CN112457709A - Preparation method and application of degradable thermal transfer printing lettering film - Google Patents

Preparation method and application of degradable thermal transfer printing lettering film Download PDF

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CN112457709A
CN112457709A CN202011371340.7A CN202011371340A CN112457709A CN 112457709 A CN112457709 A CN 112457709A CN 202011371340 A CN202011371340 A CN 202011371340A CN 112457709 A CN112457709 A CN 112457709A
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parts
resin
coating
thermal transfer
solvent
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CN112457709B (en
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陈启智
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Jian Tiancheng New Material Co ltd
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Jian Tiancheng New Material Co ltd
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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
    • 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
    • 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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
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    • 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
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • 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
    • C09D11/104—Polyesters
    • 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
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C09J11/08—Macromolecular additives
    • 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
    • C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
    • C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/04—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09J127/06—Homopolymers or copolymers of vinyl chloride
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    • C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
    • C09J193/04—Rosin
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides a preparation method and application of a heat transfer printing digital pyrograph, which utilize degradable materials with excellent comprehensive performance to ensure that a heat transfer printing film is environment-friendly and has the advantages of no deformation, high and low temperature resistance, bright color and beautiful appearance; the base film is a degradable modified high-temperature-resistant film, aging treatment is not needed before use, the manufacturing process is shortened, the time and the cost are saved, and the phenomenon that the quality of a heat transfer printing lettering film is influenced by expansion and shrinkage deformation caused by a plurality of manufacturing processes is prevented; the color layer ink adopts environment-friendly modified resin as a main body, has a degradable effect, and simultaneously has excellent mechanical properties after thermal transfer printing, so that a finished product has the characteristics of no deformation, high and low temperature resistance and water washing resistance; in addition, the adhesive layer adopts the modified rosin resin-vinyl chloride-acetate copolymer, so that the adhesive force on the surface of the printing stock is enhanced, and the adhesive layer has no irritation to the skin particularly on clothes made of pure cotton.

Description

Preparation method and application of degradable thermal transfer printing lettering film
Technical Field
The invention belongs to the technical field of thermal transfer printing, and particularly relates to a preparation method and application of a degradable thermal transfer printing lettering film.
Background
Thermal transfer printing is an emerging printing process. The printing method of the process is to print the transfer printing film, namely, firstly, patterns or characters are printed on the surface of the film, then, the patterns and characters on the printing film are transferred to the surface of the printing stock through heating and pressurizing by a thermal transfer printing processing device, the process is widely applied to the decoration of clothes, washing slush, gloves, shoes and hats and luggage textiles, however, the adhesive force of the transfer printing matter on the surface of the printing stock, particularly the clothes with the printing stock made of all cotton is general, and the phenomenon of flanging is easy to occur after the printing matter is used for a period of time.
In addition, the base film that is used for the thermoprint membrane of carving characters on the market at present adopts the PET membrane for the majority, and the advantage lies in non-deformable, and the shortcoming is general for high temperature resistant effect, and the material is soft inadequately, in addition for preventing the breathing deformation under the high temperature, the PET membrane with from the cooperation of type membrane use to going to toward needs aging treatment, and later stage as the difficult degradation of discarded object.
Aiming at the defects, the invention provides the degradable thermal transfer printing lettering film which has the advantages of simple manufacturing process, no deformation, high and low temperature resistance, bright color, beautiful appearance, excellent application adhesion, degradability and the like.
Disclosure of Invention
The invention aims to: the degradable material with excellent comprehensive performance is utilized, so that the transfer printing film is environment-friendly, and has the advantages of no deformation, high and low temperature resistance, bright color and beautiful appearance.
The invention is realized by the following technical scheme: a degradable thermal transfer lettering film is prepared by the following steps:
(1) coating an anti-sticking layer coating solution on the back of the biaxially oriented base film in a spraying mode, and controlling the stretching tension of the base film to be 6-12Kg/m2The coating speed is 55-95m/min, the oven temperature is 145-175 ℃, and the thickness of the coating after curing is 3-10 um;
(2) the stretching tension of the base film is the same as that of the step (1), the release layer pressure-sensitive adhesive is coated on the front surface of the base film stretched in the step (1), the coating speed is controlled to be 20-50m/min, the temperature of an oven is controlled to be 150-;
(3) the stretching tension of the base film is the same as that of the step (1), color layer ink is coated on the surface of the release layer by a comma scraper method, the coating speed is controlled to be 12-25m/min, the temperature of an oven is controlled to be 90-130 ℃, and the thickness of the coating after curing is 30-5 Oum;
(4) the stretching tension of the base film is the same as that of the step (1), the adhesive layer adhesive is coated on the surface of the color layer ink by using a hot melt adhesive coating machine, the temperature of a coating die head is controlled at 170 ℃ and 210 ℃, and the thickness of the coating after curing is 60-110 mu m;
(5) finally, the mixture is cut, rewound or opened to be processed into a roll or a single sheet for standby. When in use, a carving machine or a cutting machine is adopted to carve out the required pictures and texts, then materials except the pictures and texts are stripped, the materials are heated and pressed by a thermal transfer printing device to be adhered to the surface of a printing stock, and the bearing base film is peeled after cooling, so that the required pictures and texts can be obtained.
The material used by the basement membrane is degradable modified PET, and the preparation method comprises the steps of putting 20-35 parts by weight of polyethylene terephthalate, 10-15 parts by weight of fluorinated polyimide, 5-9 parts by weight of polybenzothiazole, 3-8 parts by weight of polycarbonate and 3-7 parts by weight of polybutylene succinate into a grinding machine for grinding for 25-35min, transferring into a reaction tank, heating to 80-120 ℃, stirring and blending for 30min, adding 1-3 parts by weight of environment-friendly plasticizer, heating to 150 ℃ and 200 ℃, continuing mixing for 20-30min, reducing the temperature to 60-65 ℃ at the speed of 3-5 ℃/min, transferring into a blow molding machine, and performing blow molding through a film blowing machine; the environment-friendly plasticizer is a mixture of epoxy fatty acid octyl ester and di-n-hexyl sebacate in a mass ratio of 1: 2-5.
The preparation method of the anti-sticking layer coating liquid comprises the following steps: the preparation method comprises the following steps of raw materials, by mass, 10-20 parts of vinyl ester resin, 3-8 parts of amino resin, 6-12 parts of non-drying alkyd resin, 2-5 parts of hectorite, 0.5-1.5 parts of cross-linking agent and 150 parts of solvent a 100-plus-150, premixing the vinyl ester resin, the amino resin and the non-drying alkyd resin, stirring for 10-20min at the rotating speed of 1500-plus-2000 rpm, adding the hectorite and the cross-linking agent, continuously stirring for 15-30min at the conditions of 40-50 ℃ and 1500-plus-2000 rpm to obtain a premixed solution, adding the premixed solution into the mixed solvent a, stirring for 60-120min at the rotating speed of 2000-plus-3000 rpm, and canning for later use. The solvent a is one or more of mixed solution of acetone, butanone, ethyl acetate, butyl butyrate, cyclohexanone, n-hexane, ethanol, isopropanol and butanol; the nondrying oleoyl alkyd resin is extracted from one or more of coconut oil, castor oil and palm oil.
The preparation method of the release layer pressure-sensitive adhesive comprises the following steps: the raw materials comprise, by mass, 15-25 parts of organic silicon pressure-sensitive adhesive, 10-20 parts of silica gel, 1-3 parts of catalyst and 80-120 parts of solvent b, the organic silicon pressure-sensitive adhesive and the silica gel are premixed, put into a pulverizer and pulverized to be within 50um, then added into the solvent together with the catalyst, stirred for 60-120min under the conditions of the temperature of 35-50 ℃ and the rotation speed of 2500 plus 3500rpm, and then kept stand and canned for later use. The catalyst is a zinc-bismuth bimetallic catalyst, wherein the zinc content is as follows: the content of bismuth is 1-10: 1; the solvent b is one or a mixture of toluene, xylene, dichlorotoluene, petroleum ether and ethyl acetate.
The preparation method of the color layer ink comprises the following steps: the raw materials comprise, by mass, 20-30 parts of modified resin, 5-15 parts of multicolor pigment, 2-5 parts of mixed auxiliary agent and 70-110 parts of solvent c; the modified resin is put into an ultrafine grinder to be ground to be within 20um, taken out to be mixed with the pigment, added into the solvent c, stirred at the rotating speed of 500 plus materials and 1000rpm while dropwise adding the mixed auxiliary agent, stirred for 60-120min, ground by a grinder until the particle size is 3-8um, and canned for later use. The colorful pigments can use pigments with different colors according to color requirements.
The preparation method of the modified resin comprises the following steps: mixing 25-35 parts of polyurethane resin, 10-16 parts of aliphatic polycarbonate and 12-15 parts of polylactic acid according to parts by weight, heating to 80-95 ℃, stirring and blending for 35min, adding 2-5 parts of synthetic vegetable ester, heating to 160-190 ℃, keeping mixing for 35-40min, cooling to 60-80 ℃, and grinding to below 30 mu m; the mixed auxiliary agent is prepared from the following components in a mass ratio of 1: 1-2: 0.5-1: 0.5-1 of a mixture of eugenol, tween, polyethylene wax and dimethyl phthalate; the solvent c is one or a mixture of ethanol, isopropanol, n-butanol, ethyl acetate, butyl acetate, isopropyl acetate, toluene, xylene, cyclohexanone, acetone and butanone.
The adhesive for the adhesive layer comprises, by mass, 20-50 parts of polyhydroxyalkanoate, 60-130 parts of modified rosin resin-vinyl chloride copolymer and 2-10 parts of erucamide. Wherein the modified rosin resin-vinyl chloride-vinyl acetate copolymer is prepared as follows: the raw materials comprise, by mass, 20-50 parts of natural starch extract, 2-5 parts of plasticizer, 30-65 parts of rosin resin, 35-60 parts of vinyl chloride-vinyl acetate copolymer and 1-3 parts of polyethylene wax additive; placing the natural starch extract and plasticizer into a high shear mixer, and modifying at 60-80 deg.C and 3000-3500rpm for 30-60min to obtain modified starch base material; mixing the rosin resin and the vinyl chloride-vinyl acetate copolymer, adding the modified starch base material and the polyethylene wax auxiliary agent, mixing and reacting for 50-70min at the temperature of 60-90 ℃ and the speed of 1000-2000rpm, and standing for 12-24 h. The plasticizer is prepared from glycerol and ethylene glycol in a mass ratio of 1: 1; the natural starch extract is extracted from one or more of soybean, wheat, corn and potato.
The invention has the advantages that:
1. the invention utilizes degradable materials with excellent comprehensive performance, so that the transfer printing and lettering film is environment-friendly and has the advantages of no deformation, high and low temperature resistance, bright color and beautiful appearance;
2. the base film adopts the degradable modified high-temperature resistant film, does not need aging treatment before use, shortens the manufacturing process, saves the time and the cost, and simultaneously prevents the quality of the heat transfer printing lettering film from being influenced by the expansion and contraction deformation caused by a plurality of manufacturing processes;
3. the color layer ink disclosed by the invention adopts environment-friendly modified resin as a main body, has a degradable effect, and simultaneously has excellent mechanical properties after thermal transfer printing, so that a finished product has the characteristics of no deformation, high and low temperature resistance and water washing resistance;
4. the adhesive layer of the invention adopts the modified rosin resin-vinyl chloride-acetate copolymer, enhances the adhesive force on the surface of a printing stock, particularly on clothes made of pure cotton, and has no irritation to the skin.
In order to make the preparation method and the application of the degradable thermal transfer imprinting film more clear, the invention is further described with reference to the specific embodiments.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
A degradable thermal transfer lettering film is prepared by the following steps:
(1) coating anti-sticking layer coating liquid on the back of the base film in a spraying mode, and controlling the stretching tension of the base film to be 8Kg/m2The coating speed is 70m/min, the temperature of the oven is 150 ℃, and the thickness of the coating after curing is 6 um;
(2) the stretching tension of the base film is the same as that in the step (1), the release layer pressure-sensitive adhesive is coated on the front surface of the base film subjected to biaxial stretching in the step (1), the coating speed is controlled to be 35m/min, the temperature of an oven is controlled to be 160 ℃, and the thickness of the coating after curing is 12 um;
(3) coating color layer ink on the surface of the release layer by using a comma scraper method, controlling the coating speed to be 18m/min, controlling the temperature of an oven to be 110 ℃, and curing the coating to be 40um in thickness in the same step (1) as the stretching tension of the base film;
(4) the stretching tension of the base film is the same as that in the step (1), the adhesive layer adhesive is coated on the surface of the color layer ink by using a hot melt adhesive coating machine, the temperature of a coating die head is controlled at 190 ℃, and the thickness of the coating after curing is 80 um;
(5) finally, the mixture is cut, rewound or opened to be processed into a roll or a single sheet for standby. When the printing material is used, a carving machine or a cutting machine is adopted to carve out required pictures and texts, materials except the pictures and texts are stripped, the materials are heated and pressed by a thermal transfer printing device to be adhered to the surface of a printing material, and the bearing base film is peeled after cooling to obtain the required pictures and texts.
The material used by the base film is degradable modified PET, and the preparation method comprises the steps of putting 28 parts by weight of polyethylene terephthalate, 12 parts by weight of fluorinated polyimide, 7 parts by weight of polybenzothiazole, 5 parts by weight of polycarbonate and 5 parts by weight of polybutylene succinate into a grinding machine for grinding for 30min, transferring into a reaction tank, heating to 100 ℃, stirring and blending for 30min, adding 2 parts by weight of environment-friendly plasticizer, heating to 175 ℃, continuing mixing for 25min, reducing to 62 ℃ at the speed of 4 ℃/min, transferring into an extruder, and performing blow molding through a film blow molding machine; the environment-friendly plasticizer is prepared from the following components in percentage by mass: 3.5 mixtures of octyl epoxyfatty acid esters, di-n-hexyl sebacate.
