High-fastness washable transfer film, method of making and application on cotton fabric

Abstract

The application relates to the technical field of layered materials, and discloses a high-fastness washable transfer film, a preparation method and application on cotton fabrics. The preparation method comprises the following steps: the transfer film has a multilayer structure of a glue layer, an aluminum plating layer, a protective layer and a base film, wherein the glue layer material is de-enclosed by an enclosed polyurethane during heat transfer, releases isocyanate groups, and further reacts with hydroxyl groups in the glue layer material and hydroxyl groups on the surface of the cotton fabric, so that the heat transfer film has excellent bonding fastness and washable performance when applied to the cotton fabric.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of layered materials, in particular to a high-fastness washable transfer film, a preparation method and application on cotton fabric. BACKGROUND

[0002] The heat transfer film refers to a special functional printing film that the graphics with adhesive are separated from the base film together with the protective layer under the action of heat and pressure, and firmly bonded to the surface of the printing material. The heat transfer film generally includes a base layer, a release layer, a protective layer, an ink layer and an adhesive layer. The adhesive layer material is mainly solvent-based hot melt adhesive. Its main function is to have high adhesion with the surface of the printing material. In the process of heat transfer, the adhesive layer is in a flowing state under heat and pressure, and has certain adhesive properties, so that the ink layer and the surface of the printing material obtain firm bonding force.

[0003] The heat transfer film for fabric has poor wash resistance when applied to cotton fabric, thus limiting its application. This is due to insufficient adhesion between cotton fibers and the adhesive layer, poor water resistance of the adhesive layer, and other reasons. Therefore, preparing a high-fastness and washable heat transfer film can effectively expand the application range of the heat transfer film on cotton fabric.

[0004] The heat-reactive polyurethane, also known as blocked polyurethane, is a special polyurethane containing unblocked isocyanate groups. It is stable at low temperatures, and when it rises to a certain temperature, the isocyanate groups are unblocked during application and can react with active hydrogen substances, thereby realizing the regulation of its function. The blocked waterborne polyurethane, as a block compound, contains soft segment and hard segment, and thus has the advantages of low temperature resistance, adjustable flexibility and strong adhesion, and can be applied in adhesives to improve the adhesion performance. SUMMARY

[0005] The present application aims to overcome the shortcomings of the prior art and provide a high-fastness washable transfer film, a preparation method and application on cotton fabric. The transfer film has a multi-layer structure of adhesive layer, aluminum plating layer, protective layer and base film, and has excellent adhesion and wash resistance when applied to cotton fabric.

[0006] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0007] A preparation method of a high-fastness washable transfer film, comprising the following steps:

[0008] Step (1), apply the protective layer material to the side of the base film with the release layer, and after the application is completed, solidify to obtain a protective layer / base film composite film;

[0009] Step (2), the protective layer / base film composite film with the side of the protective layer is plated with aluminum to obtain an aluminum plating layer / protective layer / base film composite film;

[0010] Step (3), the adhesive layer material is coated on the side of the aluminum plating layer / protective layer / base film composite film with the aluminum plating layer, dried to form an adhesive layer, and a high-stability water-washing-resistant transfer film is obtained.

[0011] Preferably, in the step (1), the base film is a PET release film; the protective layer material is an aliphatic polyurethane acrylate; the curing condition is: curing for 30-40s under ultraviolet light with a wavelength of 365nm; and the thickness of the protective layer is 4-6μm.

[0012] Preferably, in the step (2), the aluminum plating condition is: vacuum evaporation process is adopted to plate aluminum under a vacuum condition of 10 -4 mbar; and the thickness of the aluminum plating layer is 30-50nm.

[0013] Preferably, in the step (3), the drying condition is: drying for 24-48h under a relative humidity of 25-30% and a temperature of 25-30℃; and the thickness of the adhesive layer is 25-30μm.

[0014] Preferably, in the step (3), the adhesive layer material is prepared by the following steps:

[0015] S1, 3-mercapto propyl methyl trimethoxysilane, 1mol / L KOH aqueous solution, and octamethylcyclotetrasiloxane are mixed, reacted, cooled, the pH value is adjusted to neutral, and rotary evaporation is performed to obtain a thiol-modified hydroxyl silicone oil;

[0016] S2, the thiol-modified hydroxyl silicone oil, a photoinitiator, and acetone are mixed and ultrasonically dispersed, isobornyl acrylate and castor oil are added, reacted, and rotary evaporation is performed after the reaction to obtain a silicone-containing castor oil-based polyol;

[0017] S3, 3-methyl acryloyl dopamine, butyl acrylate, hydroxypropyl methacrylate, and ethanol are uniformly mixed, an initiator azobisisobutyronitrile is added, reacted, purified, dried, and a dopamine-containing polyacrylate is obtained.

