Patent Application
20240327586
The invention relates to a coated film and a method for preparing the same, use of the coated film for manufacturing shaped bodies, a method for manufacturing shaped bodies from the coated film, and a shaped body made therefrom.
Labels for shoes and clothing are usually made of thermoplastic polyurethane film. The pattern or text is firstly printed on the surface of the thermoplastic polyurethane film, which is then attached to the shoes or clothing. In order to prevent the pattern or text in the middle part of the film from becoming blurred due to hot pressing, edge laminating is usually used in the laminating process for the thermoplastic polyurethane film and shoes or clothing to ensure the sharpness of the printed pattern or text.
WO 2017/046091 A1 discloses a coated film comprising a plastic film and a radiation-curable aqueous coating agent, wherein the coating agent comprises a polyurethane (meth) acrylate and inorganic nanoparticles with an average particle size of 1 nm-200 nm. The coated film has anti-blocking property and elasticity, and shows good hydrolysis resistance and chemical resistance after radiation curing.
US 2014/0202749 A1 discloses a resin composition comprising methacrylate. The composition is applied to the surface of a substrate to form a coating, and a pattern may be printed on the surface of the coating. The coating formed by the composition has good waterproof performance.
WO 2006/079098 A1 discloses an aqueous dispersion for preparing nanoparticle/polyurethane composites by forming a mixture of nanoparticles and a continuous mass of a polyurethane prepolymer in the substantial absence of water and dispersing the mixture so made in aqueous medium. Alternatively, a polyurethane prepolymer or a mixture of nanoparticles and a continuous mass of a polyurethane prepolymer is dispersed into an aqueous dispersion of nanoparticles. The aqueous dispersion may have good abrasion resistance.
WO 98/00458 A1 discloses a film consisting of at least two layers, which contains a polyurethane film with Shore hardness between 70A and 80D as one layer, and a UV radiation curable system as another layer. The double-layer film has good wear resistance.
Apparently, the problem that thermoplastic polyurethane films are not resistant to hot pressing has not been solved in the prior art. It is desirable to have a film, in which the pattern or text thereon remains sharp after the hot pressing process.
The object of the invention is to provide a coated film and a method for preparing the same, use of the coated film for manufacturing shaped bodies, a method for manufacturing shaped bodies from the coated film, and a shaped body made therefrom.
A coated film according to the present invention comprises a plastic film with Shore hardness of not less than 80A and a coating formed by applying an aqueous coating composition to the plastic film, wherein the plastic film is a film of a thermoplastic polyurethane based on polyester polyol, and the aqueous coating composition comprises:
According to an aspect of the present invention, a method for preparing the coated film according to the present invention is provided, which comprises the following steps:
According to another aspect of the present invention, use of the coated film according to the present invention for manufacturing shaped bodies is provided.
According to another aspect of the present invention, a method for manufacturing shaped bodies is provided, which comprises the following steps:
According to still another aspect of the present invention, a shaped body manufactured by the method for manufacturing shaped bodies according to the present invention is provided.
According to still another aspect of the present invention, a shaped body comprising the coated film according to the present invention is provided.
The thermoplastic polyurethane film comprised in the coated film of the present invention can be firmly bonded to the substrate after hot pressing, and has excellent adhesion. The coating formed by the aqueous coating composition of the present invention on the surface of the thermoplastic polyurethane film has excellent surface dryness, anti-blocking property, and excellent heat resistance, and can withstand the hot pressing condition up to 205° C. After the coated film of the present invention is hot-pressed, the pattern or text on the coating remains sharp, and the surface has a matte effect. The coated film of the present invention is applicable to the thermal transfer and the full-area hot pressing process, and can be widely used for printing labels of shoes, clothing and the like.
The present invention provides a coated film comprising a plastic film with Shore hardness of not less than 80A and a coating formed by applying an aqueous coating composition to the plastic film, wherein the plastic film is a film of a thermoplastic polyurethane based on polyester polyol, and the aqueous coating composition comprises: a. 45% by weight to 85% by weight of a dispersion of an anionic polyurethane based on polycarbonate polyol; b. 0% by weight to 40% by weight of a dispersion of an anionic polyurethane based on polyether polyol; c. 2% by weight to 18% by weight of a dispersion of anionic silica; d. 0.5% by weight to 10% by weight of a blocked isocyanate; and e. 0.1% by weight to 10% by weight of an additive; the amounts above being relative to the total weight of the composition. The present invention further provides a method for preparing the coated film, use of the coated film for manufacturing shaped bodies and a method for manufacturing shaped bodies from the coated film, and a shaped body made therefrom.
The term “coating composition” used herein refers to a material that can be applied to the surface of an object by a variety of processes to form a continuous solid coating with firm adhesion and certain strength.
The term “drying” used herein refers to the process of removing volatile constituents.
The term “polyurethane dispersion” used herein refers to polyurethane urea dispersion and/or polyurethane polyurea dispersion and/or polyurea dispersion and/or polythiourethane dispersion.
The term “dispersion of an anionic polyurethane based on polycarbonate polyol” used herein refers to an aqueous polyurethane dispersion obtained by the reaction of a system comprising polycarbonate polyol, wherein the aqueous polyurethane dispersion comprises anionic groups.
The term “dispersion of an anionic polyurethane based on polyether polyol” used herein refers to an aqueous polyurethane dispersion obtained by the reaction of a system comprising polyether polyol, wherein the aqueous polyurethane dispersion comprises anionic groups.
The term “film of a thermoplastic polyurethane based on polyester polyol” used herein refers to a thermoplastic polyurethane film obtained by the reaction of a system comprising polyester polyol.
The term “film of a thermoplastic polyurethane based on polyether polyol” used herein refers to a thermoplastic polyurethane film obtained by the reaction of a system comprising polyether polyol.
The term “blocked isocyanate” used herein refers to an isocyanate compound in which the isocyanate group is blocked.
The term “minimum softening temperature of the thermoplastic polyurethane film” used herein refers to the TMA start temperature, and “maximum softening temperature of the thermoplastic polyurethane film” refers to the TMA end temperature.
The grade of surface dryness and anti-blocking of the coated film is preferably of level 3 to 5.
The adhesion force of the coated film is preferably of 17 N/30 mm to 50 N/30 mm, tested by using GOTECH tensile machine GOTECH/AI-3000 from GOTECH Testing Machines Inc. according to GB/T 8949-2008.
The haze value of the coated film is preferably 80 to 130, tested with haze meter BYK4601 from BYK.
The pattern sharpness of the coated film before hot pressing is preferably of level 3 to 5, and the pattern sharpness after hot pressing is preferably of level 3 to 5.
The dispersion of an anionic polyurethane based on polycarbonate polyol has preferably at least one of the following characteristics:
The weight average molecular weight of the dispersion of an anionic polyurethane based on polycarbonate polyol is of 1500000-12000000, tested by gel chromatography according to GB/T 21863-2008.
The dispersion of an anionic polyurethane based on polycarbonate polyol is preferably a dispersion of carboxyl-containing polyurethane based on polycarbonate polyol.
The carboxyl content of the dispersion of carboxyl-containing polyurethane based on polycarbonate polyol is preferably of 0.05% by weight to 2% by weight, most preferably 0.6% by weight to 1% by weight, relative to the total weight of solid constituents of the dispersion of carboxyl-containing polyurethane based on polycarbonate polyol.
The dispersion of an anionic polyurethane based on polycarbonate polyol is preferably in an amount of 52% by weight to 84% by weight, preferably 64% by weight to 82% by weight, most preferably 79% by weight to 81% by weight, relative to the total weight of the aqueous coating composition.
The solid content of the dispersion of an anionic polyurethane based on polycarbonate polyol is preferably of 30% by weight to 50% by weight, most preferably 39% by weight to 41% by weight. relative to the total weight of the dispersion of an anionic polyurethane based on polycarbonate polyol.
The residual organic solvent in the dispersion of an anionic polyurethane based on polycarbonate polyol is preferably in an amount of less than 1.0% by weight, relative to the total weight of the dispersion of an anionic polyurethane based on polycarbonate polyol.
The fusion enthalpy of the polyurethane polymer in the dispersion of an anionic polyurethane based on polycarbonate polyol at 20° C.-100° C. is preferably less than 3 J/g, obtained by measuring the first heating curve by DSC at a heating rate of 20 K/min according to DIN65467.
The tensile strength of the dispersion of an anionic polyurethane based on polycarbonate polyol is preferably of 40 MPa-60 MPa, tested according to DIN53504-S2.
The dispersion of an anionic polyurethane based on polycarbonate polyol can be directly added to the aqueous coating composition as a dispersion. Alternatively, a mixture of the anionic polyurethane based on polycarbonate polyol and water can be added to the aqueous coating composition, and mixed to form a dispersion.
The dispersion of an anionic polyurethane based on polycarbonate polyol comprises an anionic polyurethane based on polycarbonate polyol and water.
The dispersion of an anionic polyurethane based on polycarbonate polyol is preferably obtained by the reaction of a system comprising a polycarbonate polyol and a polyisocyanate.
The polycarbonate polyol is preferably obtained by reacting a carbonic acid derivative such as diphenyl carbonate, dimethyl carbonate or phosgene with a diol.
The diol is preferably one or more of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-dimethylolcyclohexane, 2-methyl-1,3-propanediol, 2,2,4-trimethylpentane-1,3-diol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol, bisphenol A, tetrabromobisphenol A and lactone-modified diols, most preferably 1,6-hexanediol and/or derivatives thereof.
Preferably, the diol comprises not less than 40% by weight of 1,6-hexanediol and/or a derivative of hexanediol, relative to the total weight of the diol.
The derivative of hexanediol is preferably a compound, in which terminal OH groups contain ether or ester groups, for example, a product obtained by reacting 1 mol of hexanediol with at least 1 mol. preferably 1-2 mol of ε-caprolactone or by etherifying the hexanediol itself to form di- or trihexanediol.
The dispersion of an anionic polyurethane based on polyether polyol has preferably at least one of the following characteristics:
The 100% modulus of the dispersion of an anionic polyurethane based on polyether polyol is preferably of 1.5 MPa-2.5 MPa, most preferably 2 MPa-2.5 MPa, tested according to DIN 53504.
The dispersion of an anionic polyurethane based on polyether polyol is preferably a dispersion of carboxyl-containing polyurethane based on polyether polyol.
The carboxyl content of the dispersion of carboxyl-containing polyurethane based on polyether polyol is preferably of 0.05% by weight to 0.5% by weight, most preferably 0.05% by weight to 0.15% by weight, relative to the total weight of solid constituents of the dispersion of carboxyl-containing polyurethane based on polyether polyol.
The dispersion of an anionic polyurethane based on polyether polyol is preferably in an amount of 0% by weight to 30% by weight, relative to the total weight of the aqueous coating composition.
The solid content of the dispersion of an anionic polyurethane based on polyether polyol is preferably of 30% by weight to 60% by weight, most preferably 39% by weight to 41% by weight, relative to the total weight of the dispersion of an anionic polyurethane based on polyether polyol.
The residual organic solvent in the dispersion of an anionic polyurethane based on polyether polyol is preferably in an amount of less than 1.0% by weight, relative to the total weight of the dispersion of an anionic polyurethane based on polyether polyol.
The dispersion of an anionic polyurethane based on polyether polyol can be directly added to the aqueous coating composition as a dispersion. Alternatively, a mixture of the anionic polyurethane based on polyether polyol and water can be added to the aqueous coating composition, and mixed to form a dispersion.
The dispersion of an anionic polyurethane based on polyether polyol comprises an anionic polyurethane based on polyether polyol and water.
The dispersion of an anionic polyurethane based on polyether polyol is preferably obtained by the reaction of a system comprising a polyether polyol and a polyisocyanate.
The polyether polyol is preferably one or more of polyaddition products of styrene oxide, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, and epichlorohydrin, and mixed addition and grafting products thereof, and condensation products of polyols or mixtures thereof, and alkoxy lation products of polyols, amines and amino alcohols.
The Z-average particle size of the dispersion of anionic silica is preferably of 10 nm-50 nm, tested according to ISO13321. Specifically, 1 drop of the dispersion of anionic silica is added to 50 ml of ultrapure water, stirred lightly to dilute, and tested with Malvern Zetasizer Nano ZS, with test temperature of 23.0±0.1° C.; test material setting: polystyrene latex (refractive index of 1.590, absorption value of 0.010): dispersant setting: water (temperature of 23.0° C., viscosity of 0.9308 centipoise, refractive index of 1.330); equilibrium time of 60 seconds; type of sample cell: disposable sample cell DTS0012: positioning method: automatic attenuation, automatic optimization of positioning optimization; analysis mode: conventional purpose (normal resolution); test angle of 173° backscatter (NIBS default). Each sample is tested for 3 rounds, 10 times per round, and each test time is of 10 seconds, and the average of all tests is taken as Z-average particle size. The Z-average particle size of the dispersion of anionic silica is further preferably of 25 nm-50 nm, most preferably 25 nm-35 nm.
The density of the dispersion of anionic silica is preferably of 1 g/cm3-2 g/cm3, most preferably 1 g/cm3-1.5 g/cm3, tested according to DIN 51757.
The pH value of the dispersion of anionic silica is preferably of 8-11, tested according to DIN ISO 976.
The dispersion of anionic silica is preferably in an amount of 2% by weight to 18% by weight, more preferably 4% by weight to 16% by weight, most preferably 6% by weight to 10% by weight, relative to the total weight of the aqueous coating composition.
The solid content of the dispersion of anionic silica is preferably of 20% by weight to 50% by weight, more preferably 25% by weight to 45% by weight, most preferably 25% by weight to 35% by weight, relative to the total weight of the dispersion of anionic silica.
The dispersion of anionic silica is preferably a dispersion of anionic amorphous silica.
The blocked isocyanate is preferably a hydrophilically modified aliphatic isocyanate.
The solid content of the blocked isocyanate is preferably of 20% by weight to 50% by weight, relative to the total weight of the blocked isocyanate.
The content of the isocyanate groups in the blocked isocyanate is preferably of 10% by weight to 15% by weight, relative to the total weight of solid constituents of the blocked isocyanate.
The viscosity of the blocked isocyanate is preferably of less than 1500 mPa·s, tested with an MV-DIN rotor according to DIN EN ISO 3219: 1994-10 at 23° C. and at a shear rate of 10 s-−1.
The blocking agent for blocking the isocyanate is preferably one or more of caprolactam, butanone oxime, dimethylpyrazole, diethyl diacetate, pyrazole and diisopropylamine.
The blocked isocyanate is preferably in an amount of 6% by weight to 10% by weight, most preferably 7% by weight to 9% by weight, relative to the total weight of the aqueous coating composition.
The additive is preferably one or more of wetting agents, defoamers, thickeners, and other additives that can be added to the aqueous coating composition as is well known to those skilled in the art.
The amount of the additive may be an amount that can be added as is well known to those skilled in the art.
The additive is preferably in an amount of 3% by weight to 6% by weight, most preferably 3.5% by weight to 4.5% by weight, relative to the total weight of the aqueous coating composition.
The film of a thermoplastic polyurethane based on polyester polyol has preferably at least one of the following characteristics:
The Shore hardness of the plastic film is preferably 82A-95A, more preferably 85A-95A, and most preferably 88 A-95 A, tested by using Shore hardness tester according to ASTM D 2240.
The dry film thickness of the coating formed by applying the aqueous coating composition to the plastic film is preferably of 0.01 mm to 0.10 mm. The coating may be single-layered or multi-layered.
The coated film may be coated on one side or on both sides, and is preferably coated on one side.
In the case of coating on one side, a thermally deformable adhesive layer may optionally be applied on the back side of the film, that is, on the surface where the coating composition is not applied. For this purpose, hot-melt adhesives or radiation-curable adhesives are preferably suitable depending on the method used. In addition, a protective layer may also be applied on the surface of the adhesive layer.
In addition, a substrate such as a fabric may be provided on the back side of the film.
Optionally, the plastic film may be painted, printed or stamped with one or more layers, after the aqueous coating composition is applied. The layer may be colored or functional, which is applied over the entire surface or only partially, for example, in the form of printed pattern.
The drying is preferably performed at 60° C. to 70° C.
A method for preparing the coated film preferably comprises the following steps:
A method for preparing the coated film further preferably comprises the following steps:
A method for preparing the coated film most preferably comprises the following steps:
The layer may be colored or functional, which is present on the entire surface or only on part thereof.
The substrate is preferably a fabric.
The shaped body is preferably a shoe or clothing.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. When the definition of a term in this specification conflicts with the meanings commonly understood by those skilled in the art, the definition described herein shall prevail.
Unless indicated otherwise, all numbers expressing quantities of constituents, reaction conditions and the like used in the specification and claims are to be understood as being modified by the term “about”. Accordingly, the numerical parameters set forth herein are approximations that can vary depending upon the desired properties to be obtained, unless indicated to the contrary.
The wording “and/or” used herein refers to one or all of the cited elements.
The wordings “include” and “comprise” used herein cover the cases, in which mentioned elements are present alone, and the cases, in which other unmentioned elements are present in addition to the mentioned elements.
All percentages in the present invention are weight percentage, unless otherwise stated.
The analysis and measurement in the present invention are all performed at 23° C., unless otherwise stated.
Unless otherwise indicated, the wording “a”, “an”, and “the” used herein are intended to include “at least one” or “one or more”. For example, the wording “a component” refers to one or more components, therefore more than one component may be considered and may be adopted or used in the implementation of the embodiments.
The solid content of the dispersion is tested by using a moisture analyzer HS153 from Mettler Toledo according to DIN-EN ISO 3251.
The grade of surface dryness and anti-blocking of the coated film (level 1 to 5, from poor to good) was tested as follows. The coated film was cut into 10 cm×5 cm sample strips. The coated surface of a same strip was stacked on the coated surface of another sample strip, and then a load of 1 kg was pressed thereon. After being left at room temperature of 23° C. for 24 hours, the load was removed, and the two samples stacked together were rated according to the degree of adhesion. If there was no adhesion, the grade of surface dryness and anti-blocking was of level 5. If there was slight adhesion to each other, and they could be separated spontaneously, the grade of surface dryness and anti-blocking was of level 4. If there was slight adhesion to each other, and they could be separated manually, the grade of surface dryness and anti-blocking was of level 3. If there was obvious adhesion, and they could be peeled off manually, the grade of surface dryness and anti-blocking was of level 2. If there was obvious adhesions, and they were stuck to each other and could not be separated immediately, the grade of surface dryness and anti-blocking was of level 1. The grade of surface dryness and anti-blocking of level 3 to 5 was regarded as qualified. The unqualified grade of surface dryness and anti-blocking of coated films may cause the coated surface of the film to stick to another plastic film during the rolling process.
The adhesion force (peeling force) of the coated film was tested in the unit of N/30 mm by using GOTECH tensile machine GOTECH/AI-3000 from GOTECH Testing Machines Inc. according to GB/T 8949-2008. The adhesion force of 17 N/30 mm-50 N/30 mm was regarded as qualified. Good adhesion ensured that the coating and the plastic film adhered firmly, otherwise the coating and the plastic film tended to separate from each other.
The haze value of coated films was tested with haze meter BYK4601 from BYK. The haze value of 80 to 130 was regarded as qualified. The lower the haze value. the higher the transparency.
The pattern sharpness was observed visually. It was rated with level 1 to 5 from poor to good. If the pattern was sharp and had no deformation, it was of level 5. If the pattern was sharp and had substantively no deformation, it was of level 4. If the pattern was relative sharp but had slight deformation, it was of level 3. If the pattern was slightly blurred and had deformation or vignetting effect, it was of level 2. If the pattern was blurred and had severe deformation or vignetting effect, it was of level 1. The pattern sharpness of level 3 to 5 was regarded as qualified.
It was tested by using a fabric hot press tester SC125X50 frin Xiangshan Yongcheng Printing Material Co., Ltd. The film was heat-pressed at 205° C. for 10 seconds with a pressure of 5 kgf/cm2. The pattern sharpness after hot pressing was observed visually. The pattern sharpness after hot pressing was rated with level 1 to 5 from poor to good. If the coating was not damaged and the pattern was sharp and had no deformation, it was of level 5. If the coating was not damaged and the pattern was sharp and had substantively no deformation, it was of level 4. If the coating was slightly damaged or the pattern was relative sharp but had slight deformation, it was of level 3. If the coating was damaged or the pattern was slightly blurred and had deformation or vignetting effect. it was of level 2. If the coating was obviously damaged or the pattern was blurred and had severe deformation or vignetting effect, it was of level 1. The pattern sharpness of level 3 to 5 was regarded as qualified.
Impranil® DLC-F: dispersion of an anionic polyurethane based on polycarbonate polyol as a milky white liquid, with solid content of 40±1% by weight, fusion enthalpy of the polyurethane of less than 3 J/g, tensile strength of about 50 MPa. 100% modulus of about 6.0 MPa. weight average molecular weight of 1630000-10600000, and carboxyl content of 0.8% by weight (based on solid content), available from Covestro.
Baybond® PU 407: dispersion of an anionic or non-ionic polyurethane based on polyester polyol as a milky white liquid, with solid content of 40±1%, available from Covestro.
Impranil® 1343: dispersion of an anionic polyurethane based on aliphatic polyether polyol as a milky white liquid, with solid content of 40+1% by weight, 100% modulus of about 2.2 MPa, weight average molecular weight of 330000-400000, and carboxyl content of 0.09% by weight (based on solid content), available from Covestro.
Impranil® DL 1069: dispersion of an anionic polyurethane based on aliphatic polyether polyol as a milky white liquid, with solid content of 50±1% by weight, fusion enthalpy of the polyurethane of less than 3 J/g, tensile strength of about 50 MPa, 100% modulus of about 1.6 MPa, and weight average molecular weight of 250000-400000, available from Covestro.
Imprafix® 2794: hydrophilically modified blocked aliphatic isocyanate with solid content of 38% by weight, isocyanate group (NCO) content of 12.7% by weight (based on solid content), and viscosity of <1500 mPa·s, available from Covestro.
Impranil® S 3000: dispersion of anionic amorphous silica as a transparent liquid, with solid content of 30% by weight, Z-average particle size of 28 nm. density of 1.21 g/cm3, and pH value of 10, available from Covestro.
Dispercoll® S 4020: dispersion of anionic amorphous silica as a translucent liquid, with solid content of 40% by weight, Z-average particle size of 46 nm, density of 1.29 g/cm3, and pH value of 9, available from Covestro.
Acematt TS 100: fumed silica as white powder, with particle size (ISO 13320-1) D50 of 9.5 μm, pH value of 6.5, and specific surface area (ISO 9277) of 250 g/m2, available from Evonik Specialty Chemicals. Method for preparing 10% aqueous dispersion of Acematt TS 100: Acematt TS 100 is dispersed in distilled water to form a dispersion with a concentration of 10%.
BYK093: silicone-containing defoamer as a turbid liquid, available from BYK.
BYK349: silicone surfactant as a light brown liquid, available from BYK.
Borchigel L75N: Rheology additive as a transparent liquid with a concentration of 20%, available from Borchers Company.
Platilon® U2102Ak: film of a thermoplastic polyurethane based on polyester polyol having the following characteristics: Shore hardness of 93A. specific gravity of 1.21, tensile strength of 65 MPa, elongation at break of 540%, 100% modulus of 10.5 MPa, minimum softening temperature of 150° C., maximum softening temperature of 180° C. and with translucent natural color, available from Covestro.
Platilon® PT7511: film of a thermoplastic polyurethane based on polyether polyol having the following characteristics: hardness of 90A. specific gravity of 1.13, tensile strength of 67 MPa, elongation at break of 550%, 100% modulus of 8.3 MPa, minimum softening temperature of 151° C., maximum softening temperature of 171° C., and with translucent natural color, available from Covestro.
Platilon® PT6411: film of a thermoplastic polyurethane based on polyether polyol having the following characteristics: Shore hardness of 71A, specific gravity of 1.16, tensile strength of 55 MPa, elongation at break of 900%, 100% modulus of 3.5 MPa, minimum softening temperature of 140° C., maximum softening temperature of 167° C., and with translucent natural color, available from Covestro.
Platilon® PS8010: film of a thermoplastic polyurethane based on polyester polyol having the following characteristics: Shore hardness of 92A, specific gravity of 1.21, tensile strength of 69 MPa, elongation at break of 610%, 100% modulus of 9.9 Mpa, minimum softening temperature of 142° C., maximum softening temperature of 163° C., and with translucent natural color, available from Covestro.
Platilon® U2100C-T: film of a thermoplastic polyurethane based on polyester polyol having the following characteristics: Shore hardness of 88A, specific gravity of 1.2, tensile strength of 54 MPa, elongation at break of 665%, 100% modulus of 6 MPa, minimum softening temperature of 125° C., maximum softening temperature of 155° C., and with translucent natural color, available from Covestro.
Platilon® HU2105C-T: based of a thermoplastic polyurethane film on polyester polyol having the following characteristics: Shore hardness of 75A, specific gravity of 1.2, tensile strength of 47 MPa, elongation at break of 861%, 100% modulus of 3.7 MPa, minimum softening temperature of 105° C., maximum softening temperature of 145° C., and with translucent natural color, available from Covestro.
Fume hood: Model 1524 X 84 DE2006-7 B6, manufactured by Schneider Electric Co., Ltd. Mechanical disperser: Model SFJ400, manufactured by Shanghai Modern Environmental Engineering Technology Co., Ltd.
Electronic balance: Model BSA4202S, Max 4200g, d=0.01 g, manufactured by Sartorius Group.
Film thickness gauge: Model SM-114, manufactured by TECLOCK Co., Ltd., Japan.
Mathis laboratory coater: Model CH-8156, manufactured by Werner Mathis AG.
Mathis laboratory dryer: Model CH-8156, manufactured by Werner Mathis AG.
Table 1 shows components of the aqueous coating compositions and content of each component;
Table 2 shows coated films comprising various plastic films and coatings formed from various aqueous coating compositions, and test results of performance of the films.
According to the components and contents shown in Table 1, an appropriate amount of polyurethane dispersion was weighed with an electronic balance (BSA4202S) into a plastic compounding cup, and dispersed with mechanical disperser (SFJ-400). Then, BYK 093, BYK 349, Imprafix® 2794, a silica dispersion and Borchigel L 75N were added dropwise in sequence. According to the viscosity change of the mixture (the viscosity being tested by Brookfield viscometer with a 64 #rotor at a rotation speed of 20 rpm), the rotation speed of the mechanical disperser was adjusted to 1500 rpm. The mixture was continuously stirred for 5-10 minutes until it was uniformly mixed, and filtered to obtain an aqueous coating composition.
