents are used when removing them, there are environmental problems such as water pollution.
- Patent Document 1 Republic of Korea Registered Patent No. 10-0498717 (June 22, 2005)
- the present invention seeks to provide a peelable composition for protecting a coating surface of an automobile or heavy equipment, which is easy to peel and has excellent adhesive strength.
- the present invention provides a coating protection film manufactured from a peelable composition for coating protection that is easy to peel and has excellent adhesive strength for protecting a coating surface of an automobile or heavy equipment, etc.
- the present invention provides a strippable composition for protecting a coating film, comprising a first acrylic emulsion and a second acrylic emulsion, wherein the first acrylic emulsion comprises an amino-modified fatty acid-based release agent, and the second acrylic emulsion comprises a zinc oxide (ZnO) curing agent.
- a strippable composition for protecting a coating film comprising a first acrylic emulsion and a second acrylic emulsion, wherein the first acrylic emulsion comprises an amino-modified fatty acid-based release agent, and the second acrylic emulsion comprises a zinc oxide (ZnO) curing agent.
- ZnO zinc oxide
- the present invention provides a coating protection film manufactured by curing a peelable composition for coating protection according to the present invention.
- a peelable composition for film protection according to one aspect of the present invention is characterized by having a fast drying speed, excellent initial adhesion and excellent adhesion retention, the film can be removed cleanly, does not leave residue after detachment, and has excellent water resistance, chemical resistance, and tensile strength.
- the “glass transition temperature” used herein is measured by a conventional method known in the art, and can be measured by, for example, thermomechanical analysis (TMA) or differential scanning calorimetry (DSC).
- TMA thermomechanical analysis
- DSC differential scanning calorimetry
- Weight average molecular weight is measured by a conventional method known in the art, and can be measured by, for example, the GPC (gel permeation chromatography) method.
- Particle diameter (D50) is measured by a conventional method known in the art, and can be measured, for example, by laser light scattering (LLS).
- viscosity is measured by a conventional method known in the art, and can be measured, for example, using a Brookfield viscometer (rotating spindle viscometer) at room temperature (25°C).
- the present invention can provide a peelable composition for protecting a coating surface of an automobile or heavy equipment, which does not react with a body coating, is easy to peel, and has excellent adhesive strength.
- a peelable composition for film protection comprises a first acrylic emulsion and a second acrylic emulsion.
- the first acrylic emulsion of the present invention contains an amino-modified fatty acid-based release agent, and the second acrylic emulsion contains a zinc oxide (ZnO) curing agent.
- ZnO zinc oxide
- the peelable composition for protecting a coating of the present invention comprises a first acrylic emulsion containing an amino-modified fatty acid-based release agent and a second acrylic emulsion containing a zinc oxide (ZnO) curing agent, and has properties within a specific range described below
- the drying speed and crosslinking density of the film are controlled to improve not only the appearance characteristics of the film but also its mechanical properties such as water resistance and solvent resistance
- the surface tension of the composition is controlled to have appropriate adhesion without reacting with the body coating, thereby having the effect of protecting the coating.
- the peelable composition for film protection of the present invention may further comprise at least one additive selected from the group consisting of a neutralizing agent, a dispersing agent, a releasing agent, an antifreeze agent, an antifoaming agent, and a thickener.
- the first acrylic emulsion serves as a main resin of a peelable composition for film protection, improving storage properties and water resistance, and securing strength, elongation, and adhesive strength of a film protection film manufactured from it.
- the first acrylic emulsion can be directly synthesized according to a known method, or a commercially available product can be used.
- the first acrylic emulsion includes units derived from one or more monomers selected from the group consisting of ethyl acrylate (EA), hydroxyethyl acrylate (HEA), butyl acrylate (BA), methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate (BMA), hydroxyethyl methacrylate (HEMA), allyl methacrylate (AMA), acrylic acid (AA), and methacrylic acid (MAA), and units derived from an acrylonitrile (AN) monomer.
- EA ethyl acrylate
- HSA hydroxyethyl acrylate
- BA butyl acrylate
- MMA methyl methacrylate
- EMA ethyl methacrylate
- BMA butyl methacrylate
- HEMA allyl
- the first acrylic emulsion can be prepared from a mixture including n-butyl methacrylate (n-BMA), methyl methacrylate (MMA), butyl acrylate (BA), acrylic acid (AA), hydroxyethyl methacrylate (HEMA), and acrylonitrile (AN) as monomers.
- n-BMA n-butyl methacrylate
- MMA methyl methacrylate
- BA butyl acrylate
- acrylic acid AA
- HEMA hydroxyethyl methacrylate
- AN acrylonitrile
- the first acrylic emulsion contains 30 to 50 parts by weight, or 35 to 45 parts by weight, of an acrylonitrile monomer based on 100 parts by weight of the total monomer content contained in the first acrylic emulsion.
- the curing density is appropriate, so that the peeling strength and tensile strength of the film are excellent, which is advantageous.
- the film adhesion increases, so that the peeling strength may be high, and when it is below the above range, the curing density decreases, which may affect the chemical resistance and water resistance of the film.
- the first acrylic emulsion contains an amino-modified fatty acid-based release agent.
- the release effect is improved due to the flexibility of the amino-modified functional group, so that the film has appropriate peel strength and adhesion, and the problem of the appearance becoming opaque and hazy when a silicone-based release agent is used can be improved.
- the release agent is dispersed at an appropriate temperature of 40° C. or lower when contained in the first acrylic emulsion, so that there is no problem of the appearance becoming poor, and the dispersibility is improved, so that the release effect can be maximized.
- the first acrylic emulsion contains 1 to 5 parts by weight, or 2 to 4 parts by weight, of an amino-modified fatty acid-based release agent based on 100 parts by weight of the total monomer content of the first acrylic emulsion.
- an amino-modified fatty acid-based release agent contained in the first acrylic emulsion is within the above range, there is an advantage of having appropriate film adhesion and peel strength.
- it exceeds the above range the release property is good but the film peel strength is low but the adhesion may be poor, and when it is below the above range, the adhesion to the coating film is good but the peeling characteristics may be poor.
- an amino-modified fatty acid-based release agent that can be used in the present invention may be ADDITOL® XL 6568, available from Allnex.
- the first acrylic emulsion contains a solid content of 40 to 50 wt%, or 43 to 47 wt%, based on the total weight of the first acrylic emulsion.
- a solid content of 40 to 50 wt%, or 43 to 47 wt% based on the total weight of the first acrylic emulsion.
- the first acrylic emulsion may have a viscosity at 25°C of 30 to 200 cps, or 40 to 150 cps.
- the viscosity at 25°C of the first acrylic emulsion is within the above range, the viscosity of the peelable composition for protecting a coating film is appropriate, thereby providing an effect of improving workability.
- the viscosity at 25°C of the first acrylic emulsion is out of the above range, the workability of the composition may be insufficient, resulting in a problem of deterioration in the appearance characteristics of the manufactured coating film.
- the first acrylic emulsion may have an acid value (Av) of 1 to 10 mgKOH/g, or 3 to 8 mgKOH/g.
- Av acid value of 1 to 10 mgKOH/g, or 3 to 8 mgKOH/g.
- the acid value of the first acrylic emulsion is within the above range, the reactivity of a composition containing it can be controlled, thereby improving the appearance properties of a film manufactured therefrom.
- the acid value of the first acrylic emulsion is below the above range, the resin stability deteriorates, which may cause a problem in that the storability of the peelable composition deteriorates, and when it exceeds the above range, the viscosity of the composition increases due to increased resin cohesion, which may cause problems in that the workability and the water resistance of the film deteriorate.
- the first acrylic emulsion may have a pH of 7 to 10, or 8 to 10.
- the pH of the first acrylic emulsion is within the above range, the viscosity of the peelable composition for protecting a coating film is appropriate, thereby improving workability and storability.
- the pH of the first acrylic emulsion is outside the above range, the viscosity of the composition is low, resulting in insufficient workability, which may cause a problem in that the appearance characteristics of the manufactured coating film deteriorate.
- the first acrylic emulsion may have a glass transition temperature (Tg) of -15 to 20°C, or -10 to 10°C.
- Tg glass transition temperature
- the glass transition temperature of the first acrylic emulsion has the effect of having appropriate adhesion without reaction with a body coating, and improving the hardness and solvent resistance of the film.
- the glass transition temperature of the first acrylic emulsion is below the above range, there is a problem that the drying speed and crosslinking density of the film are reduced, resulting in a problem that the hardness and solvent resistance of the manufactured film are insufficient, and when it exceeds the above range, the film becomes brittle, which may deteriorate the appearance characteristics and elongation of the manufactured film.
- the first acrylic emulsion may have a weight average molecular weight (Mw) of 100,000 to 200,000 g/mol, or 120,000 to 180,000 g/mol.
- Mw weight average molecular weight
- the long-term physical properties of the manufactured film such as durability, adhesion, and weather resistance, may be excellent.
- the weight average molecular weight of the first acrylic emulsion is less than the above range, the molecular weight is small, so that the water resistance and weather resistance of the manufactured film are insufficient, and when it exceeds the above range, the flowability decreases due to the increase in molecular weight, so that the workability of the peelable composition for protecting a coating film including the same is poor, and the surface smoothness is poor, which may affect the appearance.
- the first acrylic emulsion may be in the form of an emulsion dispersed in deionized water.
- the first acrylic emulsion may have particles dispersed in the deionized water having an average diameter of 100 to 200 nm, or 130 to 170 nm.
- VOCs volatile organic compounds
- the first acrylic emulsion may be included in the composition in an amount of 60 to 70 wt%, or 61 to 68 wt%, based on the total weight of the peelable composition for film protection.
- the first acrylic emulsion When the first acrylic emulsion is included within the above content range, it has the effect of improving the peel strength and elongation of the film.
- the content of the first acrylic emulsion is less than the above range, there is a problem that the peel strength and elongation of the film are lowered, and when it exceeds the above range, there may be problems with the chemical resistance and water resistance of the film.
- the second acrylic emulsion is identical to the first acrylic emulsion except as described below.
- the second acrylic emulsion is an auxiliary resin of a peelable composition for film protection and serves to secure the tensile strength and drying properties of a film protection film produced therefrom.
- the second acrylic emulsion can be prepared from a mixture comprising n-butyl methacrylate (n-BMA), methyl methacrylate (MMA), acrylic acid (AA), and hydroxyethyl methacrylate (HEMA) as monomers.
- n-BMA n-butyl methacrylate
- MMA methyl methacrylate
- AA acrylic acid
- HEMA hydroxyethyl methacrylate
- the second acrylic emulsion unlike the first acrylic emulsion, does not contain butyl acrylate (BA), acrylonitrile (AN), or a release agent.
- BA butyl acrylate
- AN acrylonitrile
- the second acrylic emulsion contains 5 to 20 parts by weight, or 10 to 15 parts by weight, of a zinc oxide (ZnO) curing agent based on 100 parts by weight of the total monomer content of the second acrylic emulsion.
- a zinc oxide curing agent the acid group of the acrylic emulsion has an anionic charge, and the zinc oxide has a cationic charge, so that an ionic bond is formed, thereby improving the tensile strength and mechanical properties of the manufactured film.
- the content of the zinc oxide (ZnO) curing agent contained in the second acrylic emulsion is within the above range, the curing density is increased, thereby improving the chemical resistance and water resistance of the film.
- it exceeds the above range the zinc oxide remains without reacting, which may deteriorate the appearance of the film, and when it is less than the above range, the curing density is reduced, which may affect the chemical resistance and water resistance of the film.
- the second acrylic emulsion may have a viscosity at 25°C of 150 to 500 cps, or 150 to 250 cps.
- the viscosity at 25°C of the second acrylic emulsion is within the above range, the viscosity of the peelable composition for film protection is appropriate, thereby providing an effect of improving workability.
- the viscosity at 25°C of the second acrylic emulsion is out of the above range, the workability of the composition is insufficient, which may cause a problem in that the appearance characteristics of the manufactured film deteriorate.
- the second acrylic emulsion may have a glass transition temperature (Tg) of 40 to 60°C, or 45 to 55°C.
- Tg glass transition temperature
- the glass transition temperature of the second acrylic emulsion has an effect of having appropriate adhesion without reaction with the body coating, and improving the tensile strength of the film.
- the glass transition temperature of the second acrylic emulsion is below the above range, there is a problem that the drying speed and crosslinking density of the film are reduced, resulting in insufficient hardness and solvent resistance of the manufactured film, and when it exceeds the above range, the coating becomes brittle, resulting in insufficient appearance characteristics, tensile strength, and elongation of the manufactured film.
- the second acrylic emulsion may have a weight average molecular weight (Mw) of 200,000 to 300,000 g/mol, or 220,000 to 280,000 g/mol.
- Mw weight average molecular weight
- the long-term physical properties of the manufactured film such as durability, adhesion, and weather resistance, may be excellent.
- the weight average molecular weight of the second acrylic emulsion is less than the above range, the molecular weight is small, so that the water resistance and weather resistance of the manufactured film are insufficient, and when it exceeds the above range, the flowability decreases due to the increase in molecular weight, so that the workability of the peelable composition for protecting a coating film including the same deteriorates, and the surface smoothness is poor, which may cause a problem of deteriorating the appearance.
- the second acrylic emulsion may be in the form of an emulsion dispersed in deionized water.
- the second acrylic emulsion may have particles dispersed in deionized water having an average diameter of 150 to 200 nm, or 160 to 190 nm.
- VOCs volatile organic compounds
- the second acrylic emulsion contains a solid content of 40 to 50 wt%, or 43 to 47 wt%, based on the total weight of the second acrylic emulsion.
- the solid content of the second acrylic emulsion is within the above range, it has an excellent workability effect.
- the second acrylic emulsion may have an acid value (Av) of 1 to 10 mgKOH/g, or 3 to 8 mgKOH/g.
- Av acid value of 1 to 10 mgKOH/g, or 3 to 8 mgKOH/g.
- the acid value of the second acrylic emulsion is within the above range, the reactivity of a composition containing it can be controlled to improve the appearance properties of a film manufactured therefrom.
- the acid value of the second acrylic emulsion is below the above range, the resin stability may deteriorate, causing a problem in that the storability of the peelable composition may deteriorate.
- the viscosity of the composition may increase due to increased resin cohesion, causing problems in that the workability and the water resistance of the film may deteriorate.
- the second acrylic emulsion may have a pH of 7 to 10, or 8 to 10.
- the pH of the second acrylic emulsion is within the above range, the viscosity of the peelable composition for film protection is appropriate, so that workability is improved and storability is improved.
- the pH of the second acrylic emulsion is outside the above range, the viscosity of the composition is low, so that workability is insufficient, and a problem of deterioration of the appearance characteristics of the manufactured film may occur.
- the second acrylic emulsion may be included in the composition in an amount of 25 to 34 wt%, or 25 to 32 wt%, based on the total weight of the peelable composition for film protection.
- the second acrylic emulsion is included within the above content range, it has the effect of improving the tensile strength, peel strength, water resistance, and elongation of the film.
- the crosslinking density of the film decreases, which may cause a problem in that the tensile strength, chemical resistance, and water resistance decrease, and when it exceeds the above range, drying may proceed quickly, resulting in insufficient workability, which may cause a problem in that the appearance and tensile strength of the film decrease and the residual amount after film detachment may increase.
- the film can be removed cleanly without residue after removal by maintaining appropriate drying properties and having appropriate adhesion to the body coating.
- the solvent is water, which can be ion-exchanged water, distilled water, or ultrapure deionized water.
- the water solvent may be included in each acrylic emulsion in an amount of 20 to 40 wt% based on the total weight of each emulsion during the production of the first and second acrylic emulsions.
- the water solvent when preparing a peelable composition for coating protection, may be included in an amount of 0.1 to 10 wt%, or 0.3 to 3 wt%, based on the total weight of the peelable composition for coating protection.
- viscosity control can be facilitated, and the smoothness and workability of the coating protection film using the peelable composition for coating protection can be excellent.
- the peelable composition for film protection of the present invention may contain one or more additives selected from the group consisting of a neutralizing agent, a dispersing agent, a releasing agent, an antifreeze agent, an antifoaming agent, and a thickener.
- Additives may be added to a peelable composition for coating protection in a predetermined content range for the purpose of providing additional effects such as improving wettability and leveling properties during painting.
- the neutralizer may be included in an amount of 0.1 to 2 wt% or 0.1 to 1 wt%
- the antifreeze may be included in an amount of 0.1 to 5 wt% or 0.3 to 3 wt%
- the defoaming agent may be included in an amount of 0.1 to 3 wt% or 0.3 to 2 wt%
- the thickener may be included in an amount of 0.1 to 3 wt% or 0.3 to 2 wt%
- the releasing agent may be included in an amount of 0.1 to 5 wt% or 0.3 to 3 wt%
- the dispersing agent may be included in an amount of 0.1 to 2 wt% or 0.1 to 1 wt%.
- the release agent is included in the peelable composition for film protection separately from the release agent included in the first acrylic emulsion.
- the present invention can provide a coating protection film manufactured from a peelable composition for coating protection that is easy to peel and has excellent adhesive strength for protecting a coating surface of an automobile or heavy equipment, etc.
- the coating protective film of the present invention can be produced by curing the peelable composition for coating protection of the present invention.
- the peelable composition for coating protection of the present invention can be applied to a thickness of 10 to 100 ⁇ m on a conductor by spraying, brushing, or roller, and then cured by drying at room temperature, curing in an oven, or curing with an IR lamp, etc., to form a coating protection film.
- experimental examples include working examples and comparative examples.
- the experimental examples are only intended to help understand the present invention and the scope of the present invention is not limited to these in any way.
- the first and second acrylic emulsions were prepared according to the procedure below with the compositions shown in Table 1.
- a peelable composition for film protection was manufactured by sequentially adding solvent and additives while stirring after adding the first and second acrylic emulsions manufactured previously, according to the compositions shown in Tables 3 and 4 below.
- a peelable composition for coating protection manufactured by mixing the compositions in Tables 3 and 4, was applied to a substrate coated with automotive clear paint by a spray method with a coating thickness of 50 ⁇ m, and then cured at 80° C. for 3 minutes to form a coating protection film.
- Peel strength The peel strength was measured to evaluate the adhesive strength and peel performance when peeling the film. A film of 25 mm x 50 mm (width x length) and 50 ⁇ m thickness was cured at 80°C for 3 minutes and measured 24 hours later. The measurement was made using a UTM (Universal Testing Machine) at a tensile speed of 300 mm/min and a peeling direction of 180 degrees. The peel strength was evaluated as good when it was 0.6 to 2.0 N.
- Tensile strength The tensile strength, which is the toughness and toughness of the film, was measured.
- the film with a size of 25 mm x 50 mm (width x length) and a film thickness of 50 ⁇ m was measured using a UTM (Universal Testing Machine) at 23°C and RH 65%.
- Wmax/A0 Wmax: maximum tensile load, A0: cross-sectional area.
- a tensile strength of 10 N or more was evaluated as good.
- Elongation The elongation, which is the extent to which the film stretches, was measured.
- a film of 25 mm x 50 mm (width x length) and 50 ⁇ m thickness was measured using a UTM (Universal Testing Machine) at 23°C and RH 65%.
- Experimental Example 14 which did not use the second acrylic emulsion but used one type of acrylic emulsion, had poor chemical resistance and water resistance.
- Experimental Example 15 which did not use the first acrylic emulsion but used one type of acrylic emulsion, had poor adhesion and tensile strength.
- Experimental Example 16 which used an acrylic emulsion that did not contain an amino-modified fatty acid-based release agent or a zinc oxide hardener, had poor adhesion and chemical resistance.
- a peelable composition for protecting a coating film comprising a first acrylic emulsion and a second acrylic emulsion, wherein the first acrylic emulsion comprises an amino-modified fatty acid-based release agent, and the second acrylic emulsion comprises a zinc oxide (ZnO) curing agent.
- a peelable composition for protecting a film wherein the first acrylic emulsion contains 30 to 50 parts by weight of an acrylonitrile monomer and 1 to 5 parts by weight of an amino-modified fatty acid-based release agent based on 100 parts by weight of the total amount of monomers contained in the first acrylic emulsion.
- a peelable composition for protecting a coating film wherein the second acrylic emulsion contains 5 to 20 parts by weight of a zinc oxide (ZnO) curing agent based on 100 parts by weight of the total amount of monomers contained in the second acrylic emulsion.
- ZnO zinc oxide
- a peelable composition for protecting a film wherein the first acrylic emulsion has a glass transition temperature (Tg) of -15 to 20°C, a solid content of 40 to 50 wt% based on the total weight of the first acrylic emulsion, a viscosity at 25°C of 30 to 200 cPs, an acid value of 1 to 10 mgKOH/g, a pH of 7 to 10, a weight average molecular weight (Mw) of 100,000 to 200,000 g/mol, and an average particle diameter of 100 to 200 nm.
- Tg glass transition temperature
- Mw weight average molecular weight
- a peelable composition for protecting a film wherein the second acrylic emulsion has a glass transition temperature (Tg) of 40 to 60°C, a solid content of 40 to 50 wt% based on the total weight of the second acrylic emulsion, a viscosity at 25°C of 150 to 500 cPs, an acid value of 1 to 10 mgKOH/g, a pH of 7 to 10, a weight average molecular weight (Mw) of 200,000 to 300,000 g/mol, and an average particle diameter of 150 to 200 nm.
- Tg glass transition temperature
- Mw weight average molecular weight
- a peelable composition for film protection comprising 60 to 70 wt% of a first acrylic emulsion and 25 to 34 wt% of a second acrylic emulsion based on the total weight of the peelable composition for film protection.
- a coating protection film manufactured by curing a peelable composition for coating protection according to the present invention is a coating protection film manufactured by curing a peelable composition for coating protection according to the present invention.
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Abstract
Description
본 발명은 자동차 또는 중장비 등의 도장면을 임시적으로 보호하고 박리가 용이하면서도 접착력이 우수한 도막 보호용 박리 가능한 조성물에 관한 것이다.The present invention relates to a peelable composition for temporarily protecting a painted surface of an automobile or heavy equipment, etc., and having excellent adhesive strength while being easy to peel.
자동차 또는 중장비 등이 최종 수요자에게 전해지기까지 일시적으로 옥외에 보관되거나 수송 중에 예컨대 모래먼지, 철분, 염류, 알칼리류, 산류, 매연, 곤충의 사해나 체액 등의 오염물이나, 태양광선, 풍우 및 그 외의 영향에 의해 이들 도장면에 외상, 얼룩, 변색, 오염 등이 발생할 가능성이 많다. 또한 물리력에 의해 재질에 외상이 발생하는 경우도 있을 수 있다.Automobiles or heavy equipment, etc., are temporarily stored outdoors or during transportation before being delivered to the final user. There is a high possibility that their painted surfaces may be damaged, stained, discolored, or contaminated by contaminants such as sand, dust, iron, salts, alkalis, acids, soot, insect waste or bodily fluids, sunlight, wind, and other influences. There may also be cases where physical force causes damage to the material.
따라서 자동차 또는 중장비 등의 표면을 오염물이나 태양광선, 풍우, 외상 등으로부터 일시적으로 보호하기 위하여 제품의 출하 단계부터 미리 표면에 도포하고, 일정 시간의 보관이 종료된 후에 쉽게 박리할 수 있는 많은 박리가능성 피복조성물이 제안되어 있다.Accordingly, many peelable coating compositions have been proposed that can be applied to the surface of a car or heavy equipment in advance at the product shipment stage to temporarily protect the surface from contaminants, sunlight, wind and rain, trauma, etc., and can be easily peeled off after a certain period of storage.
그러나 종래 피복조성물의 경우 제거시에 석유계 용제를 사용할 필요가 있어 대기오염 등 환경문제가 있다. 또한 알칼리 가용성 수지를 주성분으로 하는 조성물도 사용되고 있으나, 제거시에 알칼리 세제를 사용하므로 수질오염 등 환경오염의 문제가 있다.However, in the case of conventional coating compositions, there are environmental problems such as air pollution because petroleum-based solvents must be used when removing them. In addition, compositions containing alkali-soluble resins as their main components are also being used, but since alkaline detergents are used when removing them, there are environmental problems such as water pollution.
따라서 자동차 또는 중장비 등의 코팅면을 보호하기 위하여 박리가 용이하면서도 접착력이 우수한 도막 보호용 박리 가능한 조성물의 개발이 요구된다.Therefore, in order to protect the coating surface of automobiles or heavy equipment, the development of a peelable composition for film protection that is easy to peel and has excellent adhesive strength is required.
[선행기술문헌][Prior art literature]
(특허문헌 1) 대한민국 등록특허 제10-0498717호(2005.06.22.)(Patent Document 1) Republic of Korea Registered Patent No. 10-0498717 (June 22, 2005)
본 발명은 하나의 양상에서 자동차 또는 중장비 등의 코팅면을 보호하기 위하여 박리가 용이하면서도 접착력이 우수한 도막 보호용 박리 가능한 조성물을 제공하고자 한다.In one aspect, the present invention seeks to provide a peelable composition for protecting a coating surface of an automobile or heavy equipment, which is easy to peel and has excellent adhesive strength.
본 발명은 또 다른 양상에서 자동차 또는 중장비 등의 코팅면을 보호하기 위하여 박리가 용이하면서도 접착력이 우수한 도막 보호용 박리 가능한 조성물로부터 제조된 도막 보호 필름을 제공하고자 한다.In another aspect, the present invention provides a coating protection film manufactured from a peelable composition for coating protection that is easy to peel and has excellent adhesive strength for protecting a coating surface of an automobile or heavy equipment, etc.
본 발명은 하나의 양상에서, 제1 아크릴 에멀젼 및 제2 아크릴 에멀젼을 포함하며, 제1 아크릴 에멀젼은 아미노 변성 지방산계 이형제를 포함하며, 제2 아크릴 에멀젼은 산화아연(ZnO) 경화제를 포함하는 도막 보호용 박리 가능한 조성물을 제공한다.In one aspect, the present invention provides a strippable composition for protecting a coating film, comprising a first acrylic emulsion and a second acrylic emulsion, wherein the first acrylic emulsion comprises an amino-modified fatty acid-based release agent, and the second acrylic emulsion comprises a zinc oxide (ZnO) curing agent.
본 발명은 또 다른 양상에서, 본 발명에 따르는 도막 보호용 박리 가능한 조성물의 경화에 의해 제조되는 도막 보호 필름을 제공한다.In another aspect, the present invention provides a coating protection film manufactured by curing a peelable composition for coating protection according to the present invention.
본 발명의 하나의 양상에 따르는 도막 보호용 박리 가능한 조성물은 건조속도가 빠르고, 초기 접착력과 우수한 접착 유지력을 가지며, 필름이 깨끗하게 제거될 수 있으며, 탈착 후 잔류물을 남기지 않고 내수성, 내약품성 및 인장강도가 우수한 것을 특징으로 한다.A peelable composition for film protection according to one aspect of the present invention is characterized by having a fast drying speed, excellent initial adhesion and excellent adhesion retention, the film can be removed cleanly, does not leave residue after detachment, and has excellent water resistance, chemical resistance, and tensile strength.
이하 본 발명을 실시예를 참조하여 상세하게 설명한다. 그러나, 하기 내용에 의해서만 한정되는 것은 아니며, 필요에 따라 각 구성 요소가 다양하게 변형되거나 선택적으로 혼용될 수 있다. 따라서, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.Hereinafter, the present invention will be described in detail with reference to examples. However, it is not limited to the following contents, and each component may be variously modified or selectively mixed as needed. Therefore, it should be understood that all modifications, equivalents, or substitutes included in the spirit and technical scope of the present invention are included.
본 명세서에서 사용된 "유리전이온도"는 해당 기술 분야에 알려진 통상의 방법에 의해 측정된 것이며, 예를 들어 열기계분석법(thermomechanical analysis, TMA) 또는 시차주사열량분석법(differential scanning calorimetry, DSC)으로 측정할 수 있다. The “glass transition temperature” used herein is measured by a conventional method known in the art, and can be measured by, for example, thermomechanical analysis (TMA) or differential scanning calorimetry (DSC).
"중량평균분자량"은 해당 기술 분야에 알려진 통상의 방법에 의해 측정된 것이며, 예를 들어 GPC(gel permeation chromatograph) 방법으로 측정할 수 있다. “Weight average molecular weight” is measured by a conventional method known in the art, and can be measured by, for example, the GPC (gel permeation chromatography) method.
"산가" 및 "수산기가"와 같은 작용기가는 해당 기술 분야에 알려진 통상의 방법에 의해 측정할 수 있으며, 예를 들어 적정(titration)의 방법으로 측정한 값을 나타낼 수 있다. Functional values such as “acid value” and “hydroxyl value” can be measured by conventional methods known in the art, and can represent values measured by, for example, a titration method.
"입자 직경(D50)"은 해당 기술 분야에 알려진 통상의 방법에 의해 측정된 것이며, 예를 들어 레이저 광 산란법(laser light scattering, LLS)으로 측정할 수 있다. “Particle diameter (D50)” is measured by a conventional method known in the art, and can be measured, for example, by laser light scattering (LLS).
또한, "점도"는 해당 기술분야에 알려진 통상의 방법에 의해 측정된 것이며, 예를 들어 상온(25℃)에서 브룩필드 점도계(회전 스핀들 점도계, Brookfield Viscometer)를 사용하여 측정할 수 있다.Additionally, “viscosity” is measured by a conventional method known in the art, and can be measured, for example, using a Brookfield viscometer (rotating spindle viscometer) at room temperature (25°C).
<도막 보호용 박리 가능한<Peelable for film protection 조성물>Composition>
본 발명은 하나의 양상에서 자동차 또는 중장비 등의 코팅면을 보호하기 위하여 차체 도막과의 반응이 없고 박리가 용이하면서도 접착력이 우수한 도막 보호용 박리 가능한 조성물을 제공할 수 있다.In one aspect, the present invention can provide a peelable composition for protecting a coating surface of an automobile or heavy equipment, which does not react with a body coating, is easy to peel, and has excellent adhesive strength.
본 발명의 하나의 실시예에 따르는 도막 보호용 박리 가능한 조성물은 제1 아크릴 에멀젼 및 제2 아크릴 에멀젼을 포함한다.A peelable composition for film protection according to one embodiment of the present invention comprises a first acrylic emulsion and a second acrylic emulsion.
본 발명의 제1 아크릴 에멀젼은 아미노 변성 지방산계 이형제를 포함하고, 제2 아크릴 에멀젼은 산화아연(ZnO) 경화제를 포함한다.The first acrylic emulsion of the present invention contains an amino-modified fatty acid-based release agent, and the second acrylic emulsion contains a zinc oxide (ZnO) curing agent.
본 발명의 도막 보호용 박리 가능한 조성물이 아미노 변성 지방산계 이형제를 함유하는 제1 아크릴 에멀젼과 산화아연(ZnO) 경화제를 함유하는 제2 아크릴 에멀젼을 포함하고, 후술하는 특정 범위의 물성을 가지는 경우, 필름의 건조 속도 및 가교 밀도를 조절하여 필름의 외관 특성뿐만 아니라 내수성 및 내용제성 등의 기계적 물성을 향상시키고 조성물의 표면 장력을 조절하여 차체 도막과 반응 없이 적절한 부착성을 가져 도막을 보호하는 효과가 있다.When the peelable composition for protecting a coating of the present invention comprises a first acrylic emulsion containing an amino-modified fatty acid-based release agent and a second acrylic emulsion containing a zinc oxide (ZnO) curing agent, and has properties within a specific range described below, the drying speed and crosslinking density of the film are controlled to improve not only the appearance characteristics of the film but also its mechanical properties such as water resistance and solvent resistance, and the surface tension of the composition is controlled to have appropriate adhesion without reacting with the body coating, thereby having the effect of protecting the coating.
본 발명의 도막 보호용 박리 가능한 조성물은 중화제, 분산제, 이형제, 동결방지제, 소포제, 및 증점제로 구성된 그룹으로부터 선택되는 1종 이상의 첨가제를 더욱 포함할 수 있다.The peelable composition for film protection of the present invention may further comprise at least one additive selected from the group consisting of a neutralizing agent, a dispersing agent, a releasing agent, an antifreeze agent, an antifoaming agent, and a thickener.
이하, 상기 성분들을 구체적으로 설명한다.Below, the above components are described in detail.
제1 아크릴 에멀젼1st acrylic emulsion
제1 아크릴 에멀젼은 도막 보호용 박리 가능한 조성물의 주수지로서 저장성 및 내수성을 향상시키고, 이로부터 제조된 도막 보호 필름의 강도, 신율 및 부착력을 확보하는 역할을 한다.The first acrylic emulsion serves as a main resin of a peelable composition for film protection, improving storage properties and water resistance, and securing strength, elongation, and adhesive strength of a film protection film manufactured from it.
제1 아크릴 에멀젼은 공지된 방법에 따라 직접 합성된 것을 사용하거나, 시판되는 제품을 사용할 수 있다. 예를 들어, 제1 아크릴 에멀젼은 에틸 아크릴레이트(EA), 하이드록시에틸 아크릴레이트(HEA), 부틸 아크릴레이트(BA), 메틸 메타크릴레이트(MMA), 에틸 메타크릴레이트(EMA), 부틸 메타크릴레이트(BMA), 하이드록시에틸 메타크릴레이트(HEMA), 알릴 메타크릴레이트(AMA), 아크릴산(AA), 및 메타크릴산(MAA)으로 이루어진 군으로부터 선택된 1종 이상의 단량체 유래 단위, 및 아크릴로니트릴(AN) 단량체 유래 단위를 포함한다. 또 다른 예로, 제1 아크릴 에멀젼은 모노머로서 n-부틸 메타크릴레이트(n-BMA), 메틸 메타크릴레이트(MMA), 부틸 아크릴레이트(BA), 아크릴산(AA), 하이드록시에틸 메타크릴레이트(HEMA), 및 아크릴로니트릴(AN)을 포함하는 혼합물로부터 제조될 수 있다.The first acrylic emulsion can be directly synthesized according to a known method, or a commercially available product can be used. For example, the first acrylic emulsion includes units derived from one or more monomers selected from the group consisting of ethyl acrylate (EA), hydroxyethyl acrylate (HEA), butyl acrylate (BA), methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate (BMA), hydroxyethyl methacrylate (HEMA), allyl methacrylate (AMA), acrylic acid (AA), and methacrylic acid (MAA), and units derived from an acrylonitrile (AN) monomer. As another example, the first acrylic emulsion can be prepared from a mixture including n-butyl methacrylate (n-BMA), methyl methacrylate (MMA), butyl acrylate (BA), acrylic acid (AA), hydroxyethyl methacrylate (HEMA), and acrylonitrile (AN) as monomers.
여기서 제1 아크릴 에멀젼은, 제1 아크릴 에멀젼에 포함된 모노머 총량 100 중량부를 기준으로 아크릴로니트릴 모노머 30 내지 50 중량부, 또는 35 내지 45 중량부를 포함한다. 제1 아크릴 에멀젼에 포함되는 아크릴로니트릴 모노머의 함량이 상기 범위 이내인 경우 경화 밀도가 적절하여 필름의 박리강도, 인장강도가 우수한 장점이 있다. 상기 범위 초과인 경우 도막 부착성이 증가해서 박리강도가 높아질 수 있고, 상기 범위 미만인 경우 경화 밀도가 떨어져서 필름의 내약품성, 내수성에 영향을 미칠 수 있다 Here, the first acrylic emulsion contains 30 to 50 parts by weight, or 35 to 45 parts by weight, of an acrylonitrile monomer based on 100 parts by weight of the total monomer content contained in the first acrylic emulsion. When the content of the acrylonitrile monomer contained in the first acrylic emulsion is within the above range, the curing density is appropriate, so that the peeling strength and tensile strength of the film are excellent, which is advantageous. When it exceeds the above range, the film adhesion increases, so that the peeling strength may be high, and when it is below the above range, the curing density decreases, which may affect the chemical resistance and water resistance of the film.
제1 아크릴 에멀젼은 아미노 변성 지방산계 이형제를 포함한다. 상기 아미노 변성 지방산계 이형제를 포함하는 경우 아미노 변성 관능기의 유연성으로 인하여 이형성 효과를 향상시켜 적절한 필름의 박리강도 및 부착성을 가지며, 실리콘계 이형제를 사용할 때 외관이 불투명하게 흐릿해지는 문제점을 개선할 수 있다. 특히, 아미노 변성 지방산계 이형제가 도막 보호용 박리 가능한 조성물에만 포함되는 것에 대비하여 제1 아크릴 에멀젼에 포함될 경우 40 ℃ 이하의 적절한 온도에서 분산되어 외관이 불량해지는 문제가 없고, 분산성이 향상되어 이형성 효과를 극대화시킬 수 있다.The first acrylic emulsion contains an amino-modified fatty acid-based release agent. When the amino-modified fatty acid-based release agent is contained, the release effect is improved due to the flexibility of the amino-modified functional group, so that the film has appropriate peel strength and adhesion, and the problem of the appearance becoming opaque and hazy when a silicone-based release agent is used can be improved. In particular, when the amino-modified fatty acid-based release agent is contained only in a peelable composition for film protection, the release agent is dispersed at an appropriate temperature of 40° C. or lower when contained in the first acrylic emulsion, so that there is no problem of the appearance becoming poor, and the dispersibility is improved, so that the release effect can be maximized.
제1 아크릴 에멀젼은 제1 아크릴 에멀젼에 포함된 모노머 총량 100 중량부를 기준으로 아미노 변성 지방산계 이형제 1 내지 5 중량부, 또는 2 내지 4 중량부를 포함한다. 제1 아크릴 에멀젼에 포함되는 아미노 변성 지방산계 이형제의 함량이 상기 범위 이내인 경우 적절한 필름의 부착성과 박리강도를 가지는 장점이 있다. 상기 범위 초과인 경우 이형성이 좋아 필름의 박리강도는 낮아지나 부착성이 떨어질 수 있고, 상기 범위 미만인 경우 도막과의 부착성은 좋아지나 박리 특성이 떨어질 수 있다. The first acrylic emulsion contains 1 to 5 parts by weight, or 2 to 4 parts by weight, of an amino-modified fatty acid-based release agent based on 100 parts by weight of the total monomer content of the first acrylic emulsion. When the content of the amino-modified fatty acid-based release agent contained in the first acrylic emulsion is within the above range, there is an advantage of having appropriate film adhesion and peel strength. When it exceeds the above range, the release property is good but the film peel strength is low but the adhesion may be poor, and when it is below the above range, the adhesion to the coating film is good but the peeling characteristics may be poor.
구체적으로 본 발명에서 사용될 수 있는 아미노 변성 지방산계 이형제는 Allnex사로부터 구입가능한 ADDITOL® XL 6568일 수 있다.Specifically, an amino-modified fatty acid-based release agent that can be used in the present invention may be ADDITOL® XL 6568, available from Allnex.
제1 아크릴 에멀젼은 제1 아크릴 에멀젼 총 중량을 기준으로 40 내지 50 중량%, 또는 43 내지 47 중량%의 고형분을 포함한다. 제1 아크릴 에멀젼의 고형분 함량이 상기 범위 내일 경우 작업성이 우수한 효과가 있다.The first acrylic emulsion contains a solid content of 40 to 50 wt%, or 43 to 47 wt%, based on the total weight of the first acrylic emulsion. When the solid content of the first acrylic emulsion is within the above range, excellent workability is achieved.
제1 아크릴 에멀젼은 25℃에서의 점도가 30 내지 200 cps, 또는 40 내지 150 cps일 수 있다. 제1 아크릴 에멀젼의 25℃에서의 점도가 상기 범위 내인 경우, 도막 보호용 박리 가능한 조성물의 점도가 적절하여 작업성이 상향되는 효과가 있다. 제1 아크릴 에멀젼의 25℃에서의 점도가 상기 범위를 벗어나는 경우 조성물의 작업성이 부족하여 제조된 도막의 외관 특성이 저하되는 문제가 발생할 수 있다.The first acrylic emulsion may have a viscosity at 25°C of 30 to 200 cps, or 40 to 150 cps. When the viscosity at 25°C of the first acrylic emulsion is within the above range, the viscosity of the peelable composition for protecting a coating film is appropriate, thereby providing an effect of improving workability. When the viscosity at 25°C of the first acrylic emulsion is out of the above range, the workability of the composition may be insufficient, resulting in a problem of deterioration in the appearance characteristics of the manufactured coating film.
제1 아크릴 에멀젼은 산가(Av)가 1 내지 10 mgKOH/g, 또는 3 내지 8 mgKOH/g일 수 있다. 제1 아크릴 에멀젼의 산가가 상기 범위 내일 경우 이를 포함하는 조성물의 반응성을 조절하여 이로부터 제조된 필름의 외관 특성을 향상시킬 수 있다. 제1 아크릴 에멀젼의 산가가 상기 범위 미만인 경우 수지 안정성이 저하되어 박리 가능한 조성물의 저장성이 저하되는 문제가 발생하고, 상기 범위 초과인 경우 수지 응집성 증대로 조성물의 점도가 증가하여 작업성 및 필름의 내수성이 저하되는 문제가 발생할 수 있다.The first acrylic emulsion may have an acid value (Av) of 1 to 10 mgKOH/g, or 3 to 8 mgKOH/g. When the acid value of the first acrylic emulsion is within the above range, the reactivity of a composition containing it can be controlled, thereby improving the appearance properties of a film manufactured therefrom. When the acid value of the first acrylic emulsion is below the above range, the resin stability deteriorates, which may cause a problem in that the storability of the peelable composition deteriorates, and when it exceeds the above range, the viscosity of the composition increases due to increased resin cohesion, which may cause problems in that the workability and the water resistance of the film deteriorate.
