CN111923647A - Ultraviolet-curing high-temperature water transfer-printing decorative film and manufacturing method thereof - Google Patents

Ultraviolet-curing high-temperature water transfer-printing decorative film and manufacturing method thereof Download PDF

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Publication number
CN111923647A
CN111923647A CN202010205328.2A CN202010205328A CN111923647A CN 111923647 A CN111923647 A CN 111923647A CN 202010205328 A CN202010205328 A CN 202010205328A CN 111923647 A CN111923647 A CN 111923647A
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China
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acrylate
meth
methyl
ultraviolet
temperature water
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Chinese (zh)
Inventor
徐洋
郑军明
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Tianling Intelligent Technology Kunshan Co ltd
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Tianling Intelligent Technology Kunshan Co ltd
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Priority to CN202010205328.2A priority Critical patent/CN111923647A/en
Publication of CN111923647A publication Critical patent/CN111923647A/en
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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
    • B44C1/175—Transfer using solvent
    • B44C1/1752—Decalcomanias provided with a particular decorative layer, e.g. being specially adapted to allow the formation of a metallic or dyestuff layer on a substrate unsuitable for direct deposition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/12—Stencil printing; Silk-screen printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/025—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet
    • 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
    • B44C1/175—Transfer using solvent
    • B44C1/1754—Decalcomanias provided with a layer being specially adapted to facilitate their release from a temporary carrier
    • 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
    • C09D11/03—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
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Decoration By Transfer Pictures (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides an ultraviolet curing high-temperature water transfer printing decorative film, which comprises base paper, an image layer printed on the base paper and a film layer supporting the transfer of the image layer; wherein the image layer and the film layer are provided with a curable resin layer which can be cured by ultraviolet irradiation; the thickness of the image layer is 10-100 μm, and the thickness of the film layer is 10-50 μm. The preparation method of the ultraviolet-curing high-temperature water transfer printing decorative film provided by the invention adopts ultraviolet curing treatment, has no solvent volatilization, does not cause adverse effects on environment and personnel health, and is an environment-friendly product. Meanwhile, the ultraviolet curing treatment is adopted to replace the traditional heat drying treatment, so that the energy consumption in the using process is reduced. The ultraviolet-curing high-temperature water transfer printing decorative film has good flexibility, high reduction degree of printed patterns and bright color of sintered devices, and can be applied to the surfaces of curved materials such as ceramics, glass, enamel and the like.

Description

Ultraviolet-curing high-temperature water transfer-printing decorative film and manufacturing method thereof
Technical Field
The invention relates to a high-temperature water transfer printing decorative film, in particular to an ultraviolet light curing type high-temperature water transfer printing decorative film and a preparation method thereof, and belongs to the technical field of environment.
Background
In the prior art, the surface of kiln products such as ceramic ware, glass, enamel and the like is decorated by adopting a water transfer type drawing method. The water transfer type drawing method includes the steps of coating water soluble paste on base paper, printing pattern with kiln printing ink, forming one film layer to support transfer printing ink, soaking the printed transfer printing paper in water, stripping the pattern and the film layer, adhering to the transferred matter, drying and sintering. However, the high-temperature water transfer material prepared by the method is a solvent type product, contains 50-70% of naphtha or 2-ethoxy ethanol solvent, volatilizes when in use, is harmful to the health of operators, discharges volatile compounds (VOC) to pollute the environment, does not meet the requirements of environment and development, and simultaneously adopts heating for drying treatment, so that the energy consumption is higher. Therefore, how to overcome these difficulties is a problem to be solved.
Disclosure of Invention
The invention aims to provide an ultraviolet light curing type high-temperature water transfer printing decorative film and a preparation method thereof, which overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides an ultraviolet curing high-temperature water transfer printing decorative film, which comprises base paper, an image layer printed on the base paper and a film layer supporting transfer of the image layer;
wherein the image layer is provided with a curable resin layer which can be cured by ultraviolet irradiation, and the film layer is provided with a curable resin layer which can be cured by ultraviolet irradiation;
the thickness of the image layer is 10-100 μm, and the thickness of the film layer is 10-50 μm;
the image layer mixture comprises a ceramic pigment, a photo-curing resin/monomer and a photo-polymerization initiator, wherein the mass ratio of the ceramic pigment to the photo-curing resin/monomer to the photo-polymerization initiator is 10:3-7: 0.1-1;
the film layer mixture comprises (methyl) acrylate oligomer, (methyl) acrylate photocuring monomer and photopolymerization initiator, and the mass ratio of the (methyl) acrylate oligomer, the (methyl) acrylate photocuring monomer and the photopolymerization initiator is 4-5: 4-5: 0.1 to 1;
the glass transition temperature of the polymer after the photo-polymerization of the image layer mixture is 20-80 ℃;
the glass transition temperature of the polymer after the photopolymerization of the film layer mixture is 20-80 ℃;
the glass transition temperature of the image layer is higher than that of the film layer.