According to Table 2, a plastic film with a size of 25 cm*40 cm was fixed on the Mathis coating rack and placed on the Mathis laboratory coater. The gap between the coating blade and the plastic film was adjusted to 0.02 mm. An appropriate amount of the aqueous coating composition was coated by pulling the blade across the surface of the plastic film at a uniform speed. The Mathis coating rack was dried in the Mathis laboratory dryer firstly at 60° C. for 8 min (the upper and lower air speed of the dryer of 700 rpm), and then at 70° C. for 8 min (the upper and lower air speed of the dryer of 700 rpm). After drying, the Mathis coating rack was taken out and placed on a stainless steel test bench to cool to room temperature. Then, the coated plastic film was removed from the coating rack and placed on the storage rack steadily.
The coated film after coating and drying was cut into a 30 mm-wide strip, and placed on a printer Novex XLP504, with the coated surface facing the ribbon. Printing was performed according to the pattern set by input.
The coated films of Examples 1-9 had good grade of surface dryness, adhesion and haze value, and the patterns printed on the film surface could remain sharp before and after hot pressing.
The aqueous coating composition 7 used in Comparative Example 1 comprised a small amount of dispersion of an anionic polyurethane based on polycarbonate polyol. The coated film obtained by coating with the aqueous coating composition 7 had unqualified grade of surface dryness and anti-blocking and unqualified haze value.
The aqueous coating composition 12 used in Comparative Example 2 comprised no dispersion of an anionic polyurethane based on polycarbonate polyol. The coated film obtained by coating with the aqueous coating composition 12 had unqualified grade of surface dryness and anti-blocking, and the pattern printed on the film surface could not remain sharp after hot pressing.
The aqueous coating composition 13 used in Comparative Example 3 comprised no dispersion of an anionic polyurethane based on polycarbonate polyol. The coated film obtained by coating with the aqueous coating composition 13 had unqualified grade of surface dryness and anti-blocking, unqualified haze value and the pattern printed on the film surface could not remain sharp before and after hot pressing.
The aqueous coating composition 14 used in Comparative Example 4 comprised no dispersion of an anionic polyurethane based on polycarbonate polyol. The coated film obtained by coating with the aqueous coating composition 14 had unqualified grade of surface dryness and anti-blocking, and the pattern printed on the film surface could not remain sharp before and after hot pressing.
The plastic films used in Comparative Examples 5 and 6 were films of a thermoplastic polyurethane based on polyether polyol. The resulting coated films could not meet the requirements of adhesion, haze value, and the pattern sharpness before and after hot pressing.
The plastic film used in Comparative Example 7 was a film of a thermoplastic polyurethane based on polyester polyol with Shore hardness of 75A. The resulting coated film had poor adhesion.
The aqueous coating composition 8 used in Comparative Example 8 comprised 88% by weight of a dispersion of an anionic polyurethane based on polycarbonate polyol and comprised no dispersion of anionic silica. The coated film obtained by coating with the aqueous coating composition 8 had unqualified grade of surface dryness and anti-blocking.
The aqueous coating composition 9 used in Comparative Example 9 comprised 20% by weight of a dispersion of anionic amorphous silica. The film obtained by coating with the aqueous coating composition 9 had unqualified adhesion.
The aqueous coating composition 10 used in Comparative Example 10 comprised 20% by weight of a 10% aqueous dispersion of fumed silica Acematt TS 100, wherein the dispersion was non-ionic, and the film coated therewith had unqualified haze value.
Those skilled in the art will readily understand that the present invention is not limited to the foregoing details, and can be implemented in other specific forms without departing from the spirit or main characteristics of the present invention. Therefore, the examples should be regarded as illustrative rather than restrictive from any point of view, so that the scope of the present invention is illustrated by the claims rather than the foregoing description. Therefore, any change shall be regarded as belonging to the present invention, as long as it falls into the meaning and scope of equivalents of the claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202111251429.4 | Oct 2021 | CN | national |
| 21212678.3 | Dec 2021 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/079678 | 10/25/2022 | WO |