The preparation method of the anti-sticking layer coating liquid comprises the following steps: the preparation method comprises the following steps of mixing 15 parts by mass of vinyl ester resin, 5 parts by mass of amino resin, 9 parts by mass of non-drying oleyl acid resin, 3 parts by mass of hectorite, 1 part by mass of a cross-linking agent and 125 parts by mass of a solvent, premixing the vinyl ester resin, the amino resin and the non-drying oleyl acid resin, stirring at the rotation speed of 1750pm for 15min, adding the hectorite and the cross-linking agent, continuously stirring at the temperature of 45 ℃ and the rotation speed of 1750rpm for 20min to obtain a premixed solution, adding the premixed solution into the mixed solvent a, stirring at the rotation speed of 2500rpm for 80min, and canning for later use. The solvent a is one or more of mixed solution of acetone, butanone, ethyl acetate, butyl butyrate, cyclohexanone, n-hexane, ethanol, isopropanol and butanol; the nondrying oleoyl alkyd resin is extracted from one or more of coconut oil, castor oil and palm oil.
The preparation method of the release layer pressure-sensitive adhesive comprises the following steps: the raw materials comprise, by mass, 20 parts of organic silicon pressure-sensitive adhesive, 15 parts of silica gel, 2 parts of catalyst and 100 parts of solvent b, the organic silicon pressure-sensitive adhesive and the silica gel are premixed, put into a crusher to be crushed to be within 50um, then added into the solvent together with the catalyst, stirred for 90min at the temperature of 45 ℃ and the rotating speed of 3000rpm, and kept stand to be canned for later use. The catalyst is a zinc-bismuth bimetallic catalyst, wherein the zinc content is as follows: the bismuth content is 5: 1; the solvent b is one or a mixture of toluene, xylene, dichlorotoluene, petroleum ether and ethyl acetate.
The preparation method of the color layer ink comprises the following steps: the paint comprises the following raw materials, by mass, 25 parts of modified resin, 10 parts of multicolor pigment, 3 parts of mixed auxiliary agent and 90 parts of solvent; putting the modified resin into an ultrafine grinder to be ground to within 20um, taking out and mixing with the pigment, adding into the solvent c, stirring at the rotating speed of 800rpm while dropwise adding the mixed auxiliary agent, stirring for 90min, grinding by a grinder until the particle size is 5um, and canning for later use. The colorful pigments can use pigments with different colors according to color requirements.
The preparation method of the modified resin comprises the following steps: mixing 30 parts of polyurethane resin, 13 parts of aliphatic polycarbonate and 13 parts of polylactic acid according to parts by weight of raw materials, heating to 85 ℃, stirring and blending for 35min, adding 3 parts of synthetic vegetable ester, heating to 175 ℃, keeping mixing for 35min, cooling to 70 ℃, and grinding to be less than 30 um; the mixed auxiliary agent is prepared from the following components in a mass ratio of 1: 1.5: 0.7: 0.7 of a mixture of eugenol, tween, polyethylene wax and dimethyl phthalate; the solvent c is one or a mixture of ethanol, isopropanol, n-butanol, ethyl acetate, butyl acetate, isopropyl acetate, toluene, xylene, cyclohexanone, acetone and butanone.
The adhesive for the adhesive layer comprises, by mass, 35 parts of polyhydroxyalkanoate, 100 parts of modified rosin resin-vinyl chloride copolymer and 6 parts of erucamide. Wherein the modified rosin resin-vinyl chloride-vinyl acetate copolymer is prepared as follows: the raw materials comprise, by mass, 35 parts of a natural starch extract, 3 parts of a plasticizer, 50 parts of rosin resin, 50 parts of vinyl chloride-vinyl acetate copolymer and 2 parts of a polyethylene wax additive; placing natural starch extract and plasticizer into high shear mixer, and modifying at 70 deg.C and 3200rpm for 45min to obtain modified starch base material; mixing rosin resin and vinyl chloride-vinyl acetate copolymer, adding modified starch base material and polyethylene wax auxiliary agent, mixing and reacting at 75 ℃ and 1500rpm for 60min, and standing for 18 h. The plasticizer is prepared from glycerol and ethylene glycol in a mass ratio of 1: 1; the natural starch extract is extracted from one or more of soybean, wheat, corn and potato.
Example 2
A degradable thermal transfer lettering film is prepared by the following steps:
(1) coating an anti-sticking layer coating solution on the back of the biaxially oriented base film in a spraying mode, and controlling the stretching tension of the base film to be 6Kg/m2The coating speed is 55m/min, the oven temperature is 145 ℃, and the thickness of the coating after curing is 10 um;
(2) the stretching tension of the base film is the same as that in the step (1), the release layer pressure-sensitive adhesive is coated on the front surface of the base film subjected to biaxial stretching in the step (1), the coating speed is controlled to be 20m/min, the temperature of an oven is controlled to be 150 ℃, and the thickness of the coating after curing is 15 um;
(3) the stretching tension of the base film is the same as that in the step (1), color layer ink is coated on the surface of the release layer by using a comma scraper method, the coating speed is controlled to be 12m/min, the temperature of an oven is controlled to be 90 ℃, and the thickness of the coating after curing is 5 Oum;
(4) the stretching tension of the base film is the same as that in the step (1), the adhesive layer adhesive is coated on the surface of the color layer ink by using a hot melt adhesive coating machine, the temperature of a coating die head is controlled at 170 ℃, and the thickness of the coating after curing is 110 um;
(5) finally, the mixture is cut, rewound or opened to be processed into a roll or a single sheet for standby. When in use, a carving machine or a cutting machine is adopted to carve out the required pictures and texts, then materials except the pictures and texts are stripped, the materials are heated and pressed by a thermal transfer printing device to be adhered to the surface of a printing stock, and the bearing base film is peeled after cooling, so that the required pictures and texts can be obtained.
The material used by the base film is degradable modified PET, and the preparation method comprises the steps of putting 20 parts by weight of polyethylene terephthalate, 10 parts by weight of fluorinated polyimide, 5 parts by weight of polybenzothiazole, 3 parts by weight of polycarbonate and 3 parts by weight of polybutylene succinate into a grinding machine for grinding for 25min, transferring into a reaction tank, heating to 80 ℃, stirring and blending for 30min, adding 1 part by weight of environment-friendly plasticizer, heating to 150 ℃, continuing mixing for 20min, reducing to 60 ℃ at the speed of 3 ℃/min, transferring into an extruder, and performing blow molding through a film blow molding machine; the environment-friendly plasticizer is a mixture of epoxy fatty acid octyl ester and di-n-hexyl sebacate in a mass ratio of 1: 2.
The preparation method of the anti-sticking layer coating liquid comprises the following steps: the preparation method comprises the following steps of premixing 10-20 parts by mass of vinyl ester resin, 3-8 parts by mass of amino resin, 6 parts by mass of non-drying alkyd resin, 2 parts by mass of hectorite, 0.5 part by mass of cross-linking agent and 100 parts by mass of solvent a, stirring at 1500rpm for 10min, adding the hectorite and the cross-linking agent, continuously stirring at 40 ℃ and 1500rpm for 15min to obtain a premixed solution, adding the premixed solution into the mixed solvent a, stirring at 2000rpm for 60min, and canning for later use. The solvent a is one or more of mixed solution of acetone, butanone, ethyl acetate, butyl butyrate, cyclohexanone, n-hexane, ethanol, isopropanol and butanol; the nondrying oleoyl alkyd resin is extracted from one or more of coconut oil, castor oil and palm oil.