Further, the decorative film further comprises a transfer layer, wherein the transfer layer comprises a curable ink decorative image layer arranged on the substrate and a film layer arranged on the image layer.
Further, the photocurable resin/monomer includes an oil-soluble compound having at least two or more (meth) acryloyl groups.
More preferably, the oil-soluble compound of the (meth) acryloyl group includes any one or a combination of two or more of trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethoxylated bisphenol a di (meth) acrylate, and propane trimethacrylate tri (meth) acrylate, but is not limited thereto.
Preferably, the photopolymerization initiator includes any one or a combination of two or more of isopropyl thioxanthone, isooctyl p-dimethylaminobenzoate, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, methyl benzoylformate, benzoin bismethyl ether, benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, methyl benzoylbenzoate, 2-tert-butylanthraquinone, 1-chloroanthraquinone, and 2, 4-dimethylthioxanthone, but is not limited thereto.
Further, the base paper comprises any one or a combination of two of water-soluble base paper and/or water-swelling paste base paper.
Preferably, the (meth) acrylate oligomer includes any one or a combination of two or more of a polyester (meth) acrylate oligomer, a bisphenol a type epoxy resin (meth) acrylate oligomer, a caprolactone-and (meth) acrylate copolymer, a novolac type epoxy resin (meth) acrylate oligomer, and a cresol novolac type epoxy resin (meth) acrylate oligomer, but is not limited thereto.
More preferably, the (meth) acrylate-based photocurable monomer includes monofunctional monomers of 2-ethylhexyl acrylate, 2-isodecyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2 (2-ethoxyethoxy) ethyl (meth) acrylate, 2-phenoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, hydrogen furfuryl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, diphenoxyethyl acrylate, diphenylethoxyethyl acrylate, and mixtures thereof, Any one or a combination of two or more of ethylene glycol dicyclopentenyl ether methacrylic acid, but not limited thereto.
Preferably, the (meth) acrylate-based photocurable monomer further includes any one or a combination of two or more of multifunctional monomers, such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethoxylated bisphenol a di (meth) acrylate, and propane trimethanol tri (meth) acrylate, but is not limited thereto.
Further, the image layer mixture further includes an additive.
Further, the additive includes any one or a combination of two of a defoaming agent and a thixotropic agent, but is not limited thereto.
Further, the defoaming agent includes a silicon-based defoaming agent, but is not limited thereto.
Further, the thixotropic agent includes, but is not limited to, a hydrogenated castor oil type thixotropic agent.
Further, the film layer mixture also comprises an additive.
Further, the additive includes any one or a combination of two of a defoaming agent and a thixotropic agent, but is not limited thereto.
Further, the defoaming agent includes a silicon-based defoaming agent, but is not limited thereto.
Further, the thixotropic agent includes, but is not limited to, a hydrogenated castor oil type thixotropic agent.
The embodiment of the invention also provides a method for transferring the decorative film by ultraviolet light curing type high-temperature water, which comprises the following steps:
(1) uniformly mixing the image layer mixture ceramic pigment, the photocuring resin/monomer, the photopolymerization initiator, the defoaming agent and the thixotropic agent at normal temperature, and grinding the mixture to the fineness of less than 15 microns by using a three-roll machine to obtain image layer ink;
(2) screen printing the image layer ink prepared in the step (1) on base paper containing water-soluble or water-swelling paste by using 200-350-mesh polyester, and then carrying out curing treatment;
(3) uniformly mixing the film layer mixture (methyl) acrylate oligomer, the (methyl) acrylate photocuring monomer, the photopolymerization initiator, the defoaming agent and the thixotropic agent at normal temperature, and then performing curing treatment by screen printing on the base paper treated in the step (2) through a 60-80-mesh polyester screen;
further, the mass ratio of the ceramic pigment, the photo-curing resin/monomer and the photo-polymerization initiator is 10:3-7: 0.1-1.
