CN108819530B - High-performance white pigment foil - Google Patents

High-performance white pigment foil Download PDF

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CN108819530B
CN108819530B CN201810669920.0A CN201810669920A CN108819530B CN 108819530 B CN108819530 B CN 108819530B CN 201810669920 A CN201810669920 A CN 201810669920A CN 108819530 B CN108819530 B CN 108819530B
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white pigment
performance white
pigment foil
raw materials
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CN108819530A (en
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邵冬生
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Anhui Morning Language Science And Technology Materials Co ltd
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Tongxiang Citynaiboer Hot Stamping Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/32—Modified amine-aldehyde condensates
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

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Abstract

The invention relates to the field of pigment foils, in particular to a high-performance white pigment foil. The high-performance white pigment foil at least comprises a coloring layer; the preparation raw material of the coloring layer at least comprises acrylic resin; the raw materials for preparing the acrylic resin at least comprise methyl methacrylate, methacrylic acid and hydroxyethyl methacrylate phosphate. In the preparation raw materials of the acrylic resin, the molar ratio of methyl methacrylate, methacrylic acid and hydroxyethyl methacrylate phosphate is as follows: (5-8): (2-3): (0.1-2).

Description

High-performance white pigment foil
Technical Field
The invention relates to the field of pigment foils, in particular to a high-performance white pigment foil.
Background
Transfer printing is a special printing technology, and is generally a process of transferring a color pattern onto the surface of other materials by using an adhesive through hot pressing, so as to complete the transfer printing from a colored coating or color pattern on a transfer printing film onto the surface of other materials.
Transfer films of this type are generally: 1. heat transfer film (alumite, bronzing film): can be subdivided into an alumite hot stamping foil with an aluminum coating and a pigment foil without the aluminum coating; 2. transferring a printing film: printing and coating a color pattern on a film or paper substrate, and transferring the color pattern to the surface of other materials by an adhesive; 3. thermal transfer ribbon (digital printing film): and thermally printing the color layer on the film to the surface of other base materials by a thermal transfer printer to form character patterns.
The currently commonly used thermal transfer film has the following structure:
the first layer is a base film layer. The base film is generally a polyester film with a thickness of 12 to 16 μm. Mainly plays a role of supporting the coating. The packaging form is a reel type, and is convenient for continuous processing, storage and transportation.
The second layer is a release layer. The paint of the release layer is organic silicon resin or wax liquid, and the function of the paint is to enable the color adhesive layer to be quickly separated from the base film and adhered to an object to be hot stamped during hot stamping. The release layer has good release effect, otherwise the quality problems of hot stamping color, floating, non-uniform and the like can be caused.
The third layer is a color adhesive layer. The color adhesive layer is prepared by using pigment as main body and adding adhesive, alcohol solvent, other stuffing, etc. in certain proportion. The various colours of the coloured foil depend mainly on the application and formulation of this layer.
For white pigment foil, white titanium dioxide is more commonly used, however, when the addition amount of titanium dioxide is larger, the coloring layer obtained by the formula and the preparation process in the prior art often has the phenomenon of powder falling, and on the other hand, the formula and the process used in the prior art are slower in curing, so that the reaction time is prolonged, and the working efficiency is reduced.
Disclosure of Invention
In order to solve the above technical problems, a first aspect of the present invention provides a high-performance white pigment foil including at least a colored layer;
the preparation raw material of the coloring layer at least comprises acrylic resin;
the raw materials for preparing the acrylic resin at least comprise methyl methacrylate, methacrylic acid and hydroxyethyl methacrylate phosphate.
In a preferred embodiment of the present invention, in the raw materials for preparing the acrylic resin, the molar ratio of methyl methacrylate, methacrylic acid, and hydroxyethyl methacrylate phosphate is: (5-10): (0-5): (0.1-2).