[0018] The dopamine-containing polyacrylate, a blocked polyurethane, the silicone-containing castor oil-based polyol, and acetone are uniformly mixed to obtain the adhesive layer material.

[0019] Preferably, in the preparation of the adhesive layer material in the step (3), in S1, the mass ratio of 3-mercapto propyl methyl trimethoxysilane, 1mol / L KOH aqueous solution, and octamethylcyclotetrasiloxane is 12-18:0.8-1.2:20-30; and the reaction condition is: reaction for 6-8h under a rotation speed of 500-800r / min and a temperature of 130-150℃.

[0020] Preferably, in step (3), when preparing the adhesive layer material, the mass ratio of mercapto-modified hydroxyl silicone oil, isoborneol acrylate, castor oil, photoinitiator, and acetone in S2 is 5.2-5.5:1-1.5:19.2-20:0.04-0.05:80-100; the reaction conditions are: reacting for 3-5 hours in an ultraviolet light environment with a wavelength of 365 nm and a rotation speed of 500-800 r / min.

[0021] Preferably, in step (3), when preparing the adhesive layer material, the molar ratio of 3-methacrylamide, butyl acrylate, hydroxypropyl methacrylate, and azobisisobutyronitrile in S3 is 1.5-2:18.5:2-2.5:0.08-0.1; the reaction conditions are: reaction in a nitrogen atmosphere at 50-70°C for 24-48 hours.

[0022] Preferably, in step (3), when preparing the adhesive layer material, the purification operation in step S3 includes: adding petroleum ether to the crude reaction product to precipitate, then dissolving it with tetrahydrofuran, and finally adding n-hexane to precipitate and taking the precipitate.

[0023] Preferably, in step (3), when preparing the adhesive layer material, the mass ratio of dopamine polyacrylate, blocked polyurethane, silicone castor oil-based polyol, and acetone in S3 is 10-15:50:10-15:100-120.

[0024] Preferably, in step (3), when preparing the adhesive layer material, the closed polyurethane in S3 is prepared by the following steps:

[0025] Toluene-2,4-diisocyanate, polypropylene glycol, and dibutyltin dilaurate catalyst were mixed and reacted. After the reaction was completed, methyl ethyl ketone oxime was added and the reaction was continued. After the reaction was completed, the mixture was cooled to obtain a blocked polyurethane.

[0026] The molar ratio of toluene-2,4-diisocyanate, polypropylene glycol, and methyl ethyl ketone oxime is 2:1:2-2.2; the amount of dibutyltin dilaurate catalyst added is 0.05 wt% of the mass of polypropylene glycol; the reaction conditions are: reaction at 60-90℃ for 1-2 hours in a nitrogen atmosphere; the reaction is continued at 60-65℃ for 3-4 hours.

[0027] Preferably, a high-fastness, water-washable transfer film is prepared using the method described above.

[0028] Preferably, the application of a high-fastness, wash-resistant transfer film as described above on cotton fabrics.

[0029] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0030] This invention prepares a heat transfer film with a multi-layer structure consisting of an adhesive layer, an aluminum plating layer, a protective layer, and a base film. By preparing a multi-component adhesive containing blocked polyurethane as the adhesive layer material of the heat transfer film, the blocked polyurethane is deblocked during heat transfer, releasing isocyanate groups, which further react with the hydroxyl-containing components in the adhesive layer material and the hydroxyl groups on the surface of the cotton fabric, effectively improving the adhesion strength and washability of the heat transfer film.

[0031] This invention utilizes the polymerization of 3-mercaptopropylmethyltrimethoxysilane and octamethylcyclotetrasiloxane to form mercapto-modified hydroxyl silicone oil. Then, by utilizing the mercapto-alkene click chemical reaction between the mercapto group and the carbon-carbon double bond, the mercapto-modified hydroxyl silicone oil and isoborneol acrylate are introduced into castor oil to obtain a silicone-containing castor oil-based polyol. This polyol is then added as a third component to a blocked polyurethane and a dopamine-containing polyacrylate to form an adhesive layer material.

[0032] Among them, the dopamine-containing polyacrylate has 3-methacrylamide monomer added during polymerization, which improves the adhesion performance of the adhesive layer material to the aluminum-plated layer and cotton fabric by utilizing the catechol group; the silicone castor oil-based polyol improves the hydrophobicity, moisture and heat resistance and hydrolysis resistance of the adhesive layer material. This is due to the introduction of the rigid terpene ring structure of isoborneol acrylate, which improves the heat resistance. The silane segments in the mercapto-modified hydroxyl silicone oil improve the water resistance of the material. At the same time, during heat transfer, the isocyanate groups in the adhesive layer material react with the hydroxyl-containing components and the hydroxyl groups on the surface of the cotton fabric to form a cross-linked structure, which further improves the adhesion performance of the adhesive layer to the cotton fabric and the water washing resistance. Attached Figure Description

[0033] Figure 1 This is a schematic diagram of the structure of the high-strength, water-washable transfer membrane prepared in this invention;

[0034] Figure 2 This is a bar chart showing the tensile strength retention rate of samples 1-5 in the performance test of this invention;

[0035] Figure 3 This is a bar chart showing the peel strength retention rate of samples 1-5 in the performance test of this invention;

[0036] In the picture:

[0037] 1. Adhesive layer; 2. Aluminum plating layer; 3. Protective layer; 4. Base film. Detailed Implementation

[0038] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0039] Example 1

[0040] This embodiment discloses a method for preparing an adhesive layer material, including the following steps:

[0041] Step (1): Mix 3-mercaptopropylmethyltrimethoxysilane and 1 mol / L KOH aqueous solution, add octamethylcyclotetrasiloxane at 140℃, and react for 6 h at 140℃ and 500 r / min. After the reaction is completed, cool to room temperature, adjust the pH value to neutral with 0.1 mol / L hydrochloric acid aqueous solution, remove water by rotary evaporation, and obtain mercapto-modified hydroxyl silicone oil.

[0042] The mass ratio of 3-mercaptopropylmethyltrimethoxysilane, 1 mol / L KOH aqueous solution, and octamethylcyclotetrasiloxane is 12:0.8:20.

[0043] Thiol-modified hydroxyl silicone oil, photoinitiator 1173, and acetone were mixed and ultrasonically dispersed for 5 min. Isoborneol acrylate and castor oil were added, and the mixture was reacted for 3 h in an ultraviolet light environment with a wavelength of 365 nm and a rotation speed of 500 r / min. After the reaction was completed, the solvent acetone was removed by rotary evaporation to obtain a silicone castor oil-based polyol.

[0044] The mass ratio of mercapto-modified hydroxyl silicone oil, isoborneol acrylate, castor oil, photoinitiator 1173, and acetone is 5.2:1:19.2:0.04:80.

[0045] Step (2): Mix 3-methacrylamide, butyl acrylate, hydroxypropyl methacrylate and ethanol evenly, add the initiator azobisisobutyronitrile, and react at 70°C for 24 hours in a nitrogen atmosphere. After the reaction is completed, the crude product is obtained. Petroleum ether is added to precipitate the product, which is then dissolved in tetrahydrofuran. Finally, hexane is added to precipitate the product. The precipitate is dried at 60°C for 48 hours to obtain dopamine-containing polyacrylate.

[0046] The molar ratio of 3-methacrylamide dopamine, butyl acrylate, hydroxypropyl methacrylate, and azobisisobutyronitrile is 1.5:18.5:2.5:0.08.

[0047] Dopamine-containing polyacrylate, blocked polyurethane, silicone castor oil-based polyol, and acetone are mixed evenly in a mass ratio of 15:50:10:100 to obtain the adhesive layer material.

[0048] The closed-type polyurethane is prepared by the following steps:

[0049] Toluene-2,4-diisocyanate, polypropylene glycol, and dibutyltin dilaurate catalyst were mixed and reacted at 60°C for 2 hours under a nitrogen atmosphere. After the reaction was completed, methyl ethyl ketone oxime was added, and the reaction was continued at 60°C for another 4 hours. After the reaction was completed, the mixture was cooled to room temperature to obtain a blocked polyurethane. The molar ratio of toluene-2,4-diisocyanate, polypropylene glycol, and methyl ethyl ketone oxime was 2:1:2. The amount of dibutyltin dilaurate catalyst added was 0.05 wt% of the mass of polypropylene glycol.

[0050] Example 2

[0051] This embodiment discloses a method for preparing an adhesive layer material, including the following steps:

[0052] Step (1): Mix 3-mercaptopropylmethyltrimethoxysilane and 1 mol / L KOH aqueous solution, add octamethylcyclotetrasiloxane at 140℃, and react for 6 h at 140℃ and 500 r / min. After the reaction is completed, cool to room temperature, adjust the pH value to neutral with 0.1 mol / L hydrochloric acid aqueous solution, remove water by rotary evaporation, and obtain mercapto-modified hydroxyl silicone oil.

[0053] The mass ratio of 3-mercaptopropylmethyltrimethoxysilane, 1 mol / L KOH aqueous solution, and octamethylcyclotetrasiloxane is 15:1:25.

[0054] Thiol-modified hydroxyl silicone oil, photoinitiator 1173, and acetone were mixed and ultrasonically dispersed for 5 min. Isoborneol acrylate and castor oil were added, and the mixture was reacted for 3 h in an ultraviolet light environment with a wavelength of 365 nm and a rotation speed of 500 r / min. After the reaction was completed, the solvent acetone was removed by rotary evaporation to obtain a silicone castor oil-based polyol.

