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 problem, a first aspect of the present invention provides a 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 and methacrylic acid.
In one embodiment, the acrylic resin is prepared from raw materials comprising methyl methacrylate and methacrylic acid in a molar ratio of: (5-10): (0-5); preferably, the molar ratio of methyl methacrylate to methacrylic acid is: (6-7): (2.5-3); most preferably, the molar ratio of methyl methacrylate to methacrylic acid is: 6: 3.
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.
In a preferred embodiment, the method for preparing the acrylic resin at least comprises the following steps:
adding methyl methacrylate, methacrylic acid and azobisisobutyronitrile into a 500mL reaction bottle containing a toluene solvent according to a certain proportion, reacting for 3-5 h at 45-70 ℃ 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.
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:
the mass percentage of the raw materials is 100 percent;
and (4) proper amount of solvent.
More preferably, the preparation raw materials of the colored layer at least comprise the following components in parts by weight:
10-15% of acrylic resin;
70-90% of titanium dioxide;
3-5% of a plasticizer;
1-3% of a whitening agent;
the mass percentage of the raw materials is 100 percent;
and (4) proper amount of solvent.
Most preferably, the preparation raw materials of the colored layer at least comprise the following components in parts by weight:
10% of acrylic resin;
85% of titanium dioxide;
4% of a plasticizer;
1% of whitening agent;
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 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:
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.
Preferably, the raw materials for preparing the release layer at least comprise the following components in percentage by mass:
5-8% of an oxide;
3-7% of an amino compound;
the balance of organic solvent;
the mass percentage of the raw materials is 100 percent.
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 white pigment foil further comprises a base film layer; the base membrane layer is adjacent to the release layer.
In another preferred embodiment, the white pigment foil further comprises a base film layer; the base film layer is directly adjacent to the color layer.
In the present application, the base film layer used is a PET film layer.
In the present application, the release layer and the colored layer can be mixed to form a single layer, which is coated onto the base film layer to provide yet another product of the present application.
Another aspect of the present invention provides a process for preparing a 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 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 and methacrylic acid;
the preparation method of the acrylic resin at least comprises the following steps:
adding methyl methacrylate, methacrylic acid and azobisisobutyronitrile into a 500mL reaction bottle containing a toluene solvent according to a certain proportion, reacting for 4h at 60 ℃ under the protection of nitrogen to obtain a product, dissolving the obtained product in acetone, precipitating and washing in water, and then drying in vacuum to obtain the acrylic resin. Wherein, the mol ratio of the methyl methacrylate, the methacrylic acid and the azobisisobutyronitