CN113815340A - Preparation process of pre-coated composite transfer membrane - Google Patents
Preparation process of pre-coated composite transfer membrane Download PDFInfo
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- CN113815340A CN113815340A CN202111090813.0A CN202111090813A CN113815340A CN 113815340 A CN113815340 A CN 113815340A CN 202111090813 A CN202111090813 A CN 202111090813A CN 113815340 A CN113815340 A CN 113815340A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
- B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/58—No clear coat specified
- B05D7/584—No clear coat specified at least some layers being let to dry, at least partially, before applying the next layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2518/00—Other type of polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2601/00—Inorganic fillers
- B05D2601/20—Inorganic fillers used for non-pigmentation effect
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- 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
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Laminated Bodies (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
The invention discloses a preparation process of a pre-coating composite transfer film, wherein the pre-coating composite transfer film comprises a BOPP (biaxially-oriented polypropylene) base layer film, a silicone-containing release layer, an ink layer and an EVA (ethylene-vinyl acetate) hot melt adhesive layer. According to the invention, the protective agent is added into the separation layer, so that the composite transfer film is thinned without additionally constructing a protective layer, and the requirements of energy conservation, emission reduction and clean production are met; the hexagonal boron nitride is added into the EVA hot melt adhesive, so that the effect of the composite film and a printing stock is enhanced. The preparation method of the pre-coating composite transfer membrane is simple to operate, the prepared pre-coating composite transfer membrane can meet the requirement of thermal transfer printing, the application range is wide, and the industrial production is facilitated.
Description
Technical Field
The invention belongs to the field of thermal transfer membranes, and particularly relates to a preparation process of a pre-coating composite transfer membrane.
Background
With the continuous development of the domestic printing industry and the improvement of the living standard of people, the surface pattern decoration of industrial products such as plastics, glass, metal and the like has higher requirements, and the original traditional printing mode cannot meet the requirement of surface decoration. Thermal transfer printing has received much attention as a new printing method. Thermal transfer printing is one of the modes of specialty printing and is also a type of transfer printing. In essence, the method is a process for transferring an image previously printed on a carrier film to a substrate by means of a thermal transfer machine under conditions of heat and pressure. The printing method of the thermal transfer printing is simple, rapid and pollution-free, and the transfer printing pattern is clear, bright in color and distinct in gradation. Meanwhile, the adhesive force is good, the decorative value is high, the grade and the added value of the product are improved, the adhesive tape is suitable for mass production, and the adhesive tape can be widely used for surface processing of various industrial products such as plastics, glass, metal, wood and the like. In the thermal transfer printing method, the most central technique is a thermal transfer film. The heat transfer film is a functional film which is provided with pictures and texts formed by adhesive and ink, is separated from the base layer film together with the protective layer under the action of heat and pressure, and is adhered to the surface of a substrate. A thermal transfer film is a composite film generally having a tie layer, an ink layer, a protective layer, a release layer, and a base layer.
The BOPP film is a multilayer co-extruded film and is prepared by co-extruding polypropylene particles to form a sheet and then stretching the sheet in longitudinal and transverse directions. The stretched molecular oriented BOPP film has good physical stability, mechanical strength and air tightness, high transparency and glossiness, toughness and wear resistance, is a printing film with wide application, and is known as 'packaging queen'. Based on these characteristics, BOPP films can be effective candidates as base films for thermal transfer films. However, the surface tension of BOPP films is often required to be 38mN/m or more in printing, compounding, coating, and other operations, but since polypropylene is a non-polar polymer and the surface tension value is relatively low, surface treatment is required to increase the surface tension, improve the adhesion and wettability of the polymer, and meet the use requirements during the production of BOPP films.
CN 103707603A discloses two-sided heat-seal two-sided antifog type BOPP membrane and preparation method thereof, it comprises inner epidermis, sandwich layer and extexine, and inner epidermis, sandwich layer and extexine are formed through biaxial stretching after the coextrusion, and the material of inner epidermis and extexine comprises polypropylene and anti-sticking agent, and the mass percent that each component of inner epidermis and extexine accounts for is: 97.5-98.5% of polypropylene and 1.5-2.5% of anti-sticking agent; the core layer consists of polypropylene, an antifogging agent and a slipping agent, and the core layer comprises the following components in percentage by mass: 95.9-97.1% of polypropylene, 2.5-3.5% of antifogging agent, 0.4-0.6% of slipping agent, and the antifogging agent comprises the following components in percentage by weight: 50% of sorbitan monostearate, 35% of glycerol monooleate and 15% of polyethylene oxide (20) glycerol monostearate; the double-sided heat-sealing double-sided anti-fog BOPP film prepared by the invention has the advantages that the hydrophilicity and the anti-fog performance are obviously improved.
CN 105774283A discloses a smooth elastic heat transfer film and a preparation method thereof, comprising a BOPP basal film, a smooth layer and an elastic layer which are sequentially coated on the BOPP basal film; the thickness of the BOPP base film is 20-25 microns, the BOPP base film with the thickness has high tensile strength, high toughness and dye wettability suitable for printing, the smooth layer is composed of polyurethane resin, organic silicone oil and butanone, the surface of the heat transfer film after hot stamping can be smooth, the scratch resistance and the scratch resistance are obviously improved, and the smooth layer also has stripping performance and can separate the elastic layer from the BOPP base film; the elastic layer can make the heat transfer film have different colors and has elasticity and stretchability; after hot stamping and heat transfer, the surface layer of the elastic cloth is smooth, scratch-resistant and scratch-resistant, the color layer is continuous, the attractiveness and comfort of the cloth are improved, and the service life of the cloth is prolonged.
CN 106564256A discloses a forming method of integrated contraposition overprinting of a printed film and a highlight particle film, which comprises the steps of BOPP base film, ink color mixing, ink printing, cooling and rolling and hot pressing; printing ink by adopting a gravure printing mode, printing the ink on a base film by adopting a one-group one-color mode, drying and curing until printing and drying and curing of all color groups are completed; then melting the hot-melt glue or solvent glue, coating the melted glue on the last group of high solid plates with the lines, overprinting the glue on corresponding patterns in an alignment mode, and manufacturing a group of integrally formed base films with preset patterns.
Methods for improving the gloss and hardness of printed layers are lacking in the prior art.
Disclosure of Invention
In view of the defects in the prior art, the invention discloses a preparation process of a pre-coating composite transfer film, wherein the pre-coating composite film comprises a BOPP base layer film, a polysiloxane separation layer, an ink layer and an EVA hot melt adhesive layer.
In order to achieve the purpose, the invention provides a preparation process of a pre-coating composite transfer membrane, which comprises the following steps:
coating of S1 delamination: coating the separation layer material liquid on the surface of the BOPP base layer film by using an anilox roller, and performing sectional heating and drying to form a separation layer;
coating of S2 ink layer: coating the dye liquor on the separation layer obtained in the step S1 by using an anilox roller, and performing sectional heating and drying to form an ink layer;
coating of S3 bonding layer: coating the hot melt adhesive on the ink layer obtained in the step S2 by using a heating mesh roller for melting;
and S4, enabling the film coated with the hot melt adhesive obtained in the step S3 to pass through a cooling anilox roller, solidifying by a cold air box, and cutting and rolling to obtain the precoating composite film transfer film.
Preferably, the mass ratio of each substance in the delamination solution in the step S1 is 1-10% of a protective agent, 10-15% of cellulose acetate, 0.05-0.2% of a leveling agent, and the balance of an organic solvent.
The protective agent is one or the combination of two or more of hexamethyldisiloxane, tetravinyl tetramethylcyclotetrasiloxane and octamethylcyclotetrasiloxane.
The leveling agent is polyether siloxane copolymer type leveling agent.
The organic solvent is one or the combination of two or more of acetone, butanone, 3-pentanone, cyclohexanone and toluene.
The mesh number of the anilox rolls in the steps S1 to S4 is 100 to 250 mesh.
The thickness of the BOPP film is 15-25 mu m, and the width of the BOPP film is 1000-2000 mm.
The thickness of the separation layer is 10-20 mu m.
In the invention, the separation layer not only has a protective effect on the ink layer, but also is separated after thermal transfer printing and directly appears on the surface of a printing stock. However, since the release layer is easy to peel, the release layer has low surface polarity and low surface energy, and the release layer is difficult to wet during coating, so that the leveling property is poor, which directly affects the appearance, glossiness and even performance of the surface of the final printing material. The invention adds organic siloxane to reduce the surface energy and viscosity of the separation layer, so as to improve the wetting property and leveling property of the coating when coating and also enhance the hand feeling of the printed matter. However, an ink layer needs to be coated on the separation layer, and the organic siloxane has serious phenomena of uneven distribution and migration in the film forming process, so that the hydrophobic structure is gradually damaged. Polysiloxanes having more functional groups and more excellent surface properties can be prepared by polymerizing organosiloxanes with cyclic siloxanes.
Further preferably, the protecting agent in step S1 is a methyl vinyl siloxane polymer, and the preparation method thereof is as follows: mixing and stirring octamethylcyclotetrasiloxane, tetravinyltetramethylcyclotetrasiloxane and hexamethyldisiloxane at a molar ratio of (15-40) to (3-20) and (1-3) at a rotation speed of 200-500 r/min for 10-30 min at a temperature of 60-80 ℃, adding a catalyst accounting for 1-2% of the total mass of the mixed oxysilanes, and then reacting at 60-80 ℃ for 5-10 h; naturally cooling to 20-30 ℃, and adding sodium carbonate to adjust the pH value to 7.0-8.0; and drying at 70-90 ℃ for 5-10 h to obtain the methyl vinyl siloxane polymer.
The catalyst is one or a combination of trifluoromethanesulfonic acid and phosphoric acid.
The most preferable catalyst comprises trifluoromethanesulfonic acid and phosphoric acid in a mass ratio of (3-5): 1.
preferably, the mass ratio of each substance in the ink layer feed liquid in the step S2 is 10-20% of water-based dye, 20-30% of water-based polyurethane resin, 0.2-0.5% of defoaming agent, 0.2-0.5% of antistatic agent, 0.2-0.5% of leveling agent, and the balance cyclohexanone.
The defoaming agent is an organic silicon defoaming agent.
The antistatic agent is one or the combination of two or more of sulfuric acid derivative type, phosphoric acid derivative type, amine type, quaternary ammonium salt type, imidazole type and ethylene oxide derivative type antistatic agents.
The flatting agent is a fluorocarbon modified polyacrylate type flatting agent.
The thickness of the dye layer is 20-50 mu m.