[0055] The mass ratio of mercapto-modified hydroxyl silicone oil, isoborneol acrylate, castor oil, photoinitiator 1173, and acetone is 5.3:1.3:19.6:0.04:90.

[0056] Step (2): Mix 3-methacrylamide, butyl acrylate, hydroxypropyl methacrylate and ethanol evenly, add the initiator azobisisobutyronitrile, and react at 70°C for 24 hours in a nitrogen atmosphere. After the reaction is completed, the crude product is obtained. Petroleum ether is added to precipitate the product, which is then dissolved in tetrahydrofuran. Finally, hexane is added to precipitate the product. The precipitate is dried at 60°C for 48 hours to obtain dopamine-containing polyacrylate.

[0057] The molar ratio of 3-methacrylamide dopamine, butyl acrylate, hydroxypropyl methacrylate, and azobisisobutyronitrile is 1.8:18.5:2.2:0.09.

[0058] Dopamine-containing polyacrylate, blocked polyurethane, silicone castor oil-based polyol, and acetone are mixed evenly in a mass ratio of 12:50:13:100 to obtain an adhesive layer material.

[0059] The closed-type polyurethane is prepared by the following steps:

[0060] Toluene-2,4-diisocyanate, polypropylene glycol, and dibutyltin dilaurate catalyst were mixed and reacted at 60°C for 2 hours under a nitrogen atmosphere. After the reaction was completed, methyl ethyl ketone oxime was added, and the reaction was continued at 60°C for another 4 hours. After the reaction was completed, the mixture was cooled to room temperature to obtain a blocked polyurethane. The molar ratio of toluene-2,4-diisocyanate, polypropylene glycol, and methyl ethyl ketone oxime was 2:1:2.2. The amount of dibutyltin dilaurate catalyst added was 0.05 wt% of the mass of polypropylene glycol.

[0061] Example 3

[0062] This embodiment discloses a method for preparing an adhesive layer material, including the following steps:

[0063] Step (1): Mix 3-mercaptopropylmethyltrimethoxysilane and 1 mol / L KOH aqueous solution, add octamethylcyclotetrasiloxane at 140℃, and react for 6 h at 140℃ and 500 r / min. After the reaction is completed, cool to room temperature, adjust the pH value to neutral with 0.1 mol / L hydrochloric acid aqueous solution, remove water by rotary evaporation, and obtain mercapto-modified hydroxyl silicone oil.

[0064] The mass ratio of 3-mercaptopropylmethyltrimethoxysilane, 1 mol / L KOH aqueous solution, and octamethylcyclotetrasiloxane is 18:1.2:30.

[0065] Thiol-modified hydroxyl silicone oil, photoinitiator 1173, and acetone were mixed and ultrasonically dispersed for 5 min. Isoborneol acrylate and castor oil were added, and the mixture was reacted for 3 h in an ultraviolet light environment with a wavelength of 365 nm and a rotation speed of 500 r / min. After the reaction was completed, the solvent acetone was removed by rotary evaporation to obtain a silicone castor oil-based polyol.

[0066] The mass ratio of mercapto-modified hydroxyl silicone oil, isoborneol acrylate, castor oil, photoinitiator 1173, and acetone is 5.5:1.5:20:0.05:100.

[0067] Step (2): Mix 3-methacrylamide, butyl acrylate, hydroxypropyl methacrylate and ethanol evenly, add the initiator azobisisobutyronitrile, and react at 70°C for 24 hours in a nitrogen atmosphere. After the reaction is completed, the crude product is obtained. Petroleum ether is added to precipitate the product, which is then dissolved in tetrahydrofuran. Finally, hexane is added to precipitate the product. The precipitate is dried at 60°C for 48 hours to obtain dopamine-containing polyacrylate.

[0068] The molar ratio of 3-methacrylamide dopamine, butyl acrylate, hydroxypropyl methacrylate, and azobisisobutyronitrile is 2:18.5:2:0.1.

[0069] Dopamine-containing polyacrylate, blocked polyurethane, silicone castor oil-based polyol, and acetone are mixed evenly in a mass ratio of 10:50:15:100 to obtain the adhesive layer material.

[0070] The closed-type polyurethane is prepared by the following steps:

[0071] Toluene-2,4-diisocyanate, polypropylene glycol, and dibutyltin dilaurate catalyst were mixed and reacted at 60°C for 2 hours under a nitrogen atmosphere. After the reaction was completed, methyl ethyl ketone oxime was added, and the reaction was continued at 65°C for 3 hours. After the reaction was completed, the mixture was cooled to room temperature to obtain a blocked polyurethane. The molar ratio of toluene-2,4-diisocyanate, polypropylene glycol, and methyl ethyl ketone oxime was 2:1:2.2. The amount of dibutyltin dilaurate catalyst added was 0.05 wt% of the mass of polypropylene glycol.