The preparation method of the release layer pressure-sensitive adhesive comprises the following steps: the raw materials comprise, by mass, 15 parts of organic silicon pressure-sensitive adhesive, 10 parts of silica gel, 1 part of catalyst and 80 parts of solvent b, the organic silicon pressure-sensitive adhesive and the silica gel are premixed, put into a crusher to be crushed to be within 50um, then added into the solvent together with the catalyst, stirred for 60min under the conditions of the temperature of 35 ℃ and the rotating speed of 2500rpm, and then kept stand to be canned for later use. The catalyst is a zinc-bismuth bimetallic catalyst, wherein the zinc content is as follows: the bismuth content is 1: 1; the solvent b is one or a mixture of toluene, xylene, dichlorotoluene, petroleum ether and ethyl acetate.
The preparation method of the color layer ink comprises the following steps: the raw materials comprise, by mass, 20 parts of modified resin, 5 parts of multicolor pigment, 2 parts of mixed auxiliary agent and 70 parts of solvent c; putting the modified resin into an ultrafine grinder to be ground to within 20um, taking out and mixing with the pigment, adding into the solvent c, stirring at the rotating speed of 500rpm while dropwise adding the mixed auxiliary agent, stirring for 60min, grinding by a grinder until the particle size is 3um, and canning for later use. The colorful pigments can use pigments with different colors according to color requirements.
The preparation method of the modified resin comprises the following steps: mixing 25-35 parts of polyurethane resin, 10 parts of aliphatic polycarbonate and 12 parts of polylactic acid, heating to 80 ℃, stirring and blending for 35min, adding 2 parts of synthetic vegetable ester, heating to 160 ℃, keeping mixing for 35min, cooling to 60 ℃, grinding and crushing to below 30 um; the mixed auxiliary agent is prepared from the following components in a mass ratio of 1: 1: 0.5: 0.5 of a mixture of eugenol, tween, polyethylene wax and dimethyl phthalate; the solvent c is one or a mixture of ethanol, isopropanol, n-butanol, ethyl acetate, butyl acetate, isopropyl acetate, toluene, xylene, cyclohexanone, acetone and butanone.
The adhesive for the adhesive layer comprises, by mass, 20 parts of polyhydroxyalkanoate, 60 parts of modified rosin resin-vinyl chloride copolymer and 2 parts of erucamide. Wherein the modified rosin resin-vinyl chloride-vinyl acetate copolymer is prepared as follows: the raw materials comprise, by mass, 20 parts of a natural starch extract, 2 parts of a plasticizer, 30 parts of rosin resin, 35 parts of vinyl chloride-vinyl acetate copolymer and 1 part of a polyethylene wax additive; placing natural starch extract and plasticizer into high shear mixer, and modifying at 60 deg.C and 3000rpm for 30min to obtain modified starch base material; mixing rosin resin and vinyl chloride-vinyl acetate copolymer, adding modified starch base material and polyethylene wax auxiliary agent, mixing and reacting at 60 ℃ and 1000rpm for 50min, and standing for 12-24 h. The plasticizer is prepared from glycerol and ethylene glycol in a mass ratio of 1: 1; the natural starch extract is extracted from one or more of soybean, wheat, corn and potato.
Example 3
A degradable thermal transfer lettering film is prepared by the following steps:
(1) coating an anti-sticking layer coating solution on the back of the biaxially oriented base film in a spraying mode, and controlling the stretching tension of the base film to be 12Kg/m2Coating speed 95m/min, oven temperature 175 deg.C, coating thickness after curingIs 3 um;
(2) the stretching tension of the base film is the same as that of the step (1), the release layer pressure-sensitive adhesive is coated on the front surface of the base film subjected to biaxial stretching in the step (1), the coating speed is controlled to be 50m/min, the temperature of an oven is controlled to be 180 ℃, and the thickness of the coating after curing is 8 um;
(3) coating color layer ink on the surface of the release layer by using a comma scraper method, controlling the coating speed to be 25m/min, controlling the temperature of an oven to be 130 ℃, and curing the coating to be 30um in thickness in the same step (1) as the stretching tension of the base film;
(4) the stretching tension of the base film is the same as that in the step (1), the adhesive layer adhesive is coated on the surface of the color layer ink by using a hot melt adhesive coating machine, the temperature of a coating die head is controlled at 210 ℃, and the thickness of the coating after curing is 60 um;
(5) finally, the mixture is cut, rewound or opened to be processed into a roll or a single sheet for standby. When in use, a carving machine or a cutting machine is adopted to carve out the required pictures and texts, then materials except the pictures and texts are stripped, the materials are heated and pressed by a thermal transfer printing device to be adhered to the surface of a printing stock, and the bearing base film is peeled after cooling, so that the required pictures and texts can be obtained.
The material used by the base film is degradable modified PET, and the preparation method comprises the steps of putting 35 parts by weight of polyethylene terephthalate, 15 parts by weight of fluorinated polyimide, 9 parts by weight of polybenzothiazole, 8 parts by weight of polycarbonate and 7 parts by weight of polybutylene succinate into a grinding machine for grinding for 35min, transferring into a reaction tank for heating to 120 ℃, stirring and blending for 30min, adding 3 parts by weight of environment-friendly plasticizer, heating to 200 ℃, continuing mixing for 30min, reducing to 65 ℃ at the speed of 5 ℃/min, transferring into an extruder, and performing blow molding by a film blow molding machine; the environment-friendly plasticizer is a mixture of epoxy fatty acid octyl ester and di-n-hexyl sebacate in a mass ratio of 1: 5.
The preparation method of the anti-sticking layer coating liquid comprises the following steps: the preparation method comprises the following steps of pre-mixing 20 parts by mass of vinyl ester resin, 8 parts by mass of amino resin, 12 parts by mass of non-drying alkyd resin, 5 parts by mass of hectorite, 1.5 parts by mass of cross-linking agent and 150 parts by mass of solvent a, stirring at 2000rpm for 20min, adding the hectorite and the cross-linking agent, continuously stirring at 50 ℃ and 2000rpm for 30min to obtain a pre-mixed solution, adding the pre-mixed solution into the mixed solvent a, stirring at 3000rpm for 120min, and canning for later use. The solvent a is one or more of mixed solution of acetone, butanone, ethyl acetate, butyl butyrate, cyclohexanone, n-hexane, ethanol, isopropanol and butanol; the nondrying oleoyl alkyd resin is extracted from one or more of coconut oil, castor oil and palm oil.
The preparation method of the release layer pressure-sensitive adhesive comprises the following steps: the raw materials comprise, by mass, 25 parts of organic silicon pressure-sensitive adhesive, 20 parts of silica gel, 3 parts of catalyst and 120 parts of solvent b, the organic silicon pressure-sensitive adhesive and the silica gel are premixed, put into a crusher to be crushed to be within 50um, then added into the solvent together with the catalyst, stirred for 120min at the temperature of 50 ℃ and the rotation speed of 3500rpm, and kept stand to be canned for later use. The catalyst is a zinc-bismuth bimetallic catalyst, wherein the zinc content is as follows: the bismuth content is 10: 1; the solvent b is one or a mixture of toluene, xylene, dichlorotoluene, petroleum ether and ethyl acetate.
The preparation method of the color layer ink comprises the following steps: the raw materials comprise, by mass, 30 parts of modified resin, 15 parts of multicolor pigment, 5 parts of mixed auxiliary agent and 110 parts of solvent; putting the modified resin into an ultrafine grinder to be ground to within 20um, taking out and mixing with the pigment, adding into the solvent c, stirring at 1000rpm while dropwise adding the mixed auxiliary agent, stirring for 120min, grinding by a grinder until the particle size is 8um, and canning for later use. The colorful pigments can use pigments with different colors according to color requirements.