As a preferred technical scheme of the invention, the preparation raw materials of the coloring layer at least comprise, by mass percent:
Figure BDA0001707845420000021
as a preferred embodiment of the present invention, the plasticizer is selected from: dibutyl phthalate, dioctyl phthalate, acetyl tri-N-butyl citrate, acetyl triethyl citrate, N-ethyl o-p-toluenesulfonamide, 2-butoxyethyl stearate, N-butyl stearate, 1, 2-propylene glycol monolaurate, glycerol monolaurate, diethylene glycol monolaurate, butoxyethyl laurate, polyethylene glycol dilaurate, triethyl citrate, tri-N-butyl citrate, triethyl acetyl citrate, tri-N-butyl acetyl citrate, trihexyl acetyl citrate, epoxy acetyl methyl ricinoleate, epoxy triglyceride, and epoxy isooctyl stearate.
As a preferred embodiment of the present invention, the whitening agent is selected from: any one or a mixture of a plurality of bis-tert-butylbutylbenzothiophene, 4' -bis- (2-sulfostyryl) -biphenyl salt, 4' -bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) naphthalene thiazole derivative, 4' -bis (triazol-2-yl) stilbene derivative and bis- (triazinylaminostilbene) disulfonic acid derivative.
As a preferred embodiment of the present invention, the solvent is selected from: ethyl acetate, butyl acetate, benzene, toluene, xylene, acetone, butanone, cyclohexanone, ethanol, butanol, methyl ether, ethyl ether, butyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol, glycerol, propylene glycol methyl ether, propylene glycol ethyl ether, sulfuric acid, hydrochloric acid, formic acid, and acetic acid.
In a preferred embodiment of the present invention, the high-performance white pigment foil further includes a release layer adjacent to the colored layer.
As a preferred technical scheme of the present invention, the raw materials for preparing the release layer, calculated by mass percentage, at least comprise:
2-10% of an oxide;
0-10% of an amino compound;
the balance of organic solvent;
the mass percentage of the raw materials is 100 percent.
As a preferred technical solution of the present invention, the high-performance white pigment foil further comprises a base film layer;
the high-performance white pigment foil sequentially comprises a base film layer, a release layer and a coloring layer; or the high-performance white pigment foil sequentially comprises a base film layer and a coloring layer.
Another aspect of the present invention provides a process for preparing a high performance white pigment foil, comprising at least the steps of:
firstly, uniformly coating a release layer on a base film layer, and drying; and then uniformly coating the coloring layer on the release layer, and drying to obtain a finished product.
Has the advantages that:
1. the titanium dioxide of the dyed layer in the high performance white pigment paper tinsel in this application can not appear any phenomenon of falling powder, even through rub and the water logging after, still can not appear the phenomenon of falling powder, therefore, provides the beneficial effect of this application.
2. After hydroxyethyl methacrylate phosphate is added, the curing time is shortened, and the working efficiency is improved.
The above-described and other features, aspects, and advantages of the present application will become more apparent with reference to the following detailed description.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a high performance white pigment foil of example 1.
Wherein, 1-a coloring layer; 2-a release layer; 3-base film layer.
Detailed Description
For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
Moreover, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, i.e., having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
In order to solve the above technical problems, a first aspect of the present invention provides a high-performance white pigment foil including at least a colored layer;
the preparation raw material of the coloring layer at least comprises acrylic resin;
the raw materials for preparing the acrylic resin at least comprise methyl methacrylate, methacrylic acid and hydroxyethyl methacrylate phosphate.
In one embodiment, in the raw materials for preparing the acrylic resin, the molar ratio of methyl methacrylate, methacrylic acid and hydroxyethyl methacrylate phosphate is: (5-10): (0-5): (0.1-2); preferably, the molar ratio of methyl methacrylate, methacrylic acid and hydroxyethyl methacrylate phosphate is: (6-7): (2-3): (0.5 to 1.5); most preferably, the molar ratio of methyl methacrylate, methacrylic acid and hydroxyethyl methacrylate phosphate is: 6: 3: 1.
the applicant has surprisingly found that by uniquely setting the molar ratio of methyl methacrylate to methacrylic acid, a coloured layer with a better fixing effect on titanium dioxide can be obtained. When the addition amount of the titanium dioxide is large, the phenomenon of powder falling of the titanium dioxide is easy to occur, and the performance of the product is greatly influenced. For another aspect of the present application, hydroxyethyl methacrylate phosphate is added to the acrylic resin, and the inventors of the present application have surprisingly found that the addition of hydroxyethyl methacrylate phosphate can further enhance the fixing effect on titanium dioxide, further increase the usage amount of titanium dioxide, and still prevent the occurrence of the dusting phenomenon; meanwhile, the addition of the hydroxyethyl methacrylate phosphate can shorten the curing time of the cured layer and improve the efficiency.
In a preferred embodiment, the method for preparing the acrylic resin at least comprises the following steps:
adding methyl methacrylate, methacrylic acid, hydroxyethyl methacrylate phosphate and azobisisobutyronitrile into a 500mL reaction bottle containing a toluene solvent according to a certain proportion, reacting for 3-6 h at 50-80 ℃ under the protection of nitrogen to obtain a product, dissolving the obtained product in acetone, precipitating and washing in water, and then carrying out vacuum drying to obtain the acrylic resin.
Coloured layer
In the present application, the colored layer is not particularly limited,
in one embodiment, the raw materials for preparing the colored layer at least comprise, by mass:
Figure BDA0001707845420000051
more preferably, the preparation raw materials of the colored layer at least comprise the following components in parts by weight:
Figure BDA0001707845420000052
most preferably, the preparation raw materials of the colored layer at least comprise the following components in parts by weight:
Figure BDA0001707845420000053
the mass of the solvent is 2 times of that of the acrylic resin.
Preferably, the plasticizer is selected from: dibutyl phthalate, dioctyl phthalate, acetyl tri-N-butyl citrate, acetyl triethyl citrate, N-ethyl o-p-toluenesulfonamide, 2-butoxyethyl stearate, N-butyl stearate, 1, 2-propylene glycol monolaurate, glycerol monolaurate, diethylene glycol monolaurate, butoxyethyl laurate, polyethylene glycol dilaurate, triethyl citrate, tri-N-butyl citrate, triethyl acetyl citrate, tri-N-butyl acetyl citrate, trihexyl acetyl citrate, epoxy acetyl methyl ricinoleate, epoxy triglyceride, and epoxy isooctyl stearate.
Preferably, the whitening agent is selected from: any one or a mixture of a plurality of bis-tert-butylbutylbenzothiophene, 4' -bis- (2-sulfostyryl) -biphenyl salt, 4' -bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) naphthalene thiazole derivative, 4' -bis (triazol-2-yl) stilbene derivative and bis- (triazinylaminostilbene) disulfonic acid derivative.
Preferably, the solvent is selected from: ethyl acetate, butyl acetate, benzene, toluene, xylene, acetone, butanone, cyclohexanone, ethanol, butanol, methyl ether, ethyl ether, butyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol, glycerol, propylene glycol methyl ether, propylene glycol ethyl ether, sulfuric acid, hydrochloric acid, formic acid, and acetic acid.
In the present application, the preparation method of the colored layer is:
mixing acrylic resin, titanium dioxide, a plasticizer and a whitening agent, dissolving in an organic solvent, and uniformly dispersing to obtain the use raw material of the coloring layer.
In a preferred embodiment, the high performance white pigment foil further comprises a release layer adjacent to the colored layer.
The preparation raw materials of the separation layer at least comprise the following components in percentage by mass:
Figure BDA0001707845420000061
preferably, the raw materials for preparing the release layer at least comprise the following components in percentage by mass:
Figure BDA0001707845420000062
most preferably, the raw materials for preparing the release layer at least comprise the following components in percentage by mass:
6% of oxide;
5% of an amino compound;
and 89% of organic solvent.
Preferably, the oxides may be enumerated by: titanium dioxide, aluminum oxide, silicon dioxide, calcium oxide, magnesium oxide, zinc oxide, ferrous oxide and the like.
Preferably, the amino compounds may be exemplified by: methylated melamine resin, alkylated melamine resin, high imino melamine resin, butylated melamine resin, phenylated melamine resin, HUMM-hexamethoxy melamine resin, melamine, aniline, ethyl aniline, o-toluidine, etc.
Preferably, the organic solvent may be exemplified by: ethyl acetate, butyl acetate, benzene, toluene, xylene, acetone, butanone, cyclohexanone, ethanol, butanol, methyl ether, ethyl ether, butyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol, glycerol, propylene glycol methyl ether, propylene glycol ethyl ether, sulfuric acid, hydrochloric acid, formic acid, acetic acid, and the like.
In the present application, the preparation method of the release layer is:
and mixing and dissolving the oxide and the amino compound in an organic solvent, and uniformly dispersing to obtain a raw material for the separation layer.
In a preferred embodiment, the high performance white pigment foil further comprises a base film layer; the base membrane layer is adjacent to the release layer.
In another preferred embodiment, the high performance white pigment foil further comprises a base film layer; the base film layer is directly adjacent to the color layer. Here, the term "colored layer" refers to a single colored layer as well as a mixture of a colored layer and a release layer, both interpretations.
In the present application, the base film layer used is a PET film layer.
Another aspect of the present invention provides a process for preparing a high performance white pigment foil, comprising at least the steps of:
firstly, uniformly coating a release layer on a base film layer, and drying; and then uniformly coating the coloring layer on the release layer, and drying to obtain a finished product.
In addition, all starting materials are commercially available and are available from the website of Allibaba, unless otherwise stated.
Example 1:
embodiment 1 of the present invention provides a high performance white pigment foil, which comprises a base film layer, a release layer, and a coloring layer in this order;
the base film layer is a PET film layer;
the preparation raw materials of the separation layer at least comprise the following components in percentage by mass:
6% of oxide;
5% of an amino compound;
and 89% of organic solvent.
The preparation method of the release layer comprises the following steps:
mixing and dissolving oxide (silicon dioxide) and amino compound (butylated melamine resin) in an organic solvent (propylene glycol methyl ether), and uniformly dispersing to obtain a raw material for a release layer.
The preparation raw materials of the coloring layer at least comprise the following components in percentage by mass:
5% of acrylic resin;
95% of titanium dioxide;
the mass percentage of the raw materials is 100 percent;
the mass of the solvent is 5 times of that of the acrylic resin;
the raw materials for preparing the acrylic resin comprise methyl methacrylate, methacrylic acid and hydroxyethyl methacrylate phosphate;
the preparation method of the acrylic resin at least comprises the following steps:
adding methyl methacrylate, methacrylic acid, hydroxyethyl methacrylate phosphate and azobisisobutyronitrile into a 500mL reaction bottle containing a toluene solvent according to a certain proportion, reacting for 5h at 70 ℃ under the protection of nitrogen to obtain a product, dissolving the obtained product in acetone, precipitating and washing in water, and then carrying out vacuum drying to obtain the acrylic resin. Wherein the molar ratio of methyl methacrylate, methacrylic acid, hydroxyethyl methacrylate phosphate and azobisisobutyronitrile is 5: 2: 0.1: 0.1.
the preparation method of the coloring layer comprises the following steps:
mixing and dissolving acrylic resin and titanium dioxide in an organic solvent, and uniformly dispersing to obtain the use raw material of the coloring layer.
The preparation process of the high-performance white pigment foil at least comprises the following steps:
firstly, uniformly coating a release layer on a base film layer, and drying; and then uniformly coating the coloring layer on the release layer, and drying to obtain a finished product.
Example 2:
embodiment 2 of the present invention provides a high performance white pigment foil, which comprises a base film layer, a release layer, and a coloring layer in this order;
the base film layer is a PET film layer;
the preparation raw materials of the separation layer at least comprise the following components in percentage by mass:
6% of oxide;
5% of an amino compound;
and 89% of organic solvent.
The preparation method of the release layer comprises the following steps:
mixing and dissolving oxide (silicon dioxide) and amino compound (butylated melamine resin) in an organic solvent (propylene glycol methyl ether), and uniformly dispersing to obtain a raw material for a release layer.
The preparation raw materials of the coloring layer at least comprise the following components in percentage by mass:
Figure BDA0001707845420000091
the mass of the solvent is 5 times of that of the acrylic resin.
The raw materials for preparing the acrylic resin comprise methyl methacrylate, methacrylic acid and hydroxyethyl methacrylate phosphate;
the preparation method of the acrylic resin at least comprises the following steps:
adding methyl methacrylate, methacrylic acid, hydroxyethyl methacrylate phosphate and azobisisobutyronitrile into a 500mL reaction bottle containing a toluene solvent according to a certain proportion, reacting for 5h at 70 ℃ under the protection of nitrogen to obtain a product, dissolving the obtained product in acetone, precipitating and washing in water, and then carrying out vacuum drying to obtain the acrylic resin. Wherein the molar ratio of methyl methacrylate, methacrylic acid, hydroxyethyl methacrylate phosphate and azobisisobutyronitrile is 5: 2: 0.1: 0.1.
the plasticizer is dibutyl phthalate;
the whitening agent is di-tert-butyl benzothiophene;
the preparation method of the coloring layer comprises the following steps:
mixing acrylic resin, titanium dioxide, a plasticizer and a whitening agent, dissolving in an organic solvent, and uniformly dispersing to obtain the use raw material of the coloring layer.
The preparation process of the high-performance white pigment foil at least comprises the following steps:
firstly, uniformly coating a release layer on a base film layer, and drying; and then uniformly coating the coloring layer on the release layer, and drying to obtain a finished product.
Example 3:
embodiment 3 of the present invention provides a high performance white pigment foil, which comprises a base film layer, a release layer, and a coloring layer in this order;
the base film layer is a PET film layer;
the preparation raw materials of the separation layer at least comprise the following components in percentage by mass:
6% of oxide;
5% of an amino compound;
and 89% of organic solvent.
The preparation method of the release layer comprises the following steps:
mixing and dissolving oxide (silicon dioxide) and amino compound (butylated melamine resin) in an organic solvent (propylene glycol methyl ether), and uniformly dispersing to obtain a raw material for a release layer.
The preparation raw materials of the coloring layer at least comprise the following components in percentage by mass:
Figure BDA0001707845420000101
the mass of the solvent is 2 times of that of the acrylic resin.
The raw materials for preparing the acrylic resin comprise methyl methacrylate, methacrylic acid and hydroxyethyl methacrylate phosphate;
the preparation method of the acrylic resin at least comprises the following steps:
adding methyl methacrylate, methacrylic acid, hydroxyethyl methacrylate phosphate and azobisisobutyronitrile into a 500mL reaction bottle containing a toluene solvent according to a certain proportion, reacting for 5h at 70 ℃ under the protection of nitrogen to obtain a product, dissolving the obtained product in acetone, precipitating and washing in water, and then carrying out vacuum drying to obtain the acrylic resin. Wherein the molar ratio of methyl methacrylate, methacrylic acid, hydroxyethyl methacrylate phosphate and azobisisobutyronitrile is 5: 2: 0.1: 0.1.
the plasticizer is dibutyl phthalate;
the whitening agent is di-tert-butyl benzothiophene;
the preparation method of the coloring layer comprises the following steps:
mixing acrylic resin, titanium dioxide, a plasticizer and a whitening agent, dissolving in an organic solvent, and uniformly dispersing to obtain the use raw material of the coloring layer.
The preparation process of the high-performance white pigment foil at least comprises the following steps:
firstly, uniformly coating a release layer on a base film layer, and drying; and then uniformly coating the coloring layer on the release layer, and drying to obtain a finished product.
Example 4:
embodiment 4 of the present invention provides a high performance white pigment foil, which comprises a base film layer, a release layer, and a coloring layer in this order;
the base film layer is a PET film layer;
the preparation raw materials of the separation layer at least comprise the following components in percentage by mass:
6% of oxide;
5% of an amino compound;
and 89% of organic solvent.
The preparation method of the release layer comprises the following steps:
mixing and dissolving oxide (silicon dioxide) and amino compound (butylated melamine resin) in an organic solvent (propylene glycol methyl ether), and uniformly dispersing to obtain a raw material for a release layer.
The preparation raw materials of the coloring layer at least comprise the following components in percentage by mass:
Figure BDA0001707845420000111
the mass of the solvent is 2 times of that of the acrylic resin.
The raw materials for preparing the acrylic resin comprise methyl methacrylate, methacrylic acid and hydroxyethyl methacrylate phosphate;
the preparation method of the acrylic resin at least comprises the following steps:
adding methyl methacrylate, methacrylic acid, hydroxyethyl methacrylate phosphate and azobisisobutyronitrile into a 500mL reaction bottle containing a toluene solvent according to a certain proportion, reacting for 5h at 70 ℃ under the protection of nitrogen to obtain a product, dissolving the obtained product in acetone, precipitating and washing in water, and then carrying out vacuum drying to obtain the acrylic resin. Wherein, the mol ratio of methyl methacrylate, methacrylic acid, hydroxyethyl methacrylate phosphate and azodiisobutyronitrile is 6: 3: 1: 0.2.
the plasticizer is dibutyl phthalate;
the whitening agent is di-tert-butyl benzothiophene;
the preparation method of the coloring layer comprises the following steps:
mixing acrylic resin, titanium dioxide, a plasticizer and a whitening agent, dissolving in an organic solvent, and uniformly dispersing to obtain the use raw material of the coloring layer.
The preparation process of the high-performance white pigment foil at least comprises the following steps:
firstly, uniformly coating a release layer on a base film layer, and drying; and then uniformly coating the coloring layer on the release layer, and drying to obtain a finished product.
Example 5:
embodiment 5 of the present invention provides a high performance white pigment foil, which comprises a base film layer, a release layer, and a coloring layer in this order;
the base film layer is a PET film layer;
the preparation raw materials of the separation layer at least comprise the following components in percentage by mass:
6% of oxide;
5% of an amino compound;
and 89% of organic solvent.
The preparation method of the release layer comprises the following steps:
mixing and dissolving oxide (silicon dioxide) and amino compound (butylated melamine resin) in an organic solvent (propylene glycol methyl ether), and uniformly dispersing to obtain a raw material for a release layer.
The silica was replaced by: the mesoporous silica MCM-41 is commercially available and is purchased from Nanjing Xiancheng nanometer material science and technology Limited.
The preparation raw materials of the coloring layer at least comprise the following components in percentage by mass:
Figure BDA0001707845420000121
the mass of the solvent is 2 times of that of the acrylic resin.
The raw materials for preparing the acrylic resin comprise methyl methacrylate, methacrylic acid and hydroxyethyl methacrylate phosphate;
the preparation method of the acrylic resin at least comprises the following steps:
adding methyl methacrylate, methacrylic acid, hydroxyethyl methacrylate phosphate and azobisisobutyronitrile into a 500mL reaction bottle containing a toluene solvent according to a certain proportion, reacting for 5h at 70 ℃ under the protection of nitrogen to obtain a product, dissolving the obtained product in acetone, precipitating and washing in water, and then carrying out vacuum drying to obtain the acrylic resin. Wherein, the mol ratio of methyl methacrylate, methacrylic acid, hydroxyethyl methacrylate phosphate and azodiisobutyronitrile is 6: 3: 1: 0.2.
the plasticizer is dibutyl phthalate;
the whitening agent is di-tert-butyl benzothiophene;
the preparation method of the coloring layer comprises the following steps:
mixing acrylic resin, titanium dioxide, a plasticizer and a whitening agent, dissolving in an organic solvent, and uniformly dispersing to obtain the use raw material of the coloring layer.
The preparation process of the high-performance white pigment foil at least comprises the following steps:
firstly, uniformly coating a release layer on a base film layer, and drying; and then uniformly coating the coloring layer on the release layer, and drying to obtain a finished product.
Example 6:
embodiment 6 of the present invention provides a high performance white pigment foil, which comprises a base film layer, a release layer, and a coloring layer in this order;
the base film layer is a PET film layer;
the preparation raw materials of the separation layer at least comprise the following components in percentage by mass:
6% of oxide;
5% of an amino compound;
and 89% of organic solvent.
The preparation method of the release layer comprises the following steps:
mixing and dissolving oxide (silicon dioxide) and amino compound (butylated melamine resin) in an organic solvent (propylene glycol methyl ether), and uniformly dispersing to obtain a raw material for a release layer.
The silica was replaced by: the mesoporous silica MCM-41 is commercially available and is purchased from Nanjing Xiancheng nanometer material science and technology Limited.