The temperature of the stepwise heating in the steps S1-S2 is T1 70℃、T2 75℃、T3 80℃、T485℃。
Preferably, the hot melt adhesive in step S3 is an EVA hot melt adhesive, and the melting temperature is 130-150 ℃.
The heating anilox roller is at a temperature of 70-90 ℃.
The thickness of the bonding layer is 0.01-0.5 mm.
In actual production, different image-text styles can be designed in the ink layer, so that the ink layer does not completely cover the separation layer, and the bonding layer can be directly contacted with the separation layer, so that high requirements are provided for the performance of the bonding layer, the bonding layer has high bonding force with the ink layer and the separation layer, and also has good bonding force with a printing stock, and the three interlayer structures and properties have great differences. In some technologies, a coating is coated between an ink layer and a bonding layer, and the coating has good binding force with a separation layer, the ink layer and the bonding layer, so that the bonding layer only needs to be acted with a substrate and a newly added coating. However, such operations add process steps and cost and do not meet the need for thinning of the packaging material. It would be a more suitable method to enhance the interaction of the tie layer, ink layer and release layer. The adhesive layer of the present invention is EVA hot melt adhesive, which is solid at normal temperature, heated to certain temperature and converted into liquid adhesive with certain viscosity, and may be cooled and cured in short time after being applied. The EVA hot melt adhesive is nontoxic and pollution-free, has good optical performance, flexibility, processability and chemical corrosion resistance, and has the defects of poor adhesion, poor wettability, poor material compatibility and the like.
Hexagonal boron nitride is a two-dimensional material consisting of alternating sp' s2The hybrid film is composed of boron atoms and nitrogen atoms, has a structure similar to that of graphite, can be used as an effective heat dissipation film due to high in-plane thermal conductivity, and also improves optical transmittance due to large band gap energyBrightness. The addition of hexagonal boron nitride into EVA hot melt adhesive can improve its mechanical strength and thermal conductivity.
Preferably, after the EVA hot melt adhesive is melted in the step S3, hexagonal boron nitride is added, the mixture is mixed for 5-10 min at a speed of 100-200 r/min, and then the mixed hot melt adhesive is coated; the mass of the added hexagonal boron nitride is 0.5-1% of that of the hot melt adhesive.
However, the uniformity and adhesion quality of hexagonal boron nitride in the EVA hot melt adhesive are not ideal, and the interaction force is poor, which not only results in insufficient mechanical stability, but also results in high thermal resistance between the hexagonal boron nitride and the film layer, hindering effective heat conduction. Exfoliation of hexagonal boron nitride, reducing its size, may enhance its dispersion. The ball milling can effectively strip and functionalize the hexagonal boron nitride, and the grinding aid protective agent is added to prevent the hexagonal boron nitride from generating mechanical damage.
Most preferably, after the EVA hot melt adhesive is melted in the step S3, modified hexagonal boron nitride is added, the mixture is mixed for 5-10 min at a speed of 100-200 r/min, and then the mixed hot melt adhesive is coated; the mass of the added modified hexagonal boron nitride is 0.5-1% of that of the hot melt adhesive;
the preparation method of the modified hexagonal boron nitride comprises the following steps: ball-milling 1 part by weight of hexagonal boron nitride and 15-20 parts by weight of urea at the rotating speed of 500-1000 r/min for 5-10 h; and after the ball milling is finished, putting the powder into water, stirring for 5-10 min at the rotating speed of 300-500 r/min, dissolving urea, centrifuging at 8000-10000 r/min, washing with ethanol and water for three times respectively, and drying insoluble substances at 80-100 ℃ for 5-10 h to obtain the modified hexagonal boron nitride.
Preferably, the temperature of the cooling anilox roller in the step S4 is 15-30 ℃, and the temperature of the cold air box is 15-30 ℃.
The invention has the following beneficial effects:
(1) the protective agent is added into the separation layer, so that the composite transfer film is thinned without additionally constructing a protective layer, the requirements of energy conservation, emission reduction and clean production are met, the modified hexagonal boron nitride is added into the EVA hot melt adhesive, the synergistic effect is generated with siloxane, and the adhesiveness of the composite film and a printing stock is obviously enhanced. The method for manufacturing the pre-coating composite transfer membrane is simple to operate, the manufactured pre-coating composite transfer membrane can meet the requirement of thermal transfer printing, the application range is wide, and industrial production is facilitated.
(2) The EVA hot melt adhesive is pre-coated on the film to form the bonding layer, and the adhesive is directly heated and printed on a product, so that glue does not need to be coated in the printing process, the printing time is shortened, and the adhesive is environment-friendly and pollution-free.
Detailed Description
In the examples of the application, part of raw materials are introduced:
BOPP films, 25 μm thick and 1500mm wide, were purchased from DAHUIHUAMING packaging materials, Inc.
Aqueous dyes, purchased from denna aviation trade ltd.
The waterborne polyurethane resin is JU-5015, which is purchased from Guangdong cis-China high polymer materials Co.
Hexagonal boron nitride with a content of more than or equal to 99% is purchased from Tianyuan aviation materials (Yingkou) science and technology corporation.