The preparation method of the modified resin comprises the following steps: mixing 35 parts of polyurethane resin, 16 parts of aliphatic polycarbonate and 15 parts of polylactic acid according to parts by weight, heating to 95 ℃, stirring and blending for 35min, adding 5 parts of synthetic vegetable ester, heating to 190 ℃, keeping mixing for 40min, cooling to 80 ℃, grinding and crushing to below 30 um; the mixed auxiliary agent is prepared from the following components in a mass ratio of 1: 2: 1:1 of eugenol, tween, polyethylene wax and dimethyl phthalate; the solvent c is one or a mixture of ethanol, isopropanol, n-butanol, ethyl acetate, butyl acetate, isopropyl acetate, toluene, xylene, cyclohexanone, acetone and butanone.
The adhesive for the adhesive layer comprises, by mass, 50 parts of polyhydroxyalkanoate, 130 parts of modified rosin resin-vinyl chloride copolymer and 10 parts of an opening agent. Wherein the modified rosin resin-vinyl chloride-vinyl acetate copolymer is prepared as follows: the raw materials comprise, by mass, 50 parts of a natural starch extract, 5 parts of a plasticizer, 65 parts of rosin resin, 60 parts of vinyl chloride-vinyl acetate copolymer and 3 parts of a polyethylene wax additive; placing the natural starch extract and plasticizer into a high shear mixer, and modifying at 80 deg.C and 3500rpm for 60min to obtain modified starch base material; mixing rosin resin and vinyl chloride-vinyl acetate copolymer, adding modified starch base material and polyethylene wax auxiliary agent, mixing and reacting at 90 ℃ and 2000rpm for 70min, and standing for 24 h. The plasticizer is prepared from glycerol and ethylene glycol in a mass ratio of 1: 1; the natural starch extract is extracted from one or more of soybean, wheat, corn and potato.
Example 4
A degradable thermal transfer lettering film is prepared by the following steps:
(1) coating an anti-sticking layer coating solution on the back of the biaxially oriented base film in a spraying mode, and controlling the stretching tension of the base film to be 5Kg/m2The coating speed is 50m/min, the temperature of the oven is 140 ℃, and the thickness of the coating after curing is 12 um;
(2) the stretching tension of the base film is the same as that in the step (1), the release layer pressure-sensitive adhesive is coated on the front surface of the base film subjected to biaxial stretching in the step (1), the coating speed is controlled to be 18m/min, the temperature of an oven is controlled to be 145 ℃, and the thickness of the coating after curing is 18 um;
(3) coating color layer ink on the surface of the release layer by using a comma scraper method, controlling the coating speed to be 11m/min, controlling the temperature of an oven to be 85 ℃, and curing the coating to be 55um in thickness in the same step (1) as the stretching tension of the base film;
(4) the stretching tension of the base film is the same as that in the step (1), the adhesive layer adhesive is coated on the surface of the color layer ink by using a hot melt adhesive coating machine, the temperature of a coating die head is controlled at 165 ℃, and the thickness of the coating after curing is 115 um;
(5) finally, the mixture is cut, rewound or opened to be processed into a roll or a single sheet for standby. When in use, a carving machine or a cutting machine is adopted to carve out the required pictures and texts, then materials except the pictures and texts are stripped, the materials are heated and pressed by a thermal transfer printing device to be adhered to the surface of a printing stock, and the bearing base film is peeled after cooling, so that the required pictures and texts can be obtained.
The material used by the base film is degradable modified PET, and the preparation method comprises the steps of putting 19 parts by weight of polyethylene terephthalate, 9 parts by weight of fluorinated polyimide, 4 parts by weight of polybenzothiazole, 2 parts by weight of polycarbonate and 2 parts by weight of polybutylene succinate into a grinding machine for grinding for 20min, transferring into a reaction tank, heating to 75 ℃, stirring and blending for 30min, adding 0.5 part by weight of environment-friendly plasticizer, heating to 145 ℃, continuing mixing for 15min, reducing to 55 ℃ at the speed of 2 ℃/min, transferring into an extruder, and performing blow molding through a film blow molding machine; the environment-friendly plasticizer is a mixture of epoxy fatty acid octyl ester and di-n-hexyl sebacate in a mass ratio of 1: 1.
The preparation method of the anti-sticking layer coating liquid comprises the following steps: the preparation method comprises the following steps of mixing 9 parts by mass of vinyl ester resin, 2 parts by mass of amino resin, 5 parts by mass of non-drying oleyl acid resin, 1 part by mass of hectorite, 0.4 part by mass of a cross-linking agent and 99 parts by mass of a solvent a, premixing the vinyl ester resin, the amino resin and the non-drying oleyl acid resin, stirring at the rotating speed of 1400rpm for 9min, adding the hectorite and the cross-linking agent, continuously stirring at the temperature of 35 ℃ and the rotating speed of 1400rpm for 14min to obtain a premixed solution, adding the premixed solution into the mixed solvent a, stirring at the rotating speed of 1800rpm for 50min, and canning for later use. The solvent a is one or more of mixed solution of acetone, butanone, ethyl acetate, butyl butyrate, cyclohexanone, n-hexane, ethanol, isopropanol and butanol; the nondrying oleoyl alkyd resin is extracted from one or more of coconut oil, castor oil and palm oil.
The preparation method of the release layer pressure-sensitive adhesive comprises the following steps: the raw materials comprise, by mass, 20 parts of organic silicon pressure-sensitive adhesive, 15 parts of silica gel, 2 parts of catalyst and 75 parts of solvent b, the organic silicon pressure-sensitive adhesive and the silica gel are premixed, put into a crusher to be crushed to be within 50um, then added into the solvent together with the catalyst, stirred for 55min under the conditions of the temperature of 30 ℃ and the rotating speed of 2400rpm, and then kept stand to be canned for later use. The catalyst is a zinc-bismuth bimetallic catalyst, wherein the zinc content is as follows: the bismuth content is 0.5: 1; the solvent b is one or a mixture of toluene, xylene, dichlorotoluene, petroleum ether and ethyl acetate.
The preparation method of the color layer ink comprises the following steps: the raw materials comprise, by mass, 19 parts of modified resin, 4 parts of multicolor pigment, 1 part of mixed auxiliary agent and 69 parts of solvent; putting the modified resin into an ultrafine grinder to be ground to within 20um, taking out and mixing with the pigment, adding into the solvent c, stirring at the rotating speed of 450rpm while dropwise adding the mixed auxiliary agent, stirring for 55min, grinding by a grinder until the particle size is 2um, and canning for later use. The colorful pigments can use pigments with different colors according to color requirements.
The preparation method of the modified resin comprises the following steps: mixing 24 parts of polyurethane resin, 9 parts of aliphatic polycarbonate and 11 parts of polylactic acid according to parts by weight, heating to 75 ℃, stirring and blending for 35min, adding 1 part of synthetic vegetable ester, heating to 155 ℃, keeping mixing for 30min, cooling to 55 ℃, grinding and crushing to below 30 um; the mixed auxiliary agent is prepared from the following components in a mass ratio of 1: 0.5: 0.4: 0.4 of a mixture of eugenol, tween, polyethylene wax and dimethyl phthalate; the solvent c is one or a mixture of ethanol, isopropanol, n-butanol, ethyl acetate, butyl acetate, isopropyl acetate, toluene, xylene, cyclohexanone, acetone and butanone.
The adhesive for the adhesive layer comprises, by mass, 15 parts of polyhydroxyalkanoate, 55 parts of modified rosin resin-vinyl chloride copolymer and 1 part of erucamide. Wherein the modified rosin resin-vinyl chloride-vinyl acetate copolymer is prepared as follows: the raw materials comprise, by mass, 19 parts of a natural starch extract, 1 part of a plasticizer, 25 parts of rosin resin, 30 parts of vinyl chloride-vinyl acetate copolymer and 0.5 part of a polyethylene wax additive; placing natural starch extract and plasticizer into high shear mixer, and modifying at 55 deg.C and 2900rpm for 25min to obtain modified starch base material; mixing rosin resin and vinyl chloride-vinyl acetate copolymer, adding modified starch base material and polyethylene wax auxiliary agent, mixing and reacting at 55 ℃ and 900rpm for 45min, and standing for 11 h. The plasticizer is prepared from glycerol and ethylene glycol in a mass ratio of 1: 1; the natural starch extract is extracted from one or more of soybean, wheat, corn and potato.
Example 5
A degradable thermal transfer lettering film is prepared by the following steps:
(1) coating an anti-sticking layer coating solution on the back of the biaxially oriented base film in a spraying manner, and controlling the stretching tension of the base film to be 13Kg/m2The coating speed is 96m/min, the oven temperature is 180 ℃, and the thickness of the coating after curing is 2 um;
(2) the stretching tension of the base film is the same as that in the step (1), the release layer pressure-sensitive adhesive is coated on the front surface of the base film subjected to biaxial stretching in the step (1), the coating speed is controlled to be 52m/min, the temperature of an oven is controlled to be 185 ℃, and the thickness of the coating after curing is 6 um;
(3) coating color layer ink on the surface of the release layer by using a comma scraper method, controlling the coating speed to be 26m/min, controlling the temperature of an oven to be 135 ℃, and curing the coating to be 25um in thickness in the same step (1) as the stretching tension of the base film;
(4) the stretching tension of the base film is the same as that in the step (1), the adhesive layer adhesive is coated on the surface of the color layer ink by using a hot melt adhesive coating machine, the temperature of a coating die head is controlled at 220 ℃, and the thickness of the coating after curing is 50 um;
(5) finally, the mixture is cut, rewound or opened to be processed into a roll or a single sheet for standby. When in use, a carving machine or a cutting machine is adopted to carve out the required pictures and texts, then materials except the pictures and texts are stripped, the materials are heated and pressed by a thermal transfer printing device to be adhered to the surface of a printing stock, and the bearing base film is peeled after cooling, so that the required pictures and texts can be obtained.
The material used by the base film is degradable modified PET, and the preparation method comprises the steps of putting 36 parts by weight of polyethylene terephthalate, 16 parts by weight of fluorinated polyimide, 10 parts by weight of polybenzothiazole, 9 parts by weight of polycarbonate and 8 parts by weight of polybutylene succinate into a grinding machine for grinding for 40min, transferring into a reaction tank, heating to 125 ℃, stirring and blending for 30min, adding 4 parts by weight of environment-friendly plasticizer, heating to 210 ℃, continuing mixing for 35min, reducing to 70 ℃ at the speed of 6 ℃/min, transferring into an extruder, and performing blow molding by a film blow molding machine; the environment-friendly plasticizer is a mixture of epoxy fatty acid octyl ester and di-n-hexyl sebacate in a mass ratio of 1: 6.
The preparation method of the anti-sticking layer coating liquid comprises the following steps: the preparation method comprises the following steps of mixing, by mass, 21 parts of vinyl ester resin, 9 parts of amino resin, 13 parts of non-drying alkyd resin, 6 parts of hectorite, 1.6 parts of cross-linking agent and 155 parts of solvent a, premixing the vinyl ester resin, the amino resin and the non-drying alkyd resin, stirring at 2100rpm for 22min, adding the hectorite and the cross-linking agent, continuously stirring at 55 ℃ and 2100rpm for 35min to obtain a premixed solution, adding the premixed solution into the mixed solvent a, stirring at 3200rpm for 125min, and canning for later use. The solvent a is one or more of mixed solution of acetone, butanone, ethyl acetate, butyl butyrate, cyclohexanone, n-hexane, ethanol, isopropanol and butanol; the nondrying oleoyl alkyd resin is extracted from one or more of coconut oil, castor oil and palm oil.
The preparation method of the release layer pressure-sensitive adhesive comprises the following steps: the raw materials comprise 26 parts of organic silicon pressure-sensitive adhesive, 21 parts of silica gel, 4 parts of catalyst and 125 parts of solvent b by mass, the organic silicon pressure-sensitive adhesive and the silica gel are premixed, put into a crusher to be crushed to be within 50um, then added into the solvent together with the catalyst, stirred for 125in at the temperature of 55 ℃ and the rotating speed of 3600rpm, and kept stand to be canned for later use. The catalyst is a zinc-bismuth bimetallic catalyst, wherein the zinc content is as follows: the bismuth content was 11: 1; the solvent b is one or a mixture of toluene, xylene, dichlorotoluene, petroleum ether and ethyl acetate.
The preparation method of the color layer ink comprises the following steps: the raw materials comprise, by mass, 31 parts of modified resin, 16 parts of multicolor pigment, 6 parts of mixed auxiliary agent and 115 parts of solvent c; putting the modified resin into an ultrafine grinder to be ground to within 20um, taking out and mixing with the pigment, adding into the solvent c, stirring at 1100rpm while dropwise adding the mixed auxiliary agent, stirring for 125min, grinding by a grinder until the particle size is 9um, and canning for later use. The colorful pigments can use pigments with different colors according to color requirements.
The preparation method of the modified resin comprises the following steps: mixing 36 parts of polyurethane resin, 17 parts of aliphatic polycarbonate and 16 parts of polylactic acid according to parts by weight, heating to 96 ℃, stirring and blending for 35min, adding 6 parts of synthetic vegetable ester, heating to 200 ℃, keeping mixing for 45min, cooling to 85 ℃, and grinding to be less than 30 um; the mixed auxiliary agent is prepared from the following components in a mass ratio of 1: 3: 1.5: 1.5 of a mixture of eugenol, tween, polyethylene wax and dimethyl phthalate; the solvent c is one or a mixture of ethanol, isopropanol, n-butanol, ethyl acetate, butyl acetate, isopropyl acetate, toluene, xylene, cyclohexanone, acetone and butanone.