제1 아크릴 에멀젼은 pH가 7 내지 10, 또는 8 내지 10일 수 있다. 제1 아크릴 에멀젼의 pH가 상기 범위 내인 경우, 도막 보호용 박리 가능한 조성물의 점도가 적절하여 작업성이 상향되고 저장성이 개선되는 효과가 있다. 제1 아크릴 에멀젼의 pH가 상기 범위를 벗어나는 경우 조성물의 점도가 낮아 작업성이 부족하여 제조된 도막의 외관 특성이 저하되는 문제가 발생할 수 있다.The first acrylic emulsion may have a pH of 7 to 10, or 8 to 10. When the pH of the first acrylic emulsion is within the above range, the viscosity of the peelable composition for protecting a coating film is appropriate, thereby improving workability and storability. When the pH of the first acrylic emulsion is outside the above range, the viscosity of the composition is low, resulting in insufficient workability, which may cause a problem in that the appearance characteristics of the manufactured coating film deteriorate.
제1 아크릴 에멀젼은 유리전이온도(Tg)가 -15 내지 20℃, 또는 -10 내지 10℃일 수 있다. 제1 아크릴 에멀젼의 유리전이온도가 상기 범위 내일 경우, 차체 도막과의 반응 없이 적절한 부착력을 가지고, 필름의 경도 및 내용제성이 향상되는 효과가 있다. 제1 아크릴 에멀젼의 유리전이온도가 상기 범위 미만인 경우 필름의 건조 속도 및 가교밀도가 저하되어 제조된 필름의 경도 및 내용제성이 부족해지는 문제가 있고, 상기 범위 초과인 경우 필름이 브리틀(brittle)해져 제조된 필름의 외관 특성 및 신율이 떨어질 수 있다.The first acrylic emulsion may have a glass transition temperature (Tg) of -15 to 20°C, or -10 to 10°C. When the glass transition temperature of the first acrylic emulsion is within the above range, it has the effect of having appropriate adhesion without reaction with a body coating, and improving the hardness and solvent resistance of the film. When the glass transition temperature of the first acrylic emulsion is below the above range, there is a problem that the drying speed and crosslinking density of the film are reduced, resulting in a problem that the hardness and solvent resistance of the manufactured film are insufficient, and when it exceeds the above range, the film becomes brittle, which may deteriorate the appearance characteristics and elongation of the manufactured film.
제1 아크릴 에멀젼은 중량평균분자량(Mw)이 100,000 내지 200,000 g/mol, 또는 120,000 내지 180,000 g/mol일 수 있다. 제1 아크릴 에멀젼의 중량평균분자량이 상기 범위 내일 경우, 제조된 필름의 내구성, 부착성 및 내후성 등의 장기 물성이 우수할 수 있다. 제1 아크릴 에멀젼의 중량평균분자량이 상기 범위 미만인 경우 분자량이 작아 제조된 필름의 내수성 및 내후성이 부족해지고, 상기 범위 초과인 경우 분자량 증가에 따른 흐름성이 저하되어 이를 포함하는 도막 보호용 박리 가능한 조성물의 작업성이 불량해지고 표면평활성이 좋지 않아 외관에 영향을 줄 수 있다.The first acrylic emulsion may have a weight average molecular weight (Mw) of 100,000 to 200,000 g/mol, or 120,000 to 180,000 g/mol. When the weight average molecular weight of the first acrylic emulsion is within the above range, the long-term physical properties of the manufactured film, such as durability, adhesion, and weather resistance, may be excellent. When the weight average molecular weight of the first acrylic emulsion is less than the above range, the molecular weight is small, so that the water resistance and weather resistance of the manufactured film are insufficient, and when it exceeds the above range, the flowability decreases due to the increase in molecular weight, so that the workability of the peelable composition for protecting a coating film including the same is poor, and the surface smoothness is poor, which may affect the appearance.
제1 아크릴 에멀젼은 탈이온수(deionized water)에 분산된 에멀젼 형태일 수 있다. 제1 아크릴 에멀젼은 탈이온수에 분산된 입자의 평균 직경이 100 내지 200nm, 또는 130 내지 170nm일 수 있다. 제1 아크릴 에멀젼이 탈이온수에 분산된 에멀젼 형태일 경우, 박리 가능한 조성물의 휘발성 유기 화합물(VOC, Volatile organic compounds) 함량을 낮출 수 있는 효과가 있으며, 입자의 평균 직경이 상기 범위 내일 경우 외관 및 입자안정성이 양호하다.The first acrylic emulsion may be in the form of an emulsion dispersed in deionized water. The first acrylic emulsion may have particles dispersed in the deionized water having an average diameter of 100 to 200 nm, or 130 to 170 nm. When the first acrylic emulsion is in the form of an emulsion dispersed in deionized water, it has the effect of reducing the content of volatile organic compounds (VOCs) of the peelable composition, and when the average diameter of the particles is within the above range, the appearance and particle stability are good.
제1 아크릴 에멀젼은 도막 보호용 박리 가능한 조성물의 총 중량을 기준으로 60 내지 70 중량%, 또는 61 내지 68 중량%의 함량으로 조성물에 포함될 수 있다. 제1 아크릴 에멀젼이 상기 함량 범위 내로 포함되는 경우, 필름의 박리강도 및 신율을 개선하는 효과가 있다. 제1 아크릴 에멀젼의 함량이 상기 범위 미만인 경우 필름의 박리강도와 신율이 낮아지는 문제가 있고, 상기 범위 초과인 경우 필름의 내약품성과 내수성에 문제가 발생할 수 있다.The first acrylic emulsion may be included in the composition in an amount of 60 to 70 wt%, or 61 to 68 wt%, based on the total weight of the peelable composition for film protection. When the first acrylic emulsion is included within the above content range, it has the effect of improving the peel strength and elongation of the film. When the content of the first acrylic emulsion is less than the above range, there is a problem that the peel strength and elongation of the film are lowered, and when it exceeds the above range, there may be problems with the chemical resistance and water resistance of the film.
제2 아크릴 에멀젼2nd acrylic emulsion
제2 아크릴 에멀젼은 이하에서 설명하는 사항을 제외하고는 제1 아크릴 에멀젼과 동일하다.The second acrylic emulsion is identical to the first acrylic emulsion except as described below.
제2 아크릴 에멀젼은 도막 보호용 박리 가능한 조성물의 보조수지로서 이로부터 제된 도막 보호 필름의 인장 강도와 건조성을 확보하는 역할을 한다.The second acrylic emulsion is an auxiliary resin of a peelable composition for film protection and serves to secure the tensile strength and drying properties of a film protection film produced therefrom.
하나의 실시예에서, 제2 아크릴 에멀젼은 모노머로서 n-부틸 메타크릴레이트(n-BMA), 메틸 메타크릴레이트(MMA), 아크릴산(AA), 및 하이드록시에틸 메타크릴레이트(HEMA)를 포함하는 혼합물로부터 제조될 수 있다.In one embodiment, the second acrylic emulsion can be prepared from a mixture comprising n-butyl methacrylate (n-BMA), methyl methacrylate (MMA), acrylic acid (AA), and hydroxyethyl methacrylate (HEMA) as monomers.
여기서 제2 아크릴 에멀젼은 제1 아크릴 에멀젼과 달리, 부틸 아크릴레이트(BA), 아크릴로니트릴(AN), 및 이형제를 함유하지 않는다.Here, the second acrylic emulsion, unlike the first acrylic emulsion, does not contain butyl acrylate (BA), acrylonitrile (AN), or a release agent.
반면 제2 아크릴 에멀젼은, 제2 아크릴 에멀젼에 포함된 모노머 총량 100 중량부를 기준으로 산화아연(ZnO) 경화제 5 내지 20 중량부, 또는 10 내지 15 중량부를 포함한다. 제2 아크릴 에멀젼에 산화아연 경화제를 포함하면 아크릴 에멀젼의 산기가 음이온 전하를 가지고, 산화아연은 양이온 전하를 가져서 이온결합을 형성함으로 제조된 필름의 인장강도 기계적물성을 향상시키는 장점이 있다. 제2 아크릴 에멀젼에 포함되는 산화아연(ZnO) 경화제의 함량이 상기 범위 이내인 경우 경화밀도를 높여줘서 필름의 내약품성 및 내수성이 좋아지는 장점이 있다. 상기 범위 초과인 경우 산화아연이 반응하지 않고 남아서 필름의 외관이 불량해질 수 있고, 상기 범위 미만인 경우 경화밀도가 떨어져서 필름의 내약품성 및 내수성에 영향을 미칠 수 있다. On the other hand, the second acrylic emulsion contains 5 to 20 parts by weight, or 10 to 15 parts by weight, of a zinc oxide (ZnO) curing agent based on 100 parts by weight of the total monomer content of the second acrylic emulsion. When the second acrylic emulsion contains a zinc oxide curing agent, the acid group of the acrylic emulsion has an anionic charge, and the zinc oxide has a cationic charge, so that an ionic bond is formed, thereby improving the tensile strength and mechanical properties of the manufactured film. When the content of the zinc oxide (ZnO) curing agent contained in the second acrylic emulsion is within the above range, the curing density is increased, thereby improving the chemical resistance and water resistance of the film. When it exceeds the above range, the zinc oxide remains without reacting, which may deteriorate the appearance of the film, and when it is less than the above range, the curing density is reduced, which may affect the chemical resistance and water resistance of the film.
제2 아크릴 에멀젼은 25℃에서의 점도가 150 내지 500 cps, 또는 150 내지 250 cps일 수 있다. 제2 아크릴 에멀젼의 25℃에서의 점도가 상기 범위 내인 경우, 도막 보호용 박리 가능한 조성물의 점도가 적절하여 작업성이 상향되는 효과가 있다. 제2 아크릴 에멀젼의 25℃에서의 점도가 상기 범위를 벗어나는 경우 조성물의 작업성이 부족하여 제조된 필름의 외관 특성이 저하되는 문제가 발생할 수 있다.The second acrylic emulsion may have a viscosity at 25°C of 150 to 500 cps, or 150 to 250 cps. When the viscosity at 25°C of the second acrylic emulsion is within the above range, the viscosity of the peelable composition for film protection is appropriate, thereby providing an effect of improving workability. When the viscosity at 25°C of the second acrylic emulsion is out of the above range, the workability of the composition is insufficient, which may cause a problem in that the appearance characteristics of the manufactured film deteriorate.