The rest raw materials which are not mentioned are all materials which are commonly used in the field, and the grade is industrial grade or above.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1A Pre-coated composite transfer film
The precoating composite transfer membrane is prepared by the following method:
s1 the method comprises the steps of injecting a separation layer feed liquid into a trough, coating the feed liquid on the surface of a BOPP base layer film with the thickness of 25 mu m and the width of 1500mm by a 150-mesh wire-mesh roller belt material, and passing through a four-section oven T1 70℃、T2 75℃、T3 80℃、T4Drying at 85 deg.C to form a separation layer with a thickness of 20 μm;
s2 mixing water-soluble dye, cyclohexanone,Injecting the water-based polyurethane resin, the defoaming agent, the antistatic agent and the leveling agent into a trough, coating the feed liquid on the separation layer obtained in the step S1 by using a 150-mesh wire roller material, and passing through a four-section oven T1 70℃、T2 75℃、T3 80℃、T4Drying at 85 ℃ to form an ink layer with the thickness of 30 mu m;
s3, melting the EVA hot melt adhesive at 150 ℃, heating the reticulate pattern roller strip material at 150 meshes and 80 ℃ to coat the EVA hot melt adhesive on the ink layer obtained in the step S2;
s4, passing the film coated with the hot melt adhesive obtained in the step S3 through a 150-mesh 25 ℃ cooling anilox roller, and curing the hot melt adhesive in a cold air box at 25 ℃ to obtain a composite film containing a bonding layer, wherein the thickness of the bonding layer is 0.05 mm; and cutting and rolling to obtain the precoated composite transfer membrane of the embodiment.
In the step S1, the mass percentages of all substances in the delaminating material liquid are 3% of hexamethyldisiloxane, 15% of cellulose acetate, 81.7% of cyclohexanone and 0.3% of polyether siloxane copolymer type leveling agent;
in step S2, the ink layer feed liquid contains, by mass, 15% of a water-based dye, 25% of a water-based polyurethane resin, 0.2% of a silicone defoaming agent, 0.2% of a quaternary ammonium salt type antistatic agent, 0.2% of a fluorocarbon-modified polyacrylate type leveling agent, and 59.4% of cyclohexanone.
Embodiment 2 a precoating composite transfer film
The precoating composite transfer membrane is prepared by the following method:
s1 the method comprises the steps of injecting a separation layer feed liquid into a trough, coating the feed liquid on the surface of a BOPP base layer film with the thickness of 25 mu m and the width of 1500mm by a 150-mesh wire-mesh roller belt material, and passing through a four-section oven T1 70℃、T2 75℃、T3 80℃、T4Drying at 85 deg.C to form a separation layer with a thickness of 20 μm;
s2, injecting the water-based dye, cyclohexanone, water-based polyurethane resin, defoaming agent, antistatic agent and leveling agent into a trough, coating the feed liquid on the separation layer obtained in the step S1 by using a 150-mesh wire roller belt material, and passing through a four-section oven T1 70℃、T2 75℃、T3 80℃、T4Drying at 85 deg.C to formAn ink layer, the thickness of the ink layer is 30 μm;
s3, melting the EVA hot melt adhesive at 150 ℃, heating the reticulate pattern roller strip material at 150 meshes and 80 ℃ to coat the EVA hot melt adhesive on the ink layer obtained in the step S2;
s4, passing the film coated with the hot melt adhesive obtained in the step S3 through a 150-mesh 25 ℃ cooling anilox roller, and curing the hot melt adhesive in a cold air box at 25 ℃ to obtain a composite film containing a bonding layer, wherein the thickness of the bonding layer is 0.05 mm; and cutting and rolling to obtain the precoated composite transfer membrane of the embodiment.
In the step S1, the mass percentages of all substances in the delaminating material liquid are 3% of octamethylcyclotetrasiloxane, 15% of cellulose acetate, 81.7% of cyclohexanone and 0.3% of polyether siloxane copolymer type leveling agent;
in step S2, the ink layer feed liquid contains, by mass, 15% of a water-based dye, 25% of a water-based polyurethane resin, 0.2% of a silicone defoaming agent, 0.2% of a quaternary ammonium salt type antistatic agent, 0.2% of a fluorocarbon-modified polyacrylate type leveling agent, and 59.4% of cyclohexanone.
Example 3A Pre-coated composite transfer film
The precoating composite transfer membrane is prepared by the following method:
s1 the method comprises the steps of injecting a separation layer feed liquid into a trough, coating the feed liquid on the surface of a BOPP base layer film with the thickness of 25 mu m and the width of 1500mm by a 150-mesh wire-mesh roller belt material, and passing through a four-section oven T1 70℃、T2 75℃、T3 80℃、T4Drying at 85 deg.C to form a separation layer with a thickness of 20 μm;
s2, injecting the water-based dye, cyclohexanone, water-based polyurethane resin, defoaming agent, antistatic agent and leveling agent into a trough, coating the feed liquid on the separation layer obtained in the step S1 by using a 150-mesh wire roller belt material, and passing through a four-section oven T1 70℃、T2 75℃、T3 80℃、T4Drying at 85 ℃ to form an ink layer with the thickness of 30 mu m;
s3, melting the EVA hot melt adhesive at 150 ℃, heating the reticulate pattern roller strip material at 150 meshes and 80 ℃ to coat the EVA hot melt adhesive on the ink layer obtained in the step S2;
s4, passing the film coated with the hot melt adhesive obtained in the step S3 through a 150-mesh 25 ℃ cooling anilox roller, and curing the hot melt adhesive in a cold air box at 25 ℃ to obtain a composite film containing a bonding layer, wherein the thickness of the bonding layer is 0.05 mm; and cutting and rolling to obtain the precoated composite transfer membrane of the embodiment.