The adhesive for the adhesive layer comprises 55 parts of polyhydroxyalkanoate, 132 parts of modified rosin resin-vinyl chloride copolymer and 12 parts of erucamide by mass. Wherein the modified rosin resin-vinyl chloride-vinyl acetate copolymer is prepared as follows: the raw materials comprise, by mass, 52 parts of a natural starch extract, 6 parts of a plasticizer, 66 parts of rosin resin, 61 parts of vinyl chloride-vinyl acetate copolymer and 4 parts of a polyethylene wax additive; placing the natural starch extract and plasticizer into a high shear mixer, and modifying at 90 deg.C and 3600rpm for 65min to obtain modified starch base material; mixing rosin resin and vinyl chloride-vinyl acetate copolymer, adding modified starch base material and polyethylene wax auxiliary agent, mixing and reacting at 95 ℃ and 2100rpm for 75min, and standing for 26 h. The plasticizer is prepared from glycerol and ethylene glycol in a mass ratio of 1: 1; the natural starch extract is extracted from one or more of soybean, wheat, corn and potato.
Example 6
A degradable thermal transfer printing lettering film is prepared by putting 15 parts by weight of polyethylene terephthalate, 20 parts by weight of fluorinated polyimide, 10 parts by weight of polybenzothiazole, 10 parts by weight of polycarbonate and 10 parts by weight of polybutylene succinate into a grinding machine for grinding for 30min, transferring into a reaction tank, heating to 100 ℃, stirring and blending for 30min, adding 4 parts by weight of an environment-friendly plasticizer, heating to 175 ℃, continuing mixing for 20-30min, reducing to 62 ℃ at the speed of 4 ℃/min, transferring into an extruder, and performing blow molding by a film blowing machine;
the rest is the same as example 1.
Example 7
A degradable thermal transfer printing lettering film is prepared by putting 30 parts by weight of polyethylene terephthalate, 16 parts by weight of fluorinated polyimide, 4 parts by weight of polybenzothiazole, 2 parts by weight of polycarbonate and 2 parts by weight of polybutylene succinate into a grinding machine for grinding for 30min, transferring into a reaction tank, heating to 100 ℃, stirring and blending for 30min, adding 2 parts by weight of an environment-friendly plasticizer, heating to 175 ℃, continuing mixing for 25min, reducing to 62 ℃ at the speed of 4 ℃/min, transferring into an extruder, and performing blow molding through a film blowing machine;
the rest is the same as example 1.
Example 8
A degradable thermal transfer lettering film uses PET as a base film.
The rest is the same as example 1.
Example 9
The degradable thermal transfer lettering film comprises, by mass, 18 parts of modified resin, 10 parts of multicolor pigment, 3 parts of mixed auxiliary agent and 90 parts of solvent c.
The rest is the same as example 1.
Example 10
The degradable thermal transfer lettering film comprises, by mass, 35 parts of modified resin, 10 parts of multicolor pigment, 3 parts of mixed auxiliary agent and 90 parts of solvent c.
The rest is the same as example 1.
Example 11
The degradable thermal transfer lettering film comprises, by mass, 25 parts of modified resin, 10 parts of multicolor pigment, 3 parts of mixed auxiliary agent and 90 parts of solvent c.
The modified resin raw material is prepared by mixing 20 parts of polyurethane resin, 9 parts of aliphatic polycarbonate and 10 parts of polylactic acid in parts by weight.
The rest is the same as example 1.
Example 12
The degradable thermal transfer lettering film comprises, by mass, 35 parts of polyhydroxyalkanoate, 25 parts of rosin resin-vinyl chloride copolymer modified substance and 6 parts of erucamide.
The rest of example 1.
Example 13
The degradable thermal transfer lettering film comprises, by mass, 35 parts of polyhydroxyalkanoate, 25 parts of modified rosin resin-vinyl chloride copolymer and 6 parts of erucamide.
The rest of example 1.
Example 14
The degradable thermal transfer lettering film comprises, by mass, 35 parts of polyhydroxyalkanoate, 100 parts of modified rosin resin-vinyl chloride-acetate copolymer and 6 parts of erucamide. Wherein the modified rosin resin-vinyl chloride-vinyl acetate copolymer is prepared as follows: the raw materials comprise, by mass, 15 parts of a natural starch extract, 1 part of a plasticizer, 25 parts of rosin resin, 30 parts of vinyl chloride-vinyl acetate copolymer and 0.5 part of a polyethylene wax additive.
The rest is the same as example 1.
Example 15
Various indexes of the application of the degradable thermal transfer imprinting films prepared in examples 1 to 14 to pure cotton clothes were measured, and data were recorded as follows in tables 1 and 2; wherein the degradation performance is tested as follows: weighing the initial weight (W0) of the material before degradation, then putting the material into phosphate buffer solution (PHA) with the pH of 7.6 according to the solid-to-liquid ratio of 0.5g/mg, preserving the material at constant temperature under the condition of 35 ℃, replacing the PHA solution every 5 days, taking out the residual solid every 30 days until 180 days, and recording the weights of W30, W60, W90, W120, W150 and W180 after vacuum drying to the constant weight; the weight loss is respectively (W0-W30)/W0 × 100%, (W0-W60)/W0 × 100%, (W0-W90)/W0 × 100%, (W0-W120)/W0 × 100%, (W0-W150)/W0 × 100%, (W0-W180)/W0 × 100%; the weight loss is used to express the degradation rate.
Test of
The heat-reducing transfer printing lettering films prepared according to the above embodiments are comprehensively compared in all aspects of performances, and are specifically shown in the following tables 1 and 2;
table 1 comprehensive conditions of thermal transfer printing lettering films table 1
Figure 495831DEST_PATH_IMAGE002
TABLE 2 comprehensive conditions of thermal transfer printing lettering films TABLE 1
Figure 209709DEST_PATH_IMAGE004
Analysis of the above data leads to the following conclusions:
(1) examples 1, 2, 3 are excellent in all aspects and have a fast degradation rate, especially the best of example 1;
(2) the overall parameters of the schemes of the embodiments 4 and 5 are out of the required range of the invention, and are slightly deficient compared with the embodiments 1 to 3; compared with the examples 1, 6, 7 and 8, excessive degradable modification is added in the base film formula in the example 6, although the degradation speed is faster, the high temperature resistance and the mechanical property are not good enough, the degradable modification component in the base film formula in the example 7 is less, and although the mechanical property is excellent, the degradation rate is reduced; in example 8, PET was used as a base film, which was generally degradable and generally stable against high temperatures.
(3) In comparison with example 1 and examples 9, 10 and 11, the color layer ink of example 9 has less modified resin, and the degradation effect is general although the touch is good, on the contrary, example 10 has the modified resin formula out of the range not required by the invention, and example 11 has all the ideal comprehensive properties.
(4) Comparing example 1 with examples 12, 13 and 14, the modified rosin resin-vinyl chloride copolymer in the adhesive layer binder of example 12 is less, so that the adhesion performance on the surface of a printing stock after thermal transfer is general, the adhesion is excellent but the degradation rate is improved in the case of example 13, and the formula of the modified rosin resin-vinyl chloride copolymer of example 14 is out of the range of the invention, so that the degradation effect and the mechanical property are general.
In conclusion, the degradable thermal transfer printing lettering film prepared by the invention has the advantages of bright, full and attractive color, soft touch, no toxicity and irritation, no deformation, water washing resistance, alcohol wiping resistance and other tests, and is degradable and environment-friendly.

Claims (9)

1. A preparation method of a degradable thermal transfer printing lettering film is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) coating an anti-sticking layer coating solution on the back of the biaxially oriented base film in a spraying mode, and controlling the stretching tension of the base film to be 6-12Kg/m2The coating speed is 55-95m/min, the oven temperature is 145-175 ℃, and the thickness of the coating after curing is 3-10 um;
(2) the stretching tension of the base film is the same as that of the step (1), the release layer pressure-sensitive adhesive is coated on the front surface of the base film stretched in the step (1), the coating speed is controlled to be 20-50m/min, the temperature of an oven is controlled to be 150-;
(3) the stretching tension of the base film is the same as that of the step (1), color layer ink is coated on the surface of the release layer by a comma scraper method, the coating speed is controlled to be 12-25m/min, the temperature of an oven is controlled to be 90-130 ℃, and the thickness of the coating after curing is 30-5 Oum;
(4) the stretching tension of the base film is the same as that of the step (1), the adhesive layer adhesive is coated on the surface of the color layer ink by using a hot melt adhesive coating machine, the temperature of a coating die head is controlled at 170 ℃ and 210 ℃, and the thickness of the coating after curing is 60-110 mu m;
(5) finally, the mixture is cut, rewound or opened to be processed into a roll or a single sheet for standby; when in use, a carving machine or a cutting machine is adopted to carve out the required pictures and texts, then materials except the pictures and texts are stripped, the materials are heated and pressed by a thermal transfer printing device to be adhered to the surface of a printing stock, and the bearing substrate is stripped after cooling, so that the required pictures and texts can be obtained.
2. The method of preparing a degradable thermal transfer imprinting film according to claim 1, wherein: the base film is degradable modified PET, and the preparation method comprises the steps of putting 20-35 parts by weight of polyethylene terephthalate, 10-15 parts by weight of fluorinated polyimide, 5-9 parts by weight of polybenzothiazole, 3-8 parts by weight of polycarbonate and 3-7 parts by weight of polybutylene succinate into a grinding machine for grinding for 25-35min, transferring into a reaction tank, heating to 80-120 ℃, stirring and blending for 30min, adding 1-3 parts by weight of an environment-friendly plasticizer, heating to 150-200 ℃, continuing mixing for 20-30min, reducing the temperature to 60-65 ℃ at the speed of 3-5 ℃/min, transferring into an extruder, and performing blow molding by a film blow molding machine; the environment-friendly plasticizer is prepared from the following components in percentage by mass: 2-5 of a mixture of octyl epoxyfatty acid and di-n-hexyl sebacate.
3. The method of preparing a degradable thermal transfer imprinting film according to claim 1, wherein: the preparation method of the anti-sticking layer coating liquid comprises the following steps: the preparation method comprises the following steps of (by mass) premixing 10-20 parts of vinyl ester resin, 3-8 parts of amino resin, 6-12 parts of non-drying alkyd resin, 2-5 parts of hectorite, 0.5-1.5 parts of cross-linking agent and 150 parts of solvent a 100-containing organic acid, stirring the vinyl ester resin, the amino resin and the non-drying alkyd resin at the rotating speed of 1500-2000rpm for 10-20min, adding the hectorite and the cross-linking agent, continuously stirring at the conditions of 40-50 ℃ and 1500-containing organic acid at the rotating speed of 2000rpm for 15-30min to obtain a premixed solution, adding the premixed solution into the mixed solvent a, stirring at the rotating speed of 3000rpm of 2000-containing organic acid for 60-120min, and canning for later use; the solvent a is one or more of mixed solution of acetone, butanone, ethyl acetate, butyl butyrate, cyclohexanone, n-hexane, ethanol, isopropanol and butanol; the nondrying oleoyl alkyd resin is extracted from one or more of coconut oil, castor oil and palm oil.
4. The method of preparing a degradable thermal transfer imprinting film according to claim 1, wherein: the preparation method of the release layer pressure-sensitive adhesive comprises the following steps: the raw materials comprise, by mass, 15-25 parts of organic silicon pressure-sensitive adhesive, 10-20 parts of silica gel, 1-3 parts of catalyst and 80-120 parts of solvent b, the organic silicon pressure-sensitive adhesive and the silica gel are premixed, put into a crusher to be crushed to be within 50um, then added into the solvent together with the catalyst, stirred for 60-120min under the conditions of the temperature of 35-50 ℃ and the rotation speed of 2500 plus 3500rpm, and then kept stand and canned for standby; the catalyst is a zinc-bismuth bimetallic catalyst, wherein the zinc content is as follows: the content of bismuth is 1-10: 1; the solvent b is one or a mixture of toluene, xylene, dichlorotoluene, petroleum ether and ethyl acetate.
5. The method of preparing a degradable thermal transfer imprinting film according to claim 1, wherein: the preparation method of the color layer ink comprises the following steps: the raw materials comprise, by mass, 20-30 parts of modified resin, 5-15 parts of pigment, 2-5 parts of mixed auxiliary agent and 70-110 parts of solvent c; putting the modified resin into an ultrafine grinder to be ground to be within 20um, taking out the modified resin to be mixed with the pigment, adding the mixture into a solvent c, stirring at the rotating speed of 500 plus 1000rpm while dropwise adding a mixed auxiliary agent, stirring for 60-120min, grinding by using a grinder until the particle size is 3-8um, and canning for later use; wherein the pigment is a mixture of one or more different colors.
6. The method of claim 5 for preparing a degradable thermal transfer imprinting film, comprising: the preparation method of the modified resin comprises the following steps: mixing 25-35 parts of polyurethane resin, 10-16 parts of aliphatic polycarbonate and 12-15 parts of polylactic acid according to parts by weight, heating to 80-95 ℃, stirring and blending for 35min, adding 2-5 parts of synthetic vegetable ester, heating to 160-190 ℃, keeping mixing for 35-40min, cooling to 60-80 ℃, and grinding to below 30 mu m; the mixed auxiliary agent is prepared from the following components in a mass ratio of 1: 1-2: 0.5-1: 0.5-1 of a mixture of eugenol, tween, polyethylene wax and dimethyl phthalate; the solvent c is one or a mixture of ethanol, isopropanol, n-butanol, ethyl acetate, butyl acetate, isopropyl acetate, toluene, xylene, cyclohexanone, acetone and butanone.
7. The method of preparing a degradable thermal transfer imprinting film according to claim 1, wherein: the adhesive for the adhesive layer comprises, by mass, 20-50 parts of polyhydroxyalkanoate, 60-130 parts of modified rosin resin-vinyl chloride copolymer and 2-10 parts of erucamide.
8. The degradable thermal transfer imprinting film of claim 7, wherein: the modified rosin resin-vinyl chloride-vinyl acetate copolymer is prepared as follows: the raw materials comprise, by mass, 20-50 parts of natural starch extract, 2-5 parts of plasticizer, 30-65 parts of rosin resin, 35-60 parts of vinyl chloride-vinyl acetate copolymer and 1-3 parts of polyethylene wax additive; placing the natural starch extract and plasticizer into a high shear mixer to modify at 60-80 deg.C and 3000-; mixing rosin resin and vinyl chloride-vinyl acetate resin, adding modified starch base material and polyethylene wax auxiliary agent, mixing and reacting for 50-70min at 60-90 ℃ and 2000rpm at 1000-; the plasticizer is prepared from glycerol and ethylene glycol in a mass ratio of 1: 1; the natural starch extract is one or more of soybean, wheat, corn and potato.
9. Use of a degradable thermal transfer imprinting film prepared according to any of claims 1-8 in apparel, water wash, gloves, footwear, bags and textiles.
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