Further, the mass ratio of the (meth) acrylate oligomer, the (meth) acrylate photocurable monomer and the photopolymerization initiator is 4-5: 4-5: 0.1-1.
More preferably, the oil-soluble compound of the (meth) acryloyl group includes any one or a combination of two or more of trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethoxylated bisphenol a di (meth) acrylate, and propane trimethacrylate tri (meth) acrylate, but is not limited thereto.
Preferably, the photopolymerization initiator includes any one or a combination of two or more of isopropyl thioxanthone, isooctyl p-dimethylaminobenzoate, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, methyl benzoylformate, benzoin bismethyl ether, benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, methyl benzoylbenzoate, 2-tert-butylanthraquinone, 1-chloroanthraquinone, and 2, 4-dimethylthioxanthone, but is not limited thereto.
Preferably, the (meth) acrylate oligomer includes any one or a combination of two or more of a polyester (meth) acrylate oligomer, a bisphenol a type epoxy resin (meth) acrylate oligomer, a caprolactone-and (meth) acrylate copolymer, a novolac type epoxy resin (meth) acrylate oligomer, and a cresol novolac type epoxy resin (meth) acrylate oligomer, but is not limited thereto.
More preferably, the (meth) acrylate-based photocurable monomer includes monofunctional monomers of 2-ethylhexyl acrylate, 2-isodecyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2 (2-ethoxyethoxy) ethyl (meth) acrylate, 2-phenoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, hydrogen furfuryl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, diphenoxyethyl acrylate, diphenylethoxyethyl acrylate, and mixtures thereof, Any one or a combination of two or more of ethylene glycol dicyclopentenyl ether methacrylic acid, but not limited thereto.
Preferably, the (meth) acrylate-based photocurable monomer further includes any one or a combination of two or more of multifunctional monomers, such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethoxylated bisphenol a di (meth) acrylate, and propane trimethanol tri (meth) acrylate, but is not limited thereto.
Further, the defoaming agent includes a silicon-based defoaming agent, but is not limited thereto.
Further, the thixotropic agent includes, but is not limited to, a hydrogenated castor oil type thixotropic agent.
Compared with the prior art, the invention has the advantages that: the preparation method of the ultraviolet-curing high-temperature water transfer printing decorative film provided by the invention adopts ultraviolet curing treatment, has no solvent volatilization, does not cause adverse effects on environment and personnel health, and is an environment-friendly product. Meanwhile, the ultraviolet curing treatment is adopted to replace the traditional heat drying treatment, so that the energy consumption in the using process is reduced. The ultraviolet-curing high-temperature water transfer-printed decorative film provided by the invention has good flexibility, the reduction degree of a printed pattern is high, the color of a fired device is bright, and the ultraviolet-curing high-temperature water transfer-printed decorative film can be applied to the surfaces of curved surface materials such as ceramics, glass, enamel and the like.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
The embodiment of the invention provides an ultraviolet curing high-temperature water transfer printing decorative film, which comprises base paper, an image layer printed on the base paper and a film layer supporting transfer of the image layer;
wherein the image layer is provided with a curable resin layer which can be cured by ultraviolet irradiation, and the film layer is provided with a curable resin layer which can be cured by ultraviolet irradiation;
the thickness of the image layer is 10-100 μm, and the thickness of the film layer is 10-50 μm;
the image layer mixture comprises a ceramic pigment, a photo-curing resin/monomer and a photo-polymerization initiator, wherein the mass ratio of the ceramic pigment to the photo-curing resin/monomer to the photo-polymerization initiator is 10:3-7: 0.1-1;
the film layer mixture comprises (methyl) acrylate oligomer, (methyl) acrylate photocuring monomer and photopolymerization initiator, and the mass ratio of the (methyl) acrylate oligomer, the (methyl) acrylate photocuring monomer and the photopolymerization initiator is 4-5: 4-5: 0.1 to 1;
the glass transition temperature of the polymer after the photo-polymerization of the image layer mixture is 20-80 ℃;
the glass transition temperature of the polymer after the photopolymerization of the film layer mixture is 20-80 ℃;
the glass transition temperature of the image layer is higher than that of the film layer.
Further, the decorative film further comprises a transfer layer, wherein the transfer layer comprises a curable ink decorative image layer arranged on the substrate and a film layer arranged on the image layer.
Further, the photocurable resin/monomer includes an oil-soluble compound having at least two or more (meth) acryloyl groups.
More preferably, the oil-soluble compound of the (meth) acryloyl group includes any one or a combination of two or more of trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethoxylated bisphenol a di (meth) acrylate, and propane trimethacrylate tri (meth) acrylate, but is not limited thereto.
Preferably, the photopolymerization initiator includes any one or a combination of two or more of isopropyl thioxanthone, isooctyl p-dimethylaminobenzoate, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, methyl benzoylformate, benzoin bismethyl ether, benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, methyl benzoylbenzoate, 2-tert-butylanthraquinone, 1-chloroanthraquinone, and 2, 4-dimethylthioxanthone, but is not limited thereto.
Further, the base paper comprises any one or a combination of two of water-soluble base paper and/or water-swelling paste base paper.
Preferably, the (meth) acrylate oligomer includes any one or a combination of two or more of (polyester (meth) acrylate oligomer, bisphenol a type epoxy resin (meth) acrylate oligomer, caprolactone-and (meth) acrylate copolymer, novolac type epoxy resin (meth) acrylate oligomer, and cresol novolac type epoxy resin (meth) acrylate oligomer, but is not limited thereto.
More preferably, the (meth) acrylate-based photocurable monomer includes monofunctional monomers of 2-ethylhexyl acrylate, 2-isodecyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2 (2-ethoxyethoxy) ethyl (meth) acrylate, 2-phenoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, hydrogen furfuryl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, diphenoxyethyl acrylate, diphenylethoxyethyl acrylate, and mixtures thereof, Any one or a combination of two or more of ethylene glycol dicyclopentenyl ether methacrylic acid, but not limited thereto.
Preferably, the (meth) acrylate-based photocurable monomer further includes any one or a combination of two or more of multifunctional monomers, such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethoxylated bisphenol a di (meth) acrylate, and propane trimethanol tri (meth) acrylate, but is not limited thereto.
Further, the image layer mixture further includes an additive.
Further, the additive includes any one or a combination of two of a defoaming agent and a thixotropic agent, but is not limited thereto.
Further, the defoaming agent includes a silicon-based defoaming agent, but is not limited thereto.
Further, the thixotropic agent includes, but is not limited to, a hydrogenated castor oil type thixotropic agent.
Further, the film layer mixture also comprises an additive.
Further, the additive includes any one or a combination of two of a defoaming agent and a thixotropic agent, but is not limited thereto.
Further, the defoaming agent includes a silicon-based defoaming agent, but is not limited thereto.
Further, the thixotropic agent includes, but is not limited to, a hydrogenated castor oil type thixotropic agent.
The embodiment of the invention also provides a method for transferring the decorative film by ultraviolet light curing type high-temperature water, which comprises the following steps:
(1) uniformly mixing the image layer mixture ceramic pigment, the photocuring resin/monomer, the photopolymerization initiator, the defoaming agent and the thixotropic agent at normal temperature, and grinding the mixture to the fineness of less than 15 microns by using a three-roll machine to obtain image layer ink;
(2) screen printing the image layer ink prepared in the step (1) on base paper containing water-soluble or water-swelling paste by using 200-350-mesh polyester, and then carrying out curing treatment;
(3) uniformly mixing the film layer mixture (methyl) acrylate oligomer, the (methyl) acrylate photocuring monomer, the photopolymerization initiator, the defoaming agent and the thixotropic agent at normal temperature, and then performing curing treatment by screen printing on the base paper treated in the step (2) through a 60-80-mesh polyester screen;
further, the mass ratio of the ceramic pigment, the photo-curing resin/monomer and the photo-polymerization initiator is 10:3-7: 0.1-1.
Further, the mass ratio of the (meth) acrylate oligomer, the (meth) acrylate photocurable monomer and the photopolymerization initiator is 4-5: 4-5: 0.1-1.
More preferably, the oil-soluble compound of the (meth) acryloyl group includes any one or a combination of two or more of trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethoxylated bisphenol a di (meth) acrylate, and propane trimethacrylate tri (meth) acrylate, but is not limited thereto.
Preferably, the photopolymerization initiator includes any one or a combination of two or more of isopropyl thioxanthone, isooctyl p-dimethylaminobenzoate, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, methyl benzoylformate, benzoin bismethyl ether, benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, methyl benzoylbenzoate, 2-tert-butylanthraquinone, 1-chloroanthraquinone, and 2, 4-dimethylthioxanthone, but is not limited thereto.
Preferably, the (meth) acrylate oligomer includes any one or a combination of two or more of (meth) acrylate oligomer, polyester (meth) acrylate oligomer, bisphenol a epoxy resin (meth) acrylate oligomer, caprolactone-and (meth) acrylate copolymer, novolac epoxy resin (meth) acrylate oligomer, and cresol novolac epoxy resin (meth) acrylate oligomer, but is not limited thereto.
More preferably, the (meth) acrylate-based photocurable monomer includes monofunctional monomers of 2-ethylhexyl acrylate, 2-isodecyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2 (2-ethoxyethoxy) ethyl (meth) acrylate, 2-phenoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, hydrogen furfuryl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, diphenoxyethyl acrylate, diphenylethoxyethyl acrylate, and mixtures thereof, Any one or a combination of two or more of ethylene glycol dicyclopentenyl ether methacrylic acid, but not limited thereto.
Preferably, the (meth) acrylate-based photocurable monomer further includes any one or a combination of two or more of multifunctional monomers, such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethoxylated bisphenol a di (meth) acrylate, and propane trimethanol tri (meth) acrylate, but is not limited thereto.
Further, the defoaming agent includes a silicon-based defoaming agent, but is not limited thereto.
Further, the thixotropic agent includes, but is not limited to, a hydrogenated castor oil type thixotropic agent.
Furthermore, the photocuring resin composition in the curable resin layer is used as a carrier for bonding and dispersing the ceramic pigment to form printable slurry, has a good wetting effect on inorganic pigment, and has good developing and printing adaptability after three-roll grinding.
Furthermore, the glass transition temperature Tg of the polymer after ultraviolet photopolymerization of the curable resin layer in the image layer is 20-80 ℃, and when the Tg is less than 20 ℃, the formed film is too soft and is not favorable for supporting; when the Tg is more than 80 ℃, the pattern is liable to be cracked during transfer.
Furthermore, the film layer as a transfer support body needs to have certain flexibility so as to be suitable for water transfer printing of various curved surfaces; the glass transition temperature Tg of the polymer after ultraviolet polymerization of the film layer is 20-80 ℃, when the Tg is less than 20 ℃, the pattern is easy to deform in the process of film forming and soft transfer printing, and when the Tg is more than 80 ℃, the film is too hard to be pasted.
Further, in order to maintain the integrity of the pattern during the high-temperature firing process, it is required that the resin molecular weights, the glass transition temperature Tg and the pyrolysis temperature profile of the image layer and the film layer are matched, and the glass transition temperature of the image layer is higher than that of the film layer. Wherein the polymer after UV photopolymerization has a glass transition temperature Tg of 1/Tg ═ Wa/Tga+Wb/Tgb+Wc/Tgc+ … …, wherein Tga、Tgb、Tgc… … are the glass transition temperatures of oligomers/monomers a, b, c, … …, respectively, Wa、Wb、WcThe weight percentages of the oligomers/monomers a, b, c, … … in the UV polymerized polymer.
The preparation method of the ultraviolet-curing high-temperature water transfer printing decorative film provided by the invention adopts ultraviolet curing treatment, has no solvent volatilization, cannot cause adverse effects on environment and personnel health, adopts ultraviolet curing treatment to replace the traditional hot drying treatment, reduces energy consumption in the use process, and is an environment-friendly product.
The technical solution of the present invention is further explained below with reference to several examples.
The image layer mixture was uniformly mixed and dispersed in a mixer according to the composition ratios in table 1, and then ground by a three-roll mill to a fineness of less than 15 μm, and the film layer mixture was uniformly mixed and dispersed by a mixer.