In the step S1, the mass percentages of the substances in the delamination solution are 3% of tetravinyl tetramethylcyclotetrasiloxane, 15% of cellulose acetate, 81.7% of cyclohexanone, and 0.3% of polyether siloxane copolymer type leveling agent;
in step S2, the ink layer feed liquid contains, by mass, 15% of a water-based dye, 25% of a water-based polyurethane resin, 0.2% of a silicone defoaming agent, 0.2% of a quaternary ammonium salt type antistatic agent, 0.2% of a fluorocarbon-modified polyacrylate type leveling agent, and 59.4% of cyclohexanone.
Example 4A Pre-coated composite transfer film
The precoating composite transfer membrane is prepared by the following method:
s1 the method comprises the steps of injecting a separation layer feed liquid into a trough, coating the feed liquid on the surface of a BOPP base layer film with the thickness of 25 mu m and the width of 1500mm by a 150-mesh wire-mesh roller belt material, and passing through a four-section oven T1 70℃、T2 75℃、T3 80℃、T4Drying at 85 deg.C to form a separation layer with a thickness of 20 μm;
s2, injecting the water-based dye, cyclohexanone, water-based polyurethane resin, defoaming agent, antistatic agent and leveling agent into a trough, coating the feed liquid on the separation layer obtained in the step S1 by using a 150-mesh wire roller belt material, and passing through a four-section oven T1 70℃、T2 75℃、T3 80℃、T4Drying at 85 ℃ to form an ink layer with the thickness of 30 mu m;
s3, melting the EVA hot melt adhesive at 150 ℃, heating the reticulate pattern roller strip material at 150 meshes and 80 ℃ to coat the EVA hot melt adhesive on the ink layer obtained in the step S2;
s4, passing the film coated with the hot melt adhesive obtained in the step S3 through a 150-mesh 25 ℃ cooling anilox roller, and curing the hot melt adhesive in a cold air box at 25 ℃ to obtain a composite film containing a bonding layer, wherein the thickness of the bonding layer is 0.05 mm; and cutting and rolling to obtain the precoated composite transfer membrane of the embodiment.
In the step S1, the mass percentages of all substances in the delaminating material liquid are 3% of methyl vinyl siloxane polymer, 15% of cellulose acetate, 81.7% of cyclohexanone and 0.3% of polyether siloxane copolymer type leveling agent;
the preparation method of the methyl vinyl siloxane polymer comprises the following steps: at the temperature of 70 ℃, octamethylcyclotetrasiloxane, tetravinyltetramethylcyclotetrasiloxane and hexamethyldisiloxane are mixed in a molar ratio of 20: 15: 3, mixing and stirring for 20min at the rotating speed of 300r/min, adding a catalyst accounting for 1.5 percent of the total mass of the mixed oxysilane, and then reacting for 80h at 70 ℃; naturally cooling to 25 ℃, and adding sodium carbonate to adjust the pH value to 7.0; drying at 80 ℃ for 6h to obtain a methyl vinyl siloxane polymer;
the catalyst is phosphoric acid;
in step S2, the ink layer feed liquid contains, by mass, 15% of a water-based dye, 25% of a water-based polyurethane resin, 0.2% of a silicone defoaming agent, 0.2% of a quaternary ammonium salt type antistatic agent, 0.2% of a fluorocarbon-modified polyacrylate type leveling agent, and 59.4% of cyclohexanone.
Example 5A Pre-coated composite transfer film
The preparation method is basically consistent with that of example 4, except that:
the preparation method of the methyl vinyl siloxane polymer in the delamination feed liquid comprises the following steps: at the temperature of 70 ℃, octamethylcyclotetrasiloxane, tetravinyltetramethylcyclotetrasiloxane and hexamethyldisiloxane are mixed in a molar ratio of 20: 15: 3, mixing and stirring for 20min at the rotating speed of 300r/min, adding a catalyst accounting for 1.5 percent of the total mass of the mixed oxysilane, and then reacting for 80h at 70 ℃; naturally cooling to 25 ℃, and adding sodium carbonate to adjust the pH value to 7.0; drying at 80 ℃ for 6h gave methylvinylsiloxane polymers.
The catalyst is trifluoromethanesulfonic acid.
Example 6A Pre-coated composite transfer film
The preparation method is basically consistent with that of example 4, except that:
the preparation method of the methyl vinyl siloxane polymer in the delamination feed liquid comprises the following steps: at the temperature of 70 ℃, octamethylcyclotetrasiloxane, tetravinyltetramethylcyclotetrasiloxane and hexamethyldisiloxane are mixed in a molar ratio of 20: 15: 3, mixing and stirring at the rotating speed of 300r/min for 20min, and adding a catalyst accounting for 1.5 percent of the total mass of the mixed oxysilane; then reacting for 80h at 70 ℃; naturally cooling to 25 ℃, and adding sodium carbonate to adjust the pH value to 7.0; drying at 80 ℃ for 6h gave methylvinylsiloxane polymers.