The preparation raw materials of the coloring layer at least comprise the following components in percentage by mass:
Figure BDA0001707845420000141
the mass of the solvent is 2 times of that of the acrylic resin.
The preparation method of the acrylic resin at least comprises the following steps:
adding methyl methacrylate, methacrylic acid, hydroxyethyl methacrylate phosphate and azobisisobutyronitrile into a 500mL reaction bottle containing a toluene solvent according to a certain proportion, reacting for 5h at 70 ℃ under the protection of nitrogen to obtain a product, dissolving the obtained product in acetone, precipitating and washing in water, and then carrying out vacuum drying to obtain the acrylic resin. Wherein, the mol ratio of methyl methacrylate, methacrylic acid, hydroxyethyl methacrylate phosphate and azodiisobutyronitrile is 6: 3: 1: 0.2.
the plasticizer is dibutyl phthalate;
the whitening agent is di-tert-butyl benzothiophene;
the titanium dioxide is silane coupling agent modified titanium dioxide;
the preparation method of the silane coupling agent modified titanium dioxide at least comprises the following steps:
adding 200mL of toluene and 10g of titanium dioxide serving as a solvent into a reactor, performing ultrasonic dispersion for 30min, then adding 1g of aminosilane coupling agent, adding 10mL of triethylamine solution with the volume concentration of 10%, performing reflux reaction for 3h at 60 ℃, filtering, washing for 3 times with ethanol, and drying to obtain the silane coupling agent modified titanium dioxide.
The silane coupling agent is 3-aminopropyl triethoxysilane;
the preparation method of the coloring layer comprises the following steps:
mixing acrylic resin, titanium dioxide, a plasticizer and a whitening agent, dissolving in an organic solvent, and uniformly dispersing to obtain the use raw material of the coloring layer.
The preparation process of the high-performance white pigment foil at least comprises the following steps:
firstly, uniformly coating a release layer on a base film layer, and drying; and then uniformly coating the coloring layer on the release layer, and drying to obtain a finished product.
Comparative example 1:
comparative example 1 is the same as example 1 except that methyl methacrylate is not included in the acrylic resin.
Comparative example 2:
comparative example 2 is the same as example 1 except that methacrylic acid is not included in the acrylic resin.
Comparative example 3:
comparative example 3 is the same as example 1 except that hydroxyethyl methacrylate phosphate is not included in the acrylic resin.
Comparative example 4:
comparative example 4 is the same as example 1 except that the molar ratio between methyl methacrylate and methacrylic acid was changed to 1: 1.
comparative example 5:
comparative example 5 is the same as example 1 except that methacrylic acid was replaced with acrylic acid.
Comparative example 6:
comparative example 6 is the same as example 1 except that methyl methacrylate was replaced with acrylic acid.
Comparative example 7:
comparative example 7 is the same as example 1 except that methyl methacrylate was replaced with ethyl methacrylate.
Comparative example 8:
comparative example 8 is the same as example 1 except that hydroxyethyl methacrylate phosphate was replaced with hydroxyethyl methacrylate.
Evaluation of Performance
The test method is as follows:
1. respectively sticking the adhesive tapes on the coloring layers of the products of the examples 1-6 and the comparative examples 1-6, fully pressing to ensure that the adhesive tapes completely cover the coloring layers, tearing off the adhesive tapes, and observing that no titanium dioxide remains on the adhesive tapes and no residual titanium dioxide remains, wherein the adhesive tapes are marked as 0 level; a small amount of residual titanium dioxide is marked as grade 1; a large amount of titanium dioxide remained, as grade 2.
2. Repeatedly poking the products of examples 1-6 and comparative examples 1-6, repeating the above operation again, observing whether the titanium dioxide is wiped off or not, and marking as 0 grade without any titanium dioxide; wiping off a small amount of titanium dioxide, and marking as grade 1; a large amount of titanium dioxide was wiped off and scored as grade 2.
3. Immersing the products of examples 1-6 and comparative examples 1-6 in water at 100 ℃ for 5h, drying, repeating the operation again, observing whether the titanium dioxide is wiped off or not, and marking as 0 grade if no titanium dioxide is wiped off; wiping off a small amount of titanium dioxide, and marking as grade 1; a large amount of titanium dioxide was wiped off and scored as grade 2.