The contents of the components in example 1, example 2, comparative example 1, comparative example 2, example 3, example 4, comparative example 3 and comparative example 4 are shown in Table 1
Wherein the photocuring monomer is an A component
A-1: trimethylolpropane triacrylate, Tg 62 deg.c
A-2: 1, 4-butanediol diacrylate as a monomer,
a-3: ethoxylated bisphenol a diacrylate with a Tg of 8 deg.c
A-4: dicyclopentenyloxyethyl acrylate, Tg 35 deg.C
A-5: diphenyl oxy ethyl acrylate
The light-cured oligomer is a component B
B-1: acrylate oligomer, Mw 13000, Tg 41 ° c
B-2: polyester acrylate oligomer, Mw 10000, Tg 38 ℃
B-3: acrylate oligomer, Mw 14000, Tg 93 ° c
Thermoplastic (meth) acrylic copolymer as component C
C-1: tg of 55 ℃ and weight average molecular weight Mw of 50000
C-2: tg of 34 ℃ and weight average molecular weight Mw of 130000
The photopolymerization initiator is a component D
D-1: 2-hydroxy-2-methyl-1-phenyl-1-propanone
D-2: isooctyl p-dimethylaminobenzoate
The solvent is E component
E-1: naphtha solvent S-150
E-2: naphtha solvent S-100A
The ceramic pigment is F component
F-1: ferro327 sea blue
The defoaming agent is a component G
G-1: silicon defoaming agent
The thixotropic agent is H component
H-1: thixotropic agent of hydrogenated castor oil
(1) Uniformly mixing the image layer mixture ceramic pigment, the photocuring resin/monomer, the photopolymerization initiator, the defoaming agent and the thixotropic agent at normal temperature, and grinding the mixture to the fineness of less than 15 microns by using a three-roll machine to obtain image layer ink;
(2) printing the image layer ink prepared in the step (1) on base paper containing water-soluble or water-swelling paste through a 200-350-mesh polyester silk screen, and then carrying out curing treatment;
(3) uniformly mixing the film layer mixture (methyl) acrylate oligomer, the (methyl) acrylate photocuring monomer, the photopolymerization initiator, the defoaming agent and the thixotropic agent at normal temperature, and then performing curing treatment by screen printing on the base paper treated in the step (2) through a 60-80-mesh polyester screen;
TABLE 1
Figure BDA0002420860890000121
Figure BDA0002420860890000131
Of these, comparative examples 2 and 4 are conventional solvent-based.
The following tests were carried out on the products obtained in the examples of the invention and in the comparative examples:
1. printability
The image layer ink was printed on a base paper containing a water-soluble or water-swellable paste using a 200-350 mesh polyester screen printing plate using a semiautomatic printer, and cured using an ultraviolet curing machine (example 1, example 2, comparative example 1), and comparative example 2 was dried using a low-temperature oven. After 50 sheets of printing, the record without loss of pattern dots was ∘, and the record with loss of pattern dots was x (see table 1).
The film layer mixture was screen-printed on the dried image layer using a 60-80 mesh polyester screen using a semi-automatic printer, and cured using an ultraviolet curing machine (examples 3, 4, and 3), and comparative example 4 was dried using a low-temperature oven. After 50 sheets of printing, the recording of no bleed and stringiness was ∘, and the recording of bleed and stringiness was gamma (see table 1).
2. Water transfer adaptability
After the printed high-temperature water transfer decoration film was left at room temperature for 24 hours, the decoration film was immersed in warm water and then transferred onto curved ceramics, and the transfer film layer was recorded as x without breaking and the film layer was recorded as x with breaking (see table 1).
3. Volatile content of solvent
The content of the volatile components in the solvent is tested by adopting a drying differential method, 2g of samples are respectively taken and put in an aluminum foil, the drying is carried out for 2 hours at the temperature of 105 +/-1 ℃, and then the weight loss is calculated, namely the content of the volatile components in the solvent (shown in table 1).
4. Firing compatibility
Transferring the high-temperature water transfer decoration film to a white ceramic plate, naturally drying for 24h, putting into a kiln, firing at 780 ℃ for 1h, and observing patterns on the ceramic plate. The pattern was complete, the bright color was recorded as O, the pattern was scratched was recorded as gamma, and the untested combination was recorded as- (see Table 2).
TABLE 2
Figure BDA0002420860890000141
Figure BDA0002420860890000151
The detection results in tables 1 and 2 show that the ultraviolet-curing high-temperature water transfer decorative film provided by the invention can reduce the problems of solvent volatilization and the like caused by the prior solvent-based products while maintaining printability, water transfer property and firing matching property, and can reduce pollution and energy consumption, the printed pattern has high reduction degree, and the fired device has bright color.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (19)

1. An ultraviolet curing type high-temperature water transfer printing decorative film is characterized by comprising base paper, an image layer printed on the base paper and a film layer supporting transfer of the image layer;
wherein the image layer is provided with a curable resin layer which can be cured by ultraviolet irradiation, and the film layer is provided with a curable resin layer which can be cured by ultraviolet irradiation;
the thickness of the image layer is 10-100 μm, and the thickness of the film layer is 10-50 μm;
the image layer mixture comprises a ceramic pigment, a photo-curing resin/monomer and a photo-polymerization initiator, wherein the mass ratio of the ceramic pigment to the photo-curing resin/monomer to the photo-polymerization initiator is 10:3-7: 0.1-1;
the film layer mixture comprises (methyl) acrylate oligomer, (methyl) acrylate photocuring monomer and photopolymerization initiator, and the mass ratio of the (methyl) acrylate oligomer, the (methyl) acrylate photocuring monomer and the photopolymerization initiator is 4-5: 4-5: 0.1 to 1;
the glass transition temperature of the polymer after the photo-polymerization of the image layer mixture is 20-80 ℃;
the glass transition temperature of the polymer after the photopolymerization of the film layer mixture is 20-80 ℃;
the glass transition temperature of the image layer is higher than that of the film layer.