The catalyst is a mixture of trifluoromethanesulfonic acid and phosphoric acid, and the mass ratio of trifluoromethanesulfonic acid to phosphoric acid is 3: 1.
example 7A Pre-coated composite transfer film
The precoating composite transfer membrane is prepared by the following method:
s1 the method comprises the steps of injecting a separation layer feed liquid into a trough, coating the feed liquid on the surface of a BOPP base layer film with the thickness of 25 mu m and the width of 1500mm by a 150-mesh wire-mesh roller belt material, and passing through a four-section oven T1 70℃、T2 75℃、T3 80℃、T4Drying at 85 deg.C to form a separation layer with a thickness of 20 μm;
s2, injecting the water-based dye, cyclohexanone, water-based polyurethane resin, defoaming agent, antistatic agent and leveling agent into a trough, coating the feed liquid on the separation layer obtained in the step S1 by using a 150-mesh wire roller belt material, and passing through a four-section oven T1 70℃、T2 75℃、T3 80℃、T4Drying at 85 ℃ to form an ink layer with the thickness of 30 mu m;
s3, melting the EVA hot melt adhesive at 150 ℃, mixing the hot melt adhesive and hexagonal boron nitride accounting for 0.5 percent of the mass of the hot melt adhesive at the rotating speed of 100r/min for 5min, heating the reticulate roll strip material at 150 meshes and 80 ℃ to mix and coat the EVA hot melt adhesive and the hexagonal boron nitride on the ink layer obtained in the step S2;
s4, passing the film coated with the hot melt adhesive obtained in the step S3 through a 150-mesh 25 ℃ cooling anilox roller, and curing the hot melt adhesive in a cold air box at 25 ℃ to obtain a composite film containing a bonding layer, wherein the thickness of the bonding layer is 0.05 mm; and cutting and rolling to obtain the precoated composite transfer membrane of the embodiment.
In the step S1, the mass percentages of all substances in the delaminating material liquid are 3% of methyl vinyl siloxane polymer, 15% of cellulose acetate, 81.7% of cyclohexanone and 0.3% of polyether siloxane copolymer type leveling agent;
the procedure for the preparation of the methylvinylsiloxane polymer is as described in example 6;
in step S2, the ink layer feed liquid contains, by mass, 15% of a water-based dye, 25% of a water-based polyurethane resin, 0.2% of a silicone defoaming agent, 0.2% of a quaternary ammonium salt type antistatic agent, 0.2% of a fluorocarbon-modified polyacrylate type leveling agent, and 59.4% of cyclohexanone.
Embodiment 8A Pre-coated composite transfer film
The precoating composite transfer membrane is prepared by the following method:
s1 the method comprises the steps of injecting a separation layer feed liquid into a trough, coating the feed liquid on the surface of a BOPP base layer film with the thickness of 25 mu m and the width of 1500mm by a 150-mesh wire-mesh roller belt material, and passing through a four-section oven T1 70℃、T2 75℃、T3 80℃、T4Drying at 85 deg.C to form a separation layer with a thickness of 20 μm;
s2, injecting the water-based dye, cyclohexanone, water-based polyurethane resin, defoaming agent, antistatic agent and leveling agent into a trough, coating the feed liquid on the separation layer obtained in the step S1 by using a 150-mesh wire roller belt material, and passing through a four-section oven T1 70℃、T2 75℃、T3 80℃、T4Drying at 85 ℃ to form an ink layer with the thickness of 30 mu m;
s3, melting the EVA hot melt adhesive at 150 ℃, mixing the hot melt adhesive and modified hexagonal boron nitride accounting for 0.5 percent of the mass of the hot melt adhesive at the rotating speed of 100r/min for 5min, heating the reticulate roll strip material at 150 meshes and 80 ℃ to mix and coat the EVA hot melt adhesive and the modified hexagonal boron nitride on the ink layer obtained in the step S2;
s4, passing the film coated with the hot melt adhesive obtained in the step S3 through a 150-mesh 25 ℃ cooling anilox roller, and curing the hot melt adhesive in a cold air box at 25 ℃ to obtain a composite film containing a bonding layer, wherein the thickness of the bonding layer is 0.05 mm; and cutting and rolling to obtain the precoated composite transfer membrane of the embodiment.
In the step S1, the mass percentages of all substances in the delaminating material liquid are 3% of methyl vinyl siloxane polymer, 15% of cellulose acetate, 81.7% of cyclohexanone and 0.3% of polyether siloxane copolymer type leveling agent;
the procedure for the preparation of the methylvinylsiloxane polymer is as described in example 6;
in step S2, the ink layer feed liquid contains, by mass, 15% of a water-based dye, 25% of a water-based polyurethane resin, 0.2% of a silicone defoaming agent, 0.2% of a quaternary ammonium salt type antistatic agent, 0.2% of a fluorocarbon-modified polyacrylate type leveling agent, and 59.4% of cyclohexanone.
The preparation method of the modified hexagonal boron nitride in the step S3 comprises the following steps: ball milling 1 part by weight of hexagonal boron nitride and 20 parts by weight of urea at the rotating speed of 800r/min for 8 hours; and after the ball milling is finished, putting the powder into water, stirring for 5min at the rotating speed of 300r/min, dissolving urea, centrifuging at the speed of 8000r/min, washing with ethanol and water for three times respectively, and drying the insoluble substance at the temperature of 80 ℃ for 6h to obtain the modified hexagonal boron nitride.
Test example 1 Water permeability and mechanical Properties of transfer Membrane
The water permeability and the mechanical strength of the transfer membrane are important indexes for evaluating the performance of the transfer membrane, and the water permeability and the mechanical strength of the precoated composite transfer membrane prepared in the embodiment 6-8 of the invention are tested:
the water permeability test of the transfer membrane is determined by referring to the national standard GB/T26253-;
the tearing strength of the transfer film is determined according to the national standard GB/T16578.1-2008' tear resistance of plastic films and thin sheets part 1: trouser tear method.