제2 아크릴 에멀젼은 유리전이온도(Tg)가 40 내지 60℃, 또는 45 내지 55℃일 수 있다. 제2 아크릴 에멀젼의 유리전이온도가 상기 범위 내일 경우, 차체 도막과의 반응 없이 적절한 부착력을 가지고, 필름의 인장강도가 향상되는 효과가 있다. 제2 아크릴 에멀젼의 유리전이온도가 상기 범위 미만인 경우 필름의 건조 속도 및 가교밀도가 저하되어 제조된 필름의 경도 및 내용제성이 부족해지는 문제가 있고, 상기 범위 초과인 경우 도막이 브리틀(brittle)해져 제조된 필름의 외관 특성, 인장강도 및 신율이 부족해질 수 있다.The second acrylic emulsion may have a glass transition temperature (Tg) of 40 to 60°C, or 45 to 55°C. When the glass transition temperature of the second acrylic emulsion is within the above range, it has an effect of having appropriate adhesion without reaction with the body coating, and improving the tensile strength of the film. When the glass transition temperature of the second acrylic emulsion is below the above range, there is a problem that the drying speed and crosslinking density of the film are reduced, resulting in insufficient hardness and solvent resistance of the manufactured film, and when it exceeds the above range, the coating becomes brittle, resulting in insufficient appearance characteristics, tensile strength, and elongation of the manufactured film.
제2 아크릴 에멀젼은 중량평균분자량(Mw)이 200,000 내지 300,000 g/mol, 또는 220,000 내지 280,000 g/mol일 수 있다. 제2 아크릴 에멀젼의 중량평균분자량이 상기 범위 내일 경우, 제조된 필름의 내구성, 부착성, 및 내후성 등의 장기 물성이 우수할 수 있다. 제2 아크릴 에멀젼의 중량평균분자량이 상기 범위 미만인 경우 분자량이 작아 제조된 필름의 내수성 및 내후성이 부족해지고, 상기 범위 초과인 경우 분자량 증가에 따른 흐름성이 저하되어 이를 포함하는 도막 보호용 박리 가능한 조성물의 작업성이 불량해지고 표면평활성이 좋지 않아 외관을 저해하는 문제가 발생할 수 있다.The second acrylic emulsion may have a weight average molecular weight (Mw) of 200,000 to 300,000 g/mol, or 220,000 to 280,000 g/mol. When the weight average molecular weight of the second acrylic emulsion is within the above range, the long-term physical properties of the manufactured film, such as durability, adhesion, and weather resistance, may be excellent. When the weight average molecular weight of the second acrylic emulsion is less than the above range, the molecular weight is small, so that the water resistance and weather resistance of the manufactured film are insufficient, and when it exceeds the above range, the flowability decreases due to the increase in molecular weight, so that the workability of the peelable composition for protecting a coating film including the same deteriorates, and the surface smoothness is poor, which may cause a problem of deteriorating the appearance.
제2 아크릴 에멀젼은 탈이온수(deionized water)에 분산된 에멀젼 형태일 수 있다. 제2 아크릴 에멀젼은 탈이온수에 분산된 입자의 평균 직경이 150 내지 200nm, 또는 160 내지 190nm일 수 있다. 제2 아크릴 에멀젼이 탈이온수에 분산된 에멀젼 형태일 경우, 박리 가능한 조성물의 휘발성 유기 화합물(VOC, Volatile organic compounds) 함량을 낮출 수 있는 효과가 있으며, 입자의 평균 직경이 상기 범위 내일 경우 외관 및 입자안정성이 양호하다.The second acrylic emulsion may be in the form of an emulsion dispersed in deionized water. The second acrylic emulsion may have particles dispersed in deionized water having an average diameter of 150 to 200 nm, or 160 to 190 nm. When the second acrylic emulsion is in the form of an emulsion dispersed in deionized water, it has the effect of reducing the content of volatile organic compounds (VOCs) of the peelable composition, and when the average diameter of the particles is within the above range, the appearance and particle stability are good.
제2 아크릴 에멀젼은 제2 아크릴 에멀젼 총 중량을 기준으로 40 내지 50 중량%, 또는 43 내지 47 중량%의 고형분을 포함한다. 제2 아크릴 에멀젼의 고형분 함량이 상기 범위 내일 경우 작업성이 우수한 효과가 있다The second acrylic emulsion contains a solid content of 40 to 50 wt%, or 43 to 47 wt%, based on the total weight of the second acrylic emulsion. When the solid content of the second acrylic emulsion is within the above range, it has an excellent workability effect.
제2 아크릴 에멀젼은 산가(Av)가 1 내지 10 mgKOH/g, 또는 3 내지 8 mgKOH/g일 수 있다. 제2 아크릴 에멀젼의 산가가 상기 범위 내일 경우 이를 포함하는 조성물의 반응성을 조절하여 이로부터 제조된 필름의 외관 특성을 향상시킬 수 있다. 제2 아크릴 에멀젼의 산가가 상기 범위 미만인 경우 수지 안정성이 저하되어 박리 가능한 조성물의 저장성이 저하되는 문제가 발생하고, 상기 범위 초과인 경우 수지 응집성 증대로 조성물의 점도가 증가하여 작업성 및 필름의 내수성이 저하되는 문제가 발생할 수 있다.The second acrylic emulsion may have an acid value (Av) of 1 to 10 mgKOH/g, or 3 to 8 mgKOH/g. When the acid value of the second acrylic emulsion is within the above range, the reactivity of a composition containing it can be controlled to improve the appearance properties of a film manufactured therefrom. When the acid value of the second acrylic emulsion is below the above range, the resin stability may deteriorate, causing a problem in that the storability of the peelable composition may deteriorate. When the acid value exceeds the above range, the viscosity of the composition may increase due to increased resin cohesion, causing problems in that the workability and the water resistance of the film may deteriorate.
제2 아크릴 에멀젼은 pH가 7 내지 10, 또는 8 내지 10일 수 있다. 제2 아크릴 에멀젼의 pH가 상기 범위 내인 경우, 도막 보호용 박리 가능한 조성물의 점도가 적절하여 작업성이 상향되고 저장성이 개선되는 효과가 있다. 제2 아크릴 에멀젼의 pH가 상기 범위를 벗어나는 경우 조성물의 점도가 낮아 작업성이 부족하여 제조된 도막의 외관 특성이 저하되는 문제가 발생할 수 있다The second acrylic emulsion may have a pH of 7 to 10, or 8 to 10. When the pH of the second acrylic emulsion is within the above range, the viscosity of the peelable composition for film protection is appropriate, so that workability is improved and storability is improved. When the pH of the second acrylic emulsion is outside the above range, the viscosity of the composition is low, so that workability is insufficient, and a problem of deterioration of the appearance characteristics of the manufactured film may occur.
제2 아크릴 에멀젼은 도막 보호용 박리 가능한 조성물의 총 중량을 기준으로 25 내지 34 중량%, 또는 25 내지 32 중량%의 함량으로 조성물에 포함될 수 있다. 제2 아크릴 에멀젼이 상기 함량 범위 내로 포함되는 경우, 필름의 인장강도, 박리강도, 내수성 및 신율을 개선하는 효과가 있다. 제2 아크릴 에멀젼의 함량이 상기 범위 미만인 경우 필름의 가교밀도가 낮아져 인장강도, 내약품성 및 내수성이 저하되는 문제가 있고, 상기 범위 초과인 경우 건조가 빨리 진행되어 작업성이 부족하여 필름의 외관 및 인장강도가 저하되고 필름 탈착 후 잔류량이 많아지는 문제가 발생할 수 있다.The second acrylic emulsion may be included in the composition in an amount of 25 to 34 wt%, or 25 to 32 wt%, based on the total weight of the peelable composition for film protection. When the second acrylic emulsion is included within the above content range, it has the effect of improving the tensile strength, peel strength, water resistance, and elongation of the film. When the content of the second acrylic emulsion is less than the above range, the crosslinking density of the film decreases, which may cause a problem in that the tensile strength, chemical resistance, and water resistance decrease, and when it exceeds the above range, drying may proceed quickly, resulting in insufficient workability, which may cause a problem in that the appearance and tensile strength of the film decrease and the residual amount after film detachment may increase.
제1 아크릴 에멀젼 및 제2 아크릴 에멀젼의 혼합비가 전술한 범위에 해당될 경우, 적절한 건조성을 유지하여 차체 도막과의 적절한 부착성을 가지며, 탈착 후 잔류물 없이 필름이 깨끗하게 제거될 수 있다.When the mixing ratio of the first acrylic emulsion and the second acrylic emulsion falls within the above-mentioned range, the film can be removed cleanly without residue after removal by maintaining appropriate drying properties and having appropriate adhesion to the body coating.
용제solvent
용제는 물이며, 물은 이온 교환수, 증류수, 또는 초순수인 탈이온수일 수 있다. The solvent is water, which can be ion-exchanged water, distilled water, or ultrapure deionized water.
물 용제는 제1, 제2 아크릴 에멀젼의 제조시에 각각의 에멀젼 총 중량을 기준으로 20 내지 40 중량%의 함량으로 각각의 아크릴 에멀젼에 포함될 수 있다.The water solvent may be included in each acrylic emulsion in an amount of 20 to 40 wt% based on the total weight of each emulsion during the production of the first and second acrylic emulsions.
한편 도막 보호용 박리 가능한 조성물의 제조시, 물 용제는 도막 보호 용 박리 가능한 조성물의 총 중량을 기준으로 0.1 내지 10 중량%, 또는 0.3 내지 3 중량%의 함량으로 포함될 수 있다. 상기 범위 내에서 사용되는 경우 점도 조절이 용이할 수 있고, 도막 보호용 박리 가능한 조성물을 사용한 도막 보호 필름의 평활성 및 작업성이 우수할 수 있다.Meanwhile, when preparing a peelable composition for coating protection, the water solvent may be included in an amount of 0.1 to 10 wt%, or 0.3 to 3 wt%, based on the total weight of the peelable composition for coating protection. When used within the above range, viscosity control can be facilitated, and the smoothness and workability of the coating protection film using the peelable composition for coating protection can be excellent.
첨가제Additives
본 발명의 도막 보호용 박리 가능한 조성물은 중화제, 분산제, 이형제, 동결방지제, 소포제, 및 증점제로 구성된 그룹으로부터 선택되는 1종 이상의 첨가제를 포함할 수 있다.The peelable composition for film protection of the present invention may contain one or more additives selected from the group consisting of a neutralizing agent, a dispersing agent, a releasing agent, an antifreeze agent, an antifoaming agent, and a thickener.
첨가제는 도막 보호용 박리 가능한 조성물에 소정 함량 범위로 첨가되어 도장시 습윤성 및 레벨링성 등을 향상시키기 위한 추가적인 효과를 발휘하기 위한 목적으로 포함될 수 있다.Additives may be added to a peelable composition for coating protection in a predetermined content range for the purpose of providing additional effects such as improving wettability and leveling properties during painting.
도막 보호용 박리 가능한 조성물의 총 중량을 기준으로, 중화제는 0.1 내지 2 중량% 또는 0.1 내지 1 중량%, 동결방지제는 0.1 내지 5 중량% 또는 0.3 내지 3 중량%, 소포제는 0.1 내지 3 중량% 또는 0.3 내지 2 중량%, 증점제는 0.1 내지 3 중량% 또는 0.3 내지 2 중량%, 이형제는 0.1 내지 5 중량% 또는 0.3 내지 3 중량%, 그리고 분산제는 0.1 내지 2 중량% 또는 0.1 내지 1 중량%의 함량으로 도막 보호용 박리 가능한 조성물에 포함될 수 있다.Based on the total weight of the peelable composition for coating protection, the neutralizer may be included in an amount of 0.1 to 2 wt% or 0.1 to 1 wt%, the antifreeze may be included in an amount of 0.1 to 5 wt% or 0.3 to 3 wt%, the defoaming agent may be included in an amount of 0.1 to 3 wt% or 0.3 to 2 wt%, the thickener may be included in an amount of 0.1 to 3 wt% or 0.3 to 2 wt%, the releasing agent may be included in an amount of 0.1 to 5 wt% or 0.3 to 3 wt%, and the dispersing agent may be included in an amount of 0.1 to 2 wt% or 0.1 to 1 wt%.
여기서 이형제는 제1 아크릴 에멀젼에 포함된 이형제와는 별도로 도막 보호 용 박리 가능한 조성물에 포함된다.Here, the release agent is included in the peelable composition for film protection separately from the release agent included in the first acrylic emulsion.
<도막 보호 필름><Protective film for coating>
본 발명은 또 다른 양상에서 자동차 또는 중장비 등의 코팅면을 보호하기 위하여 박리가 용이하면서도 접착력이 우수한 도막 보호용 박리 가능한 조성물로부터 제조된 도막 보호 필름을 제공할 수 있다.In another aspect, the present invention can provide a coating protection film manufactured from a peelable composition for coating protection that is easy to peel and has excellent adhesive strength for protecting a coating surface of an automobile or heavy equipment, etc.
본 발명의 도막 보호 필름은 본 발명의 도막 보호용 박리 가능한 조성물의 경화에 의해 제조될 수 있다.The coating protective film of the present invention can be produced by curing the peelable composition for coating protection of the present invention.
구체적으로 본 발명의 도막 보호용 박리 가능한 조성물을 피도체 위에 스프레이, 브러쉬, 또는 롤러 등의 방법으로 10 ~ 100 ㎛ 두께로 도포한 후 상온 건조, 오븐 경화 또는 IR 램프 등으로 경화하여 도막 보호 필름을 형성할 수 있다.Specifically, the peelable composition for coating protection of the present invention can be applied to a thickness of 10 to 100 ㎛ on a conductor by spraying, brushing, or roller, and then cured by drying at room temperature, curing in an oven, or curing with an IR lamp, etc., to form a coating protection film.
<실험예><Experimental example>
이하, 실험예를 통해 본 발명을 더욱 구체적으로 설명한다.Hereinafter, the present invention will be described more specifically through experimental examples.
본 발명에서 실험예는 실시예와 비교예를 포함하는 것이며, 실험예는 본 발명의 이해를 돕기 위한 것일 뿐 어떠한 의미로든 본 발명의 범위가 이들로 한정되는 것은 아니다.In the present invention, experimental examples include working examples and comparative examples. The experimental examples are only intended to help understand the present invention and the scope of the present invention is not limited to these in any way.
제1, 제2 아크릴 에멀젼 제조Preparation of first and second acrylic emulsions
표 1에 나타낸 조성으로 아래 절차에 따라 제1, 제2 아크릴 에멀젼을 제조하였다.The first and second acrylic emulsions were prepared according to the procedure below with the compositions shown in Table 1.
1) PART1을 반응기에 넣고 80℃ 승온한다.1) Place PART1 in the reactor and heat to 80℃.
2) PART3 미리 혼합하여 프리-에멀젼(pre-emulsion)을 만든다.2) PART3 Mix in advance to create a pre-emulsion.
3) 80℃에 도달하면 프리-에멀젼의 10% 적가 후 10분 유지한다.3) When the temperature reaches 80℃, add 10% of the pre-emulsion and maintain for 10 minutes.
4) PART2 적가 후 10분 유지한다.4) PART2 Maintain for 10 minutes after adding.
5) PART3의 나머지를 30분 적가 후 30분 유지한다.5) Add the rest of PART3 for 30 minutes and then maintain for 30 minutes.
6) PART4 투입 후 30분 유지한다.6) After adding PART4, keep for 30 minutes.
7) 40℃ 이하로 냉각 후 PART5 투입 후 10분 유지한다.7) After cooling to below 40℃, add PART5 and keep for 10 minutes.
8-1) 제2 아크릴 에멀젼 경우: 40℃ 이하에서 PART6 투입 후 30분 유지한다.8-1) In the case of the second acrylic emulsion: Add PART6 at 40℃ or lower and maintain for 30 minutes.
8-2) 제1 아크릴 에멀젼 경우: PART7 투입 후 30분 유지한다.8-2) For the first acrylic emulsion: After adding PART7, keep for 30 minutes.
표 1의 제1, 제2 아크릴 에멀젼의 제조에 사용된 구체적인 성분을 아래 표 2에 나타낸다.The specific ingredients used in the manufacture of the first and second acrylic emulsions in Table 1 are shown in Table 2 below.
도막 보호용 박리 가능한Peelable for film protection 조성물 제조Composition Preparation
하기 표 3 및 표 4에 나타낸 조성으로, 앞서 제조된 제1, 제2 아크릴 에멀젼을 투입한 후 교반하면서 용제 및 첨가제를 순차적으로 투입하는 과정을 통해 도막 보호용 박리 가능한 조성물을 제조하였다.A peelable composition for film protection was manufactured by sequentially adding solvent and additives while stirring after adding the first and second acrylic emulsions manufactured previously, according to the compositions shown in Tables 3 and 4 below.
표 3 및 표 4의 도막 보호용 박리 가능한 조성물의 제조에 사용된 구체적인 성분을 아래 표 5에 나타낸다.Specific ingredients used in the preparation of the peelable compositions for film protection of Tables 3 and 4 are shown in Table 5 below.
도막 보호 필름 형성Formation of a protective film on the coating
표 3 및 표 4의 조성으로 혼합하여 제조된 도막 보호용 박리 가능한 조성물을 자동차 클리어가 도장된 피도체 위에 스프레이 방법으로 50㎛ 도막 두께로 도포한 후 80℃에서 3분 동안 경화하여 도막 보호 필름을 형성하였다.A peelable composition for coating protection, manufactured by mixing the compositions in Tables 3 and 4, was applied to a substrate coated with automotive clear paint by a spray method with a coating thickness of 50 μm, and then cured at 80° C. for 3 minutes to form a coating protection film.
물성 평가Property Evaluation
제조된 도막 보호 필름의 물성 평가를 아래 방법으로 수행하고 그 결과를 표 6 및 표 7에 나타낸다.The physical properties of the manufactured coating protective film were evaluated using the following method, and the results are shown in Tables 6 and 7.
1) 박리 강도: 필름 박리시 힘을 측정하여 접착력과 박리성능을 평가하였다. 25mm x 50mm(가로 x 세로), 50㎛ 도막 두께의 필름을 80℃에서 3분 동안 경화한 후 24시간 뒤 측정하였다. 인장속도 300 mm/min, 박리방향 180도로 UTM(Universal Testing Machine) 기기로 측정하였다. 박리 강도가 0.6 내지 2.0N인 경우 양호한 것으로 평가하였다.1) Peel strength: The peel strength was measured to evaluate the adhesive strength and peel performance when peeling the film. A film of 25 mm x 50 mm (width x length) and 50 μm thickness was cured at 80°C for 3 minutes and measured 24 hours later. The measurement was made using a UTM (Universal Testing Machine) at a tensile speed of 300 mm/min and a peeling direction of 180 degrees. The peel strength was evaluated as good when it was 0.6 to 2.0 N.
2) 인장 강도: 필름의 강인성과 질긴 정도인 인장강도 측정하였다. 25mm x 50mm(가로 x 세로), 50㎛ 도막 두께의 필름을 23℃, RH 65% 기준으로 UTM (Universal Testing Machine) 기기로 측정하였다. Wmax/A0 (Wmax:최대인장하중, A0: 단면적). 인장 강도가 10N 이상인 경우 양호한 것으로 평가하였다.2) Tensile strength: The tensile strength, which is the toughness and toughness of the film, was measured. The film with a size of 25 mm x 50 mm (width x length) and a film thickness of 50 μm was measured using a UTM (Universal Testing Machine) at 23°C and RH 65%. Wmax/A0 (Wmax: maximum tensile load, A0: cross-sectional area). A tensile strength of 10 N or more was evaluated as good.
3) 신율: 필름이 늘어나는 정도인 신율을 측정하였다. 25mm x 50mm(가로 x 세로), 50㎛ 도막 두께의 필름을 23℃, RH 65% 기준으로 UTM (Universal Testing Machine) 기기로 측정하였다. 3) Elongation: The elongation, which is the extent to which the film stretches, was measured. A film of 25 mm x 50 mm (width x length) and 50 μm thickness was measured using a UTM (Universal Testing Machine) at 23°C and RH 65%.
(L-L0)x100/L0.(L:필름이 끊어지기 전까지의 길이, LO :필름의 초기 길이)(LL 0 )x100/L 0. (L: length before the film breaks, L O : initial length of the film)
신율이 200% 이상인 경우 양호한 것으로 평가하였다.A rate of 200% or higher was evaluated as good.
4) 내수성: 50℃, RH 98% 기준으로 100시간 및 실온 1시간 거치 후 측정하였다. 필름 제거 후 피착체에 잔사, 이색, 이질감, 및 외관의 이상이 없고 필름의 끊김이 없는 경우 양호한 것으로 평가하였다.4) Water resistance: Measured after 100 hours at 50℃, RH 98% and 1 hour at room temperature. If there is no residue, discoloration, foreign texture, or appearance abnormality on the adherend after film removal and there is no breakage of the film, it is evaluated as good.
5) 내약품성: 가솔린 0.5mL 드롭 후 70℃, 3시간 이후 외관을 측정하였다. 필름 제거 후 도장면의 변색, 팽윤 등의 외관 이상 없는 경우 양호한 것으로 평가하였다.5) Chemical resistance: The appearance was measured at 70℃ for 3 hours after dropping 0.5 mL of gasoline. If there was no abnormality in appearance, such as discoloration or swelling of the painted surface after removing the film, it was evaluated as good.
표 6 및 표 7에 제시된 바와 같이, 도막 보호 필름은 실험예 1 내지 실험예 3에서 물성이 양호하였고, 실험예 4 및 실험예 5에서는 다소 열세하였으며, 실험예 6 내지 실험예 16에서는 열세하였다. 구체적으로 제1 아크릴 에멀젼에 포함된 아크릴로니트릴 모노머 함량이 미만인 실험예 6은 인장강도, 신율, 내약품성 및 내수성이 열세하였고, 제1 아크릴 에멀젼에 포함된 아크릴로니트릴 모노머 함량이 초과인 실험예 7은 박리성이 열세하였고, 제2 아크릴 에멀젼에 산화아연 경화제를 포함하지 않는 실험예 8은 인장강도, 신율, 내약품성 및 내수성이 열세하였고, 제2 아크릴 에멀젼에 포함된 산화아연 경화제를 과량 포함하는 실험예 9은 신율 및 내약품성이 열세하였고, 제1 아크릴 에멀젼의 유리전이온도가 범위 미만인 실험예 10 및 초과하는 실험예 11은 인장강도, 신율 또는 내수성에서 하나 이상 물성이 열세하였고, 제1 아크릴 에멀젼에 아미노 변성 지방산계의 이형제를 포함하지 않는 실험예 12 및 함량이 과량인 실험예 13은 박리성 또는 박리강도가 낮아 부착성이 열세하였고, 제2 아크릴 에멀젼을 사용하지 않고 1종의 아크릴 에멀젼을 사용하는 실험예 14는 내약품성 및 내수성이 열세하였고, 제1 아크릴 에멀젼을 사용하지 않고 1종의 아크릴 에멀젼을 사용하는 실험예 15는 부착성 및 인장강도가 열세하였고, 아미노 변성 지방산계의 이형제 또는 산화아연 경화제를 포함하지 않는 아크릴 에멀젼을 사용한 실험예 16은 부착성 및 내약품성이 열세하였다. As shown in Tables 6 and 7, the properties of the coating protective film were good in Experimental Examples 1 to 3, somewhat inferior in Experimental Examples 4 and 5, and inferior in Experimental Examples 6 to 16. Specifically, Experimental Example 6, in which the content of acrylonitrile monomer in the first acrylic emulsion was less than the content, had inferior tensile strength, elongation, chemical resistance and water resistance, and Experimental Example 7, in which the content of acrylonitrile monomer in the first acrylic emulsion was greater than the content, had inferior peelability, and Experimental Example 8, in which the second acrylic emulsion did not contain a zinc oxide hardener, had inferior tensile strength, elongation, chemical resistance and water resistance, and Experimental Example 9, in which the content of a zinc oxide hardener in the second acrylic emulsion was greater than the content, had inferior elongation and chemical resistance, and Experimental Example 10, in which the glass transition temperature of the first acrylic emulsion was less than the range and Experimental Example 11, in which the glass transition temperature of the first acrylic emulsion was greater than the range, had inferior tensile strength, elongation or water resistance in at least one property, and Experimental Example 12, in which the first acrylic emulsion did not contain an amino-modified fatty acid-based release agent and Experimental Example 13, in which the content was greater than the content, had inferior peelability or The peel strength was low, so the adhesion was poor. Experimental Example 14, which did not use the second acrylic emulsion but used one type of acrylic emulsion, had poor chemical resistance and water resistance. Experimental Example 15, which did not use the first acrylic emulsion but used one type of acrylic emulsion, had poor adhesion and tensile strength. Experimental Example 16, which used an acrylic emulsion that did not contain an amino-modified fatty acid-based release agent or a zinc oxide hardener, had poor adhesion and chemical resistance.
이하 본 발명의 다양한 실시 형태를 설명한다.Hereinafter, various embodiments of the present invention will be described.
(1) 제1 아크릴 에멀젼 및 제2 아크릴 에멀젼을 포함하며, 제1 아크릴 에멀젼은 아미노 변성 지방산계 이형제를 포함하며, 제2 아크릴 에멀젼은 산화아연(ZnO) 경화제를 포함하는, 도막 보호용 박리 가능한 조성물.(1) A peelable composition for protecting a coating film, comprising a first acrylic emulsion and a second acrylic emulsion, wherein the first acrylic emulsion comprises an amino-modified fatty acid-based release agent, and the second acrylic emulsion comprises a zinc oxide (ZnO) curing agent.
(2) 제1 아크릴 에멀젼은 제1 아크릴 에멀젼에 포함된 모노머 총량 100중량부를 기준으로 아크릴로니트릴 모노머 30 내지 50 중량부 및 아미노 변성 지방산계 이형제 1 내지 5 중량부를 포함하는, 도막 보호용 박리 가능한 조성물.(2) A peelable composition for protecting a film, wherein the first acrylic emulsion contains 30 to 50 parts by weight of an acrylonitrile monomer and 1 to 5 parts by weight of an amino-modified fatty acid-based release agent based on 100 parts by weight of the total amount of monomers contained in the first acrylic emulsion.
(3) 제2 아크릴 에멀젼은 제2 아크릴 에멀젼에 포함된 모노머 총량 100 중량부를 기준으로 산화아연(ZnO) 경화제 5 내지 20 중량부를 포함하는, 도막 보호 용 박리 가능한 조성물.(3) A peelable composition for protecting a coating film, wherein the second acrylic emulsion contains 5 to 20 parts by weight of a zinc oxide (ZnO) curing agent based on 100 parts by weight of the total amount of monomers contained in the second acrylic emulsion.
(4) 제1 아크릴 에멀젼은 유리전이온도(Tg)가 -15 내지 20℃이고, 제1 아크릴 에멀젼 총 중량을 기준으로 고형분 함량이 40 내지 50 중량%이고, 25℃에서의 점도가 30 내지 200 cPs이고, 산가가 1 내지 10 mgKOH/g이고, pH가 7 내지 10이고, 중량평균분자량(Mw)이 100,000 내지 200,000 g/mol이고, 입자의 평균 직경이 100 내지 200nm인, 도막 보호용 박리 가능한 조성물.(4) A peelable composition for protecting a film, wherein the first acrylic emulsion has a glass transition temperature (Tg) of -15 to 20°C, a solid content of 40 to 50 wt% based on the total weight of the first acrylic emulsion, a viscosity at 25°C of 30 to 200 cPs, an acid value of 1 to 10 mgKOH/g, a pH of 7 to 10, a weight average molecular weight (Mw) of 100,000 to 200,000 g/mol, and an average particle diameter of 100 to 200 nm.
(5) 제2 아크릴 에멀젼는 유리전이온도(Tg)가 40 내지 60℃이며, 제2 아크릴 에멀젼 총 중량을 기준으로 고형분 함량이 40 내지 50 중량%이고, 25℃에서의 점도가 150 내지 500 cPs이고, 산가가 1 내지 10 mgKOH/g이고, pH가 7 내지 10이고, 중량평균분자량(Mw)이 200,000 내지 300,000 g/mol이고, 입자의 평균 직경이 150 내지 200nm인, 도막 보호용 박리 가능한 조성물.(5) A peelable composition for protecting a film, wherein the second acrylic emulsion has a glass transition temperature (Tg) of 40 to 60°C, a solid content of 40 to 50 wt% based on the total weight of the second acrylic emulsion, a viscosity at 25°C of 150 to 500 cPs, an acid value of 1 to 10 mgKOH/g, a pH of 7 to 10, a weight average molecular weight (Mw) of 200,000 to 300,000 g/mol, and an average particle diameter of 150 to 200 nm.
(6) 도막 보호용 박리 가능한 조성물 총 중량을 기준으로 제1 아크릴 에멀젼 60 내지 70 중량% 및 제2 아크릴 에멀젼 25 내지 34 중량%를 포함하는, 도막 보호용 박리 가능한 조성물.(6) A peelable composition for film protection, comprising 60 to 70 wt% of a first acrylic emulsion and 25 to 34 wt% of a second acrylic emulsion based on the total weight of the peelable composition for film protection.
(7) 본 발명에 따르는 도막 보호용 박리 가능한 조성물의 경화에 의해 제조되는 도막 보호 필름.(7) A coating protection film manufactured by curing a peelable composition for coating protection according to the present invention.
Claims (6)
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JPS60161465A (en) * | 1984-01-31 | 1985-08-23 | Mitsui Toatsu Chem Inc | Aqueous strippable paint |
KR20130031216A (en) * | 2011-09-20 | 2013-03-28 | 닛토덴코 가부시키가이샤 | Removable pressure-sensitive adhesive composition, removable pressure-sensitive adhesive layer, and removable pressure-sensitive adhesive sheet |
KR20160077753A (en) * | 2014-12-24 | 2016-07-04 | (주)엘지하우시스 | Acrylic adhesive sheet, adhesive tape for medical treatment and method of producing the same |
JP2019209675A (en) * | 2017-06-27 | 2019-12-12 | 王子ホールディングス株式会社 | Releasable film |
JP2021098845A (en) * | 2019-12-20 | 2021-07-01 | 日本化工塗料株式会社 | Thermosetting release coating agent and laminate, and method for producing laminate |
Family Cites Families (1)
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KR100498717B1 (en) | 1997-10-20 | 2005-10-26 | 가부시키가이샤 린레이 | Peelable coating agent |
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2023
- 2023-04-27 KR KR1020230055507A patent/KR20240158610A/en not_active Application Discontinuation
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS60161465A (en) * | 1984-01-31 | 1985-08-23 | Mitsui Toatsu Chem Inc | Aqueous strippable paint |
KR20130031216A (en) * | 2011-09-20 | 2013-03-28 | 닛토덴코 가부시키가이샤 | Removable pressure-sensitive adhesive composition, removable pressure-sensitive adhesive layer, and removable pressure-sensitive adhesive sheet |
KR20160077753A (en) * | 2014-12-24 | 2016-07-04 | (주)엘지하우시스 | Acrylic adhesive sheet, adhesive tape for medical treatment and method of producing the same |
JP2019209675A (en) * | 2017-06-27 | 2019-12-12 | 王子ホールディングス株式会社 | Releasable film |
JP2021098845A (en) * | 2019-12-20 | 2021-07-01 | 日本化工塗料株式会社 | Thermosetting release coating agent and laminate, and method for producing laminate |
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