2. The ultraviolet-curable high-temperature water transfer decorative film according to claim 1, wherein: the decorative film further includes a transfer layer including a curable ink decorative image layer disposed on the substrate and a film layer disposed on the image layer.
3. The ultraviolet-curable high-temperature water transfer decorative film according to claim 1, wherein: an oil-soluble compound comprising at least two or more (meth) acryloyl groups in the photocurable resin/monomer.
4. The ultraviolet-curable high-temperature water transfer decorative film according to claim 3, wherein: the oil-soluble compound of the (meth) acryloyl group includes any one or a combination of two or more of trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethoxylated bisphenol a di (meth) acrylate, and propane trimethanol tri (meth) acrylate.
5. The ultraviolet-curable high-temperature water transfer decorative film according to claim 1, wherein: the photopolymerization initiator comprises any one or the combination of more than two of isopropyl thioxanthone, isooctyl p-dimethylaminobenzoate, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, methyl benzoylformate, benzoin dimethyl ether, benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, methyl benzoylbenzoate, 2-tert-butylanthraquinone, 1-chloroanthraquinone and 2, 4-dimethylthioxanthone.
6. The ultraviolet-curable high-temperature water transfer decorative film according to claim 1, wherein: the base paper comprises any one or the combination of two of water-soluble base paper and water swelling paste base paper.
7. The ultraviolet-curable high-temperature water transfer decorative film according to claim 1, wherein: the (meth) acrylate oligomer includes any one or a combination of two or more of a polyester (meth) acrylate oligomer, a bisphenol A type epoxy resin (meth) acrylate oligomer, a caprolactone-and (meth) acrylate copolymer, a novolac type epoxy resin (meth) acrylate oligomer, and a cresol novolac epoxy resin (meth) acrylate oligomer.
8. The ultraviolet-curable high-temperature water transfer decorative film according to claim 1, wherein: the (methyl) acrylate photocuring monomer comprises a monofunctional group monomer, wherein the monofunctional group monomer comprises 2-ethylhexyl acrylate, 2-isodecyl (methyl) acrylate, hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 2-hydroxybutyl (methyl) acrylate, 2-ethoxyethyl (methyl) acrylate, 2 (2-ethoxyethoxy) ethyl- (methyl) acrylate, 2-phenoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, hydrogen furfuryl (methyl) acrylate, dicyclopentenyloxyethyl (methyl) acrylate, diphenoxyethyl acrylate, diphenylethoxy ethyl acrylate, N-, Any one or a combination of two or more of ethylene glycol dicyclopentenyl ether methacrylic acid.
9. The ultraviolet-curable high-temperature water transfer decorative film according to claim 1, wherein: the (meth) acrylate-based photocurable monomer further comprises a multifunctional monomer, wherein the multifunctional monomer comprises any one or a combination of more than two of trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethoxylated bisphenol A di (meth) acrylate and trimethylolpropane trimethacrylate.
10. The ultraviolet-curable high-temperature water transfer decorative film according to claim 1, wherein: the image layer mixture further comprises an additive, wherein the additive comprises any one or combination of two of an antifoaming agent and a thixotropic agent, the antifoaming agent comprises a silicon-based antifoaming agent, and the thixotropic agent comprises a hydrogenated castor oil thixotropic agent.
11. The ultraviolet-curable high-temperature water transfer decorative film according to claim 1, wherein: the film layer mixture also comprises an additive, wherein the additive comprises any one or combination of two of an antifoaming agent and a thixotropic agent, the antifoaming agent comprises a silicon antifoaming agent, and the thixotropic agent comprises a hydrogenated castor oil thixotropic agent.