Specific data are shown in table 1.
Table 1 results of performance testing
Examples Rating of dusting Rub poke dusting grade Grade of powder falling after soaking in water
Example 1 Level 0 Level 0 Level 1
Example 2 Level 0 Level 0 Level 1
Example 3 Level 0 Level 0 Level 1
Example 4 Level 0 Level 0 Level 1
Example 5 Level 0 Level 0 Level 0
Example 6 Level 0 Level 0 Level 0
Comparative example 1 Level 1 Level 1 Level 1
Comparative example 2 Level 0 Level 1 Level 1
Comparative example 3 Level 0 Level 1 Level 1
Comparative example 4 Level 1 Level 1 Level 1
Comparative example 5 Level 0 Level 1 Stage 2
Comparative example 6 Level 0 Level 1 Stage 2
Comparative example 7 Level 1 Level 1 Level 1
Comparative example 8 Level 1 Level 1 Level 1

Claims (8)

1. A high-performance white pigment foil, characterized in that the high-performance white pigment foil comprises at least a coloring layer;
the preparation raw materials of the coloring layer are calculated by mass percent as follows:
Figure FDA0002485442030000011
the mass percentage of the raw materials is 100 percent;
a proper amount of solvent;
the preparation raw materials of the acrylic resin are methyl methacrylate, methacrylic acid and hydroxyethyl methacrylate phosphate;
in the preparation raw materials of the acrylic resin, the molar ratio of methyl methacrylate, methacrylic acid and hydroxyethyl methacrylate phosphate is (5-8): (2-3): (0.1-2).
2. The high performance white pigment foil of claim 1, wherein the plasticizer is selected from the group consisting of: dibutyl phthalate, dioctyl phthalate, acetyl tri-N-butyl citrate, acetyl triethyl citrate, N-ethyl o-p-toluenesulfonamide, 2-butoxyethyl stearate, N-butyl stearate, 1, 2-propylene glycol monolaurate, glycerol monolaurate, diethylene glycol monolaurate, butoxyethyl laurate, polyethylene glycol dilaurate, triethyl citrate, tri-N-butyl citrate, triethyl acetyl citrate, tri-N-butyl acetyl citrate, trihexyl acetyl citrate, epoxy acetyl methyl ricinoleate, epoxy triglyceride, and epoxy isooctyl stearate.
3. The high performance white pigment foil of claim 1, wherein the whitening agent is selected from the group consisting of: any one or a mixture of a plurality of bis-tert-butylbutylbenzothiophene, 4' -bis- (2-sulfostyryl) -biphenyl salt, 4' -bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) naphthalene thiazole derivative, 4' -bis (triazol-2-yl) stilbene derivative and bis- (triazinylaminostilbene) disulfonic acid derivative.
4. The high performance white pigment foil of claim 1, wherein the solvent is selected from the group consisting of: ethyl acetate, butyl acetate, benzene, toluene, xylene, acetone, butanone, cyclohexanone, ethanol, butanol, methyl ether, ethyl ether, butyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol, glycerol, propylene glycol methyl ether, propylene glycol ethyl ether, sulfuric acid, hydrochloric acid, formic acid, and acetic acid.
5. The high performance white pigment foil of claim 1, further comprising a release layer, wherein the release layer is adjacent to the colored layer.
6. The high performance white pigment foil according to claim 5, wherein the release layer is prepared from a raw material comprising, in mass percent, at least:
2-10% of an oxide;
0-10% of an amino compound;
the balance of organic solvent;
the mass percentage of the raw materials is 100 percent.
7. The high performance white pigment foil of claim 1, further comprising a base film layer;
the high-performance white pigment foil sequentially comprises a base film layer, a release layer and a coloring layer; or the high-performance white pigment foil sequentially comprises a base film layer and a coloring layer.
8. The process for preparing a high performance white pigment foil according to claim 7, comprising at least the steps of:
firstly, uniformly coating a release layer on a base film layer, and drying; then uniformly coating the coloring layer on the release layer, and drying to obtain a finished product; or directly and uniformly coating the coloring layer on the base film layer and drying.
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