TABLE 1 Water permeability and mechanical Properties testing of transfer membranes
| Water vapor transmission rate [ g/(m)2·24h)] | Tear Strength (kN/m) | |
| Example 6 | 1.51 | 3.1 |
| Example 7 | 1.38 | 3.2 |
| Example 8 | 1.13 | 3.5 |
The test results of examples 6 to 8 are shown in Table 1. As can be seen from the test results in Table 1, after the hexagonal boron nitride is added into the bonding layer, the water vapor permeability is reduced, and the tearing strength is enhanced; example 8 these changes were more pronounced with the addition of modified hexagonal boron nitride. This is probably because the two-dimensional planar structure of hexagonal boron nitride has barrier properties against water vapor, and the presence of hexagonal boron nitride having higher mechanical strength in the bonding layer improves the strength of the transfer film. In addition, the ball-milled and stripped modified hexagonal boron nitride has a smaller size, the oxygen-containing functional groups of the hexagonal boron nitride are increased, the dispersity of the hexagonal boron nitride in the bonding layer is improved, the interaction of the bonding layer and the ink layer is enhanced, and the contact is firmer. Therefore, the transfer film prepared by adding the modified hexagonal boron nitride into the bonding layer has the lowest water vapor transmission rate and the maximum tearing strength.
Test example 2 printing Performance test of transfer film
After the transfer film is subjected to thermal transfer printing, the transfer film is transferred to the surface of a substrate, the separation layer is separated, and the ink layer is directly presented. The hardness, glossiness and adhesiveness of the ink layer after transfer printing are main indexes for evaluating the performance of the transfer film.
And transferring the thermal transfer film to the surface of the flat ABS plastic at 150 ℃, and tearing off the release layer.
The hardness of the ink layer transferred on the ABS plastic is measured according to the national standard GB/T6739-.
The gloss of the ink layer transferred onto ABS plastic is determined by means of a reflectometer at a geometrical angle of 60 ℃ in accordance with the national standard GB/T9754 2007 determination of the specular gloss of paint films of metallic pigment-free paints at 20, 60 and 85 ℃.
TABLE 2 hardness and gloss testing of post-transfer ink layers
| Hardness of | Degree of gloss (°) | |
| Example 1 | HB | 72.5 |
| Example 2 | HB | 75.6 |
| Example 3 | HB | 73.8 |
| Example 4 | H | 83.2 |
| Example 5 | H | 86.7 |
| Example 6 | 2H | 92.3 |
Hardness standard:
gloss: the higher the gloss, the brighter the surface.
From the test results in table 2, in comparison with examples 1 to 4, it can be seen that the addition of the methylvinylsiloxane polymer in the delamination layer can increase the hardness of the ink layer by two levels (from HB → H), which may be that the organic silicon chain and the medium vinyl species of the methylvinylsiloxane polymer are easy to phase separate and obviously transfer to the surface of the ink layer, so that the uniform organic silicon layer is enriched, which has an effect of improving the mechanical properties of the surface. The gloss of example 4 reached 83.2 ° because the methylvinylsiloxane polymer had a lower surface energy for the siloxane monomers, increasing the reflection of light.
Example 6 using a methylvinylsiloxane polymer prepared using trifluoromethanesulfonic acid and phosphoric acid as catalysts as a delamination protectant, the hardness of the ink layer after transfer was 2H and the gloss was 92.3 °, which is likely to be that the mixed catalyst system allows the methylvinylsiloxane polymer surface to have more functional groups, to have stronger permeability to the ink layer, lower surface tension, and further improves the hardness and gloss of the ink layer.
The adhesion of the ink layer transferred onto ABS plastic was tested using the cross-hatch method according to the national standard GB T9286-1998 test cross-hatch of paint and varnish films.
TABLE 3 adhesion rating of ink layers
| Adhesion grading | |
| Example 1 | 3 |
| Example 2 | 3 |
| Example 3 | 3 |
| Example 4 | 2 |
| Example 5 | 2 |
| Example 6 | 1 |
| Example 7 | 1 |
| Example 8 | 0 |
The adhesion reflects the degree of adhesion between the ink printed on the surface of the substrate and the substrate. The adhesion grading is usually 0-5 grades and 6 grades, the lower the grading is, the better the adhesion is represented, and for general purposes, the first three grades, namely 0-2 grades, reach the standard. A rating of 0 indicates no shedding in the test; a classification of 1 indicates shedding, with a shedding area of less than 5%; a rating of 2 represents a shed area of greater than 5% but not greater than 15%; a rating of 3 represents a shed area of greater than 15% but not greater than 35%.