12. A method for preparing the ultraviolet-curable high-temperature water transfer decorative film of any one of claims 1 to 11, comprising the steps of:
(1) uniformly mixing the image layer mixture ceramic pigment, the photocuring resin/monomer, the photopolymerization initiator, the defoaming agent and the thixotropic agent at normal temperature, and grinding the mixture to the fineness of less than 15 microns by using a three-roll machine to obtain image layer ink;
(2) printing the image layer ink prepared in the step (1) on base paper containing water-soluble or water-swelling paste through a 200-350-mesh polyester silk screen, and then carrying out curing treatment;
(3) and (3) uniformly mixing the film layer mixture (methyl) acrylate oligomer, the (methyl) acrylate photocuring monomer, the photopolymerization initiator, the defoaming agent and the thixotropic agent at normal temperature, and then performing screen printing on the base paper treated in the step (2) through a 60-80-mesh polyester screen to perform curing treatment.
13. The method for preparing the ultraviolet-curable high-temperature water transfer decorative film according to claim 12, wherein the method comprises the following steps: the mass ratio of the ceramic pigment to the photo-curing resin/monomer to the photo-polymerization initiator is 10:3-7: 0.1-1.
14. The method for preparing the ultraviolet-curable high-temperature water transfer decorative film according to claim 12, wherein the method comprises the following steps: the mass ratio of the (methyl) acrylate oligomer, the (methyl) acrylate photocuring monomer and the photopolymerization initiator is 4-5: 4-5: 0.1-1.
15. The method for preparing the ultraviolet-curable high-temperature water transfer decorative film according to claim 12, wherein the method comprises the following steps: the oil-soluble compound of the (meth) acryloyl group includes any one or a combination of two or more of trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethoxylated bisphenol a di (meth) acrylate, and propane trimethanol tri (meth) acrylate.
16. The method for preparing the ultraviolet-curable high-temperature water transfer decorative film according to claim 12, wherein the method comprises the following steps: the photopolymerization initiator comprises any one or the combination of more than two of isopropyl thioxanthone, isooctyl p-dimethylaminobenzoate, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, methyl benzoylformate, benzoin dimethyl ether, benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, methyl benzoylbenzoate, 2-tert-butylanthraquinone, 1-chloroanthraquinone and 2, 4-dimethylthioxanthone.
17. The method for preparing the ultraviolet-curable high-temperature water transfer decorative film according to claim 12, wherein the method comprises the following steps: the (meth) acrylate oligomer includes any one or a combination of two or more of a polyester (meth) acrylate oligomer, a bisphenol A type epoxy resin (meth) acrylate oligomer, a caprolactone-and (meth) acrylate copolymer, a novolac type epoxy resin (meth) acrylate oligomer, and a cresol novolac epoxy resin (meth) acrylate oligomer.
18. The method for preparing the ultraviolet-curable high-temperature water transfer decorative film according to claim 12, wherein the method comprises the following steps: the (methyl) acrylate photocuring monomer comprises a monofunctional group monomer, wherein the monofunctional group monomer comprises 2-ethylhexyl acrylate, 2-isodecyl (methyl) acrylate, hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 2-hydroxybutyl (methyl) acrylate, 2-ethoxyethyl (methyl) acrylate, 2 (2-ethoxyethoxy) ethyl- (methyl) acrylate, 2-phenoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, hydrogen furfuryl (methyl) acrylate, dicyclopentenyloxyethyl (methyl) acrylate, diphenoxyethyl acrylate, diphenylethoxy ethyl acrylate, N-, Any one or the combination of more than two of ethylene glycol dicyclopentenyl ether methacrylic acid; the (meth) acrylate-based photocurable monomer further comprises a multifunctional group, wherein the multifunctional group comprises any one or a combination of more than two of monomers of trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethoxylated bisphenol A di (meth) acrylate and propane trimethanol tri (meth) acrylate.
19. The method for preparing the ultraviolet-curable high-temperature water transfer decorative film according to claim 12, wherein the method comprises the following steps: the defoaming agent comprises a silicon defoaming agent, and the thixotropic agent comprises a hydrogenated castor oil thixotropic agent.
CN202010205328.2A 2020-03-23 2020-03-23 Ultraviolet-curing high-temperature water transfer-printing decorative film and manufacturing method thereof Pending CN111923647A (en)

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