[0072] Example 4

[0073] This embodiment discloses a method for preparing a high-strength, water-washable transfer film, comprising the following steps:

[0074] Step (1): Use PET release film as the base film and aliphatic polyurethane acrylate as the protective layer material.

[0075] The protective layer material is coated on the side of the base film with the release layer. After coating, it is cured in ultraviolet light with a wavelength of 365nm for 40s to form a protective layer with a thickness of 4μm, thus obtaining a protective layer / base film composite film.

[0076] Step (2): The protective layer side of the protective layer / base film composite film is vacuum-deposited at 10°C. -4 Aluminum was deposited under mbar vacuum conditions to form an aluminum layer with a thickness of 50nm, resulting in an aluminum layer / protective layer / base film composite film.

[0077] Step (3): The adhesive material prepared in Example 1 is coated on the side of the aluminum-plated layer / protective layer / base film composite film with the aluminum plating layer, and dried at a relative humidity of 25% and a temperature of 25°C for 48 hours to form an adhesive layer with a thickness of 25μm, thereby obtaining a high-strength water-resistant transfer film.

[0078] Example 5

[0079] This embodiment discloses a method for preparing a high-strength, water-washable transfer film, comprising the following steps:

[0080] Step (1): Use PET release film as the base film and aliphatic polyurethane acrylate as the protective layer material.

[0081] The protective layer material is coated on the side of the base film with the release layer. After coating, it is cured in ultraviolet light with a wavelength of 365nm for 40s to form a protective layer with a thickness of 4μm, thus obtaining a protective layer / base film composite film.

[0082] Step (2): The protective layer side of the protective layer / base film composite film is vacuum-deposited at 10°C. -4 Aluminum was deposited under mbar vacuum conditions to form an aluminum layer with a thickness of 50nm, resulting in an aluminum layer / protective layer / base film composite film.

[0083] Step (3): The adhesive material prepared in Example 2 is coated on the side of the aluminum-plated layer / protective layer / base film composite film with the aluminum plating layer, and dried at a relative humidity of 25% and a temperature of 25°C for 48 hours to form an adhesive layer with a thickness of 25μm, thereby obtaining a high-strength water-resistant transfer film.

[0084] Example 6

[0085] This embodiment discloses a method for preparing a high-strength, water-washable transfer film, comprising the following steps:

[0086] Step (1): Use PET release film as the base film and aliphatic polyurethane acrylate as the protective layer material.

[0087] The protective layer material is coated on the side of the base film with the release layer. After coating, it is cured in ultraviolet light with a wavelength of 365nm for 40s to form a protective layer with a thickness of 4μm, thus obtaining a protective layer / base film composite film.

[0088] Step (2): The protective layer side of the protective layer / base film composite film is vacuum-deposited at 10°C. -4 Aluminum was deposited under mbar vacuum conditions to form an aluminum layer with a thickness of 50nm, resulting in an aluminum layer / protective layer / base film composite film.

[0089] Step (3): The adhesive material prepared in Example 3 is coated on the side of the aluminum-plated layer / protective layer / base film composite film with the aluminum plating layer, and dried at a relative humidity of 25% and a temperature of 25°C for 48 hours to form an adhesive layer with a thickness of 25μm, thereby obtaining a high-strength water-resistant transfer film.

[0090] Comparative Example 1

[0091] This comparative example discloses a method for preparing an adhesive layer material, including the following steps:

[0092] Step (1): Mix 3-methacrylamide, butyl acrylate, hydroxypropyl methacrylate and ethanol evenly, add the initiator azobisisobutyronitrile, and react at 70°C for 24 hours in a nitrogen atmosphere. After the reaction is completed, the crude product is obtained. Petroleum ether is added to precipitate the product, which is then dissolved in tetrahydrofuran. Finally, hexane is added to precipitate the product. The precipitate is dried at 60°C for 48 hours to obtain dopamine-containing polyacrylate.

[0093] The molar ratio of 3-methacrylamide dopamine, butyl acrylate, hydroxypropyl methacrylate, and azobisisobutyronitrile is 1.5:18.5:2.5:0.08.

[0094] Dopamine-containing polyacrylate, blocked polyurethane, castor oil, and acetone are mixed evenly in a mass ratio of 15:50:10:100 to obtain the adhesive layer material.

[0095] The closed-type polyurethane is prepared by the following steps:

[0096] Toluene-2,4-diisocyanate, polypropylene glycol, and dibutyltin dilaurate catalyst were mixed and reacted at 60°C for 2 hours under a nitrogen atmosphere. After the reaction was completed, methyl ethyl ketone oxime was added, and the reaction was continued at 60°C for another 4 hours. After the reaction was completed, the mixture was cooled to room temperature to obtain a blocked polyurethane. The molar ratio of toluene-2,4-diisocyanate, polypropylene glycol, and methyl ethyl ketone oxime was 2:1:2. The amount of dibutyltin dilaurate catalyst added was 0.05 wt% of the mass of polypropylene glycol.

[0097] Comparative Example 2

[0098] This comparative example discloses a method for preparing an adhesive layer material, including the following steps:

[0099] Step (1): Mix 3-mercaptopropylmethyltrimethoxysilane and 1 mol / L KOH aqueous solution, add octamethylcyclotetrasiloxane at 140℃, and react for 6 h at 140℃ and 500 r / min. After the reaction is completed, cool to room temperature, adjust the pH value to neutral with 0.1 mol / L hydrochloric acid aqueous solution, remove water by rotary evaporation, and obtain mercapto-modified hydroxyl silicone oil.

[0100] The mass ratio of 3-mercaptopropylmethyltrimethoxysilane, 1 mol / L KOH aqueous solution, and octamethylcyclotetrasiloxane is 12:0.8:20.

[0101] Thiol-modified hydroxyl silicone oil, photoinitiator 1173, and acetone were mixed and ultrasonically dispersed for 5 min. Isoborneol acrylate and castor oil were added, and the mixture was reacted for 3 h in an ultraviolet light environment with a wavelength of 365 nm and a rotation speed of 500 r / min. After the reaction was completed, the solvent acetone was removed by rotary evaporation to obtain a silicone castor oil-based polyol.

[0102] The mass ratio of mercapto-modified hydroxyl silicone oil, isoborneol acrylate, castor oil, photoinitiator 1173, and acetone is 5.2:1:19.2:0.04:80.

[0103] Step (2): Mix the closed polyurethane, silicone castor oil-based polyol, and acetone in a mass ratio of 50:10:100 to obtain the adhesive layer material.

[0104] The closed-type polyurethane is prepared by the following steps:

[0105] Toluene-2,4-diisocyanate, polypropylene glycol, and dibutyltin dilaurate catalyst were mixed and reacted at 60°C for 2 hours under a nitrogen atmosphere. After the reaction was completed, methyl ethyl ketone oxime was added, and the reaction was continued at 60°C for another 4 hours. After the reaction was completed, the mixture was cooled to room temperature to obtain a blocked polyurethane. The molar ratio of toluene-2,4-diisocyanate, polypropylene glycol, and methyl ethyl ketone oxime was 2:1:2. The amount of dibutyltin dilaurate catalyst added was 0.05 wt% of the mass of polypropylene glycol.

[0106] Comparative Example 3

[0107] This comparative example discloses a method for preparing a transfer membrane, comprising the following steps:

[0108] Step (1): Use PET release film as the base film and aliphatic polyurethane acrylate as the protective layer material.

[0109] The protective layer material is coated on the side of the base film with the release layer. After coating, it is cured in ultraviolet light with a wavelength of 365nm for 40s to form a protective layer with a thickness of 4μm, thus obtaining a protective layer / base film composite film.

[0110] Step (2): The protective layer side of the protective layer / base film composite film is vacuum-deposited at 10°C. -4 Aluminum was deposited under mbar vacuum conditions to form an aluminum layer with a thickness of 50nm, resulting in an aluminum layer / protective layer / base film composite film.

[0111] Step (3): The adhesive material prepared in Comparative Example 1 is coated on the side of the aluminum-plated layer / protective layer / base film composite film with the aluminum plating layer, and dried at a relative humidity of 25% and a temperature of 25℃ for 48 hours to form an adhesive layer with a thickness of 25μm, thus obtaining a transfer film.

[0112] Comparative Example 4

[0113] This comparative example discloses a method for preparing a transfer membrane, comprising the following steps:

[0114] Step (1): Use PET release film as the base film and aliphatic polyurethane acrylate as the protective layer material.

[0115] The protective layer material is coated on the side of the base film with the release layer. After coating, it is cured in ultraviolet light with a wavelength of 365nm for 40s to form a protective layer with a thickness of 4μm, thus obtaining a protective layer / base film composite film.

[0116] Step (2): The protective layer side of the protective layer / base film composite film is vacuum-deposited at 10°C. -4 Aluminum was deposited under mbar vacuum conditions to form an aluminum layer with a thickness of 50nm, resulting in an aluminum layer / protective layer / base film composite film.

[0117] Step (3): The adhesive material prepared in Comparative Example 2 is coated on the side of the aluminum-plated layer / protective layer / base film composite film with the aluminum plating layer, and dried at a relative humidity of 25% and a temperature of 25℃ for 48 hours to form an adhesive layer with a thickness of 25μm, thus obtaining a transfer film.

[0118] In the above examples and comparative examples: the polypropylene glycol is polypropylene glycol 2000; the castor oil has an Mn of 933; the CAS number of 3-methacrylamide is 471915-89-6; and the aliphatic polyurethane acrylate is EBECREL 8413.

[0119] Test case

[0120] (1) The adhesive materials prepared in Examples 1-3 and Comparative Examples 1-2 were coated onto the release film with a coating thickness of 1 mm. The coatings were cured at 130°C for 3 minutes. After curing, the release film was removed to obtain samples 1-5, which were then tested for mechanical properties and resistance to damp heat. Specific test results are shown in Table 1.

[0121] Table 1

[0122] Tensile strength (MPa) Tensile strength retention (%) Sample 1 36.9 91.2 Sample 2 37.3 90.6 Sample 3 37.2 91.0 Sample 4 37.0 72.3 Sample 5 36.8 91.1

[0123] The tests for each indicator in Table 1 were conducted according to the following standards: Tensile strength was determined in accordance with GB / T 528-2009 "Determination of Tensile Stress-Strain Properties of Vulcanized Rubber or Thermoplastic Rubber"; Moist heat resistance was expressed by the tensile strength retention rate. Samples 1-5 were placed in water at 100℃ for a damp heat aging test for 12 hours, then removed for tensile testing, and the tensile strength retention rate was calculated.

[0124] As can be seen from the test results in Table 1, the adhesive layer material prepared by this invention has excellent resistance to damp heat. This is because the silicone castor oil-based polyol improves the hydrophobicity, resistance to damp heat, and resistance to hydrolysis of the adhesive layer material. The rigid terpene ring structure of isoborneol acrylate improves the heat resistance of the material, while the silane segments in the mercapto-modified hydroxyl silicone oil improve the water resistance of the material. Furthermore, during the thermosetting process, the isocyanate groups in the adhesive layer material react with the hydroxyl-containing components to form a cross-linked structure, further improving the mechanical properties and water resistance.

[0125] In Comparative Example 1, the castor oil was not modified, and the improvement effect of isoborneol acrylate and mercapto-modified hydroxyl silicone oil on the moisture and heat resistance of the adhesive layer material was lacking. Therefore, the moisture and heat resistance of Sample 4 prepared in Comparative Example 1 was not as good as that of the sample prepared in the Example.

[0126] (2) The transfer films prepared in Examples 4-6 and Comparative Examples 3-4 were bonded to the surface of a cotton fabric base, with the adhesive layer side of the transfer film in contact with the cotton fabric base. The films were then pressed and cooled at 130°C, and these samples were designated as samples 1-5. The adhesion and washability of samples 1-5 were tested. The specific test results are shown in Table 2.

[0127] Table 2

[0128] Peel strength (N) Peel strength retention (%) Specimen 1 17.8 98.1 Specimen 2 18.1 98.3 Specimen 3 18.4 98.2 Specimen 4 17.7 89.5 Specimen 5 15.3 98.2

[0129] The tests for each indicator in Table 2 were conducted according to the following standards: Peel strength was tested according to FZ / T 80007.1-2006 "Test Method for Peel Strength of Coated Fabrics for Membrane Structures"; Washability was expressed by peel strength retention rate, after washing samples 1-5 50 times with water, peel strength was tested and peel strength retention rate was calculated.

[0130] As can be seen from the test results in Table 1, the heat transfer film prepared by this invention exhibits excellent adhesion and washability. This is because the adhesive layer material contains blocked polyurethane, dopamine-containing polyacrylate, and silicone castor oil-based polyol. The dopamine-containing polyacrylate utilizes catechol groups to improve the adhesion between the adhesive layer material and the aluminum-plated layer and the cotton fabric. The silicone castor oil-based polyol improves the hydrophobicity, moisture resistance, and hydrolysis resistance of the adhesive layer material. During heat transfer, the blocked polyurethane is deblocked, and the isocyanate groups react with the hydroxyl-containing components and the hydroxyl groups on the surface of the cotton fabric to form a cross-linked structure, further improving the peel strength and washability of the adhesive layer on the cotton fabric. Sample 4, representing Comparative Example 3, uses the adhesive layer material prepared in Comparative Example 1. The castor oil was not modified, resulting in reduced hydrophobicity of the adhesive layer material and decreased washability of the transfer film. Therefore, the peel strength retention rate of Sample 4 is reduced.

[0131] Sample 5, representing Comparative Example 4, uses the adhesive material prepared in Comparative Example 2. It does not contain dopamine-containing polyacrylate. The lack of dopamine-containing polyacrylate improves the adhesion performance of the adhesive material to the aluminum-plated layer and cotton fabric by utilizing catechol groups, so the peel strength of Sample 5 is reduced.

[0132] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a high-strength, water-washable transfer film, characterized in that, Includes the following steps: Step (1): Coat the protective layer material on the side of the base film with the release layer. After coating, cure to obtain a protective layer / base film composite film. Step (2): Aluminum is plated on the side of the protective layer / base film composite film to obtain the aluminum-plated layer / protective layer / base film composite film; Step (3): Mix dopamine-containing polyacrylate, blocked polyurethane, silicone castor oil-based polyol, and acetone evenly to obtain the adhesive layer material; The silicon-containing castor oil-based polyol is prepared by the following steps: S1. Mix 3-mercaptopropylmethyltrimethoxysilane and 1 mol / L KOH aqueous solution, add octamethylcyclotetrasiloxane, react, cool after the reaction is complete, adjust the pH to neutral, and rotary evaporate to obtain mercapto-modified hydroxyl silicone oil. S2. Mix mercapto-modified hydroxyl silicone oil, photoinitiator, and acetone, disperse by ultrasonication, add isobornyl acrylate and castor oil, react, and after the reaction is complete, rotary evaporate to obtain silicone-containing castor oil-based polyol. Dopamine-containing polyacrylates are prepared by the following steps: 3-Methacrylamide, butyl acrylate, hydroxypropyl methacrylate, and ethanol were mixed evenly, and the initiator azobisisobutyronitrile was added. After the reaction was completed, the mixture was purified and dried to obtain dopamine-containing polyacrylate. The adhesive material is coated on the side of the aluminum-plated layer / protective layer / base film composite film with the aluminum plating layer, and dried to form an adhesive layer, resulting in a high-strength, water-resistant transfer film.

2. The method for preparing a high-strength, water-washable transfer film according to claim 1, characterized in that, In step (1): the base film is a release film; the protective layer material is a UV-curable resin; the curing conditions are: curing in UV light with a wavelength of 365nm for 30-40s; the thickness of the protective layer is 4-6μm.

3. The method for preparing a high-strength, water-washable transfer film according to claim 1, characterized in that, In step (2), the aluminum plating conditions are: vacuum evaporation process at 10 -4 Aluminum plating is performed under mbar vacuum conditions; the thickness of the aluminum plating layer is 30-50 nm.

4. The method for preparing a high-strength, water-washable transfer film according to claim 1, characterized in that, In step (3): the mass ratio of dopamine polyacrylate, blocked polyurethane, silicone castor oil-based polyol and acetone is 10-15:50:10-15:100-120; the drying conditions are: drying at a relative humidity of 25-30% and a temperature of 25-30℃ for 24-48 hours; the thickness of the adhesive layer is 25-30μm.

5. The method for preparing a high-strength, water-washable transfer film according to claim 1, characterized in that, In step (3), when preparing the silicon-containing castor oil-based polyol, in S1: the mass ratio of 3-mercaptopropylmethyltrimethoxysilane, 1 mol / L KOH aqueous solution, and octamethylcyclotetrasiloxane is 12-18:0.8-1.2:20-30; the reaction conditions are: reaction at 500-800 r / min and 130-150℃ for 6-8 h; in S2: the mass ratio of mercapto-modified hydroxyl silicone oil, isobornyl acrylate, castor oil, photoinitiator, and acetone is 5.2-5.5:1-1.5:19.2-20:0.04-0.05:80-100; the reaction conditions are: reaction in an ultraviolet light environment with a wavelength of 365 nm and a rotation speed of 500-800 r / min for 3-5 h.

6. The method for preparing a high-strength, water-washable transfer film according to claim 1, characterized in that, In step (3), when preparing dopamine-containing polyacrylate, the molar ratio of 3-methacryloyldopamine, butyl acrylate, hydroxypropyl methacrylate, and azobisisobutyronitrile is 1.5-2:18.5:2-2.5:0.08-0.1; the reaction conditions are: reaction in a nitrogen atmosphere at 50-70℃ for 24-48h.

7. The method for preparing a high-strength, water-washable transfer film according to claim 1, characterized in that, In step (3), the closed polyurethane is prepared by the following steps: Toluene-2,4-diisocyanate, polypropylene glycol, and dibutyltin dilaurate catalyst were mixed and reacted. After the reaction was completed, methyl ethyl ketone oxime was added and the reaction was continued. After the reaction was completed, the mixture was cooled to obtain a blocked polyurethane. The molar ratio of toluene-2,4-diisocyanate, polypropylene glycol, and methyl ethyl ketone oxime is 2:1:2-2.2; the amount of dibutyltin dilaurate catalyst added is 0.05 wt% of the mass of polypropylene glycol; the reaction conditions are: reaction at 60-90℃ for 1-2 hours in a nitrogen atmosphere; the reaction is continued at 60-65℃ for 3-4 hours.

8. A high-fastness, water-washable transfer film prepared by the method described in any one of claims 1-7.

9. The application of a high-fastness, wash-resistant transfer film as described in claim 8 on cotton fabrics.

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