The test results of the examples 1-3 in the table 3 are all 3 grades, which shows that the interaction among the EVA hot melt adhesive, the ink layer and the ABS plastic is not strong; the adhesion of the methyl vinyl siloxane polymer added to the separation layers in examples 4 to 6 is increased in stages, which is probably because the organic silicon chain and the medium vinyl species of the methyl vinyl siloxane polymer are easy to phase separate and obviously transfer to the surface of the ink layer, so that the uniform organic silicon layer is enriched, the interaction of the EVA hot melt adhesive, the ink layer and the ABS plastic is enhanced by permeating into the ink layer, and the adhesion is improved. The adhesion grading of example 6, in which hexagonal boron nitride was added to the EVA hot melt, was unchanged from example 7; however, example 8 with the addition of modified hexagonal boron nitride had an adhesion rating of 0. The reason is probably that the hexagonal boron nitride is added into the EVA hot melt adhesive, so that the axial stress of the hot melt adhesive is increased, and the mechanical strength of the hot melt adhesive is improved; the penetrated methyl vinyl siloxane polymer can be used together with hexagonal boron nitride to improve the adhesion; the acting force between the hexagonal boron nitride with small particle size and the methyl vinyl siloxane polymer which are more uniformly distributed in the hot melt adhesive is stronger, and the adhesiveness of the transfer film is further improved.
Claims (10)
1. A preparation process of a pre-coating composite transfer membrane is characterized by comprising the following steps:
coating of S1 delamination: coating the separation layer material liquid on the surface of the BOPP base layer film by using an anilox roller, and performing sectional heating and drying to form a separation layer;
coating of S2 ink layer: coating the dye liquor on the separation layer obtained in the step S1 by using an anilox roller, and performing sectional heating and drying to form an ink layer;
coating of S3 bonding layer: coating the hot melt adhesive on the ink layer obtained in the step S2 by using a heating mesh roller for melting;
and S4, passing the film coated with the hot melt adhesive obtained in the step S3 through a cooling anilox roller, solidifying by a cold air box, and cutting and rolling to obtain the pre-coating composite film transfer film.
2. The preparation process of the pre-coating composite transfer film as claimed in claim 1, wherein the mass ratio of each substance in the delamination solution of the step S1 is 1-10% of a protective agent, 10-15% of cellulose acetate, 0.05-0.2% of a leveling agent, and the balance of an organic solvent;
the protective agent is one or the combination of two or more of hexamethyldisiloxane, tetravinyl tetramethylcyclotetrasiloxane and octamethylcyclotetrasiloxane;
the leveling agent is polyether siloxane copolymer type leveling agent;
the organic solvent is one or the combination of two or more of acetone, butanone, 3-pentanone, cyclohexanone and toluene.
3. The process for preparing a pre-coated composite transfer film as claimed in claim 2, wherein the protective agent in the delamination solution is a methyl vinyl siloxane polymer;
the preparation method of the methyl vinyl siloxane polymer comprises the following steps: mixing and stirring octamethylcyclotetrasiloxane, tetravinyltetramethylcyclotetrasiloxane and hexamethyldisiloxane at a molar ratio of (15-40) to (3-20) and (1-3) at a rotation speed of 200-500 r/min for 10-30 min at a temperature of 60-80 ℃, adding a catalyst accounting for 1-2% of the total mass of the mixed oxysilanes, and then reacting at 60-80 ℃ for 5-10 h; naturally cooling to 20-30 ℃, and adding sodium carbonate to adjust the pH value to 7.0-8.0; and drying at 70-90 ℃ for 5-10 h to obtain the methyl vinyl siloxane polymer.
4. The process for preparing a pre-coated composite transfer membrane according to claim 3, wherein the catalyst is one or a combination of trifluoromethanesulfonic acid and phosphoric acid.
5. The preparation process of the pre-coating composite transfer film according to claim 1, wherein the mass ratio of the materials in the ink layer feed liquid in the step S2 is 10-20% of water-based dye, 20-30% of water-based polyurethane resin, 0.2-0.5% of defoaming agent, 0.2-0.5% of antistatic agent, 0.2-0.5% of leveling agent, and the balance of cyclohexanone;
the defoaming agent is an organic silicon defoaming agent;
the antistatic agent is one or the combination of two or more of sulfuric acid derivative type, phosphoric acid derivative type, amine type, quaternary ammonium salt type, imidazole type and ethylene oxide derivative type antistatic agents;
the flatting agent is a fluorocarbon modified polyacrylate type flatting agent.
6. The preparation process of the pre-coating composite transfer film as claimed in claim 1, wherein after the hot melt adhesive is melted in the step S3, hexagonal boron nitride is further added, mixed for 5-10 min at a speed of 100-200 r/min, and then the mixed hot melt adhesive is coated; the mass of the added hexagonal boron nitride is 0.5-1% of that of the hot melt adhesive.
7. The process for preparing a pre-coated composite transfer film according to claim 6, wherein the hexagonal boron nitride is modified to obtain modified hexagonal boron nitride;
the preparation method of the modified hexagonal boron nitride comprises the following steps: ball-milling 1 part by weight of hexagonal boron nitride and 15-20 parts by weight of urea at the rotating speed of 500-1000 r/min for 5-10 h; and after the ball milling is finished, putting the powder into water, stirring for 5-10 min at the rotating speed of 300-500 r/min, dissolving urea, centrifuging at 8000-10000 r/min, washing with ethanol and water for three times respectively, and drying insoluble substances at 80-100 ℃ for 5-10 h to obtain the modified hexagonal boron nitride.
8. The process for preparing a pre-coated composite transfer film as claimed in claim 1, wherein the melting temperature of the hot melt adhesive in S3 is 130-150 ℃.
9. The process for preparing a pre-coated composite transfer film according to claim 1, wherein: the mesh numbers of the anilox roll, the heating anilox roll and the cooling anilox roll in the steps S1-S4 are 100-250 meshes respectively and independently.
10. A pre-coated composite transfer film prepared by the method of any one of claims 1 to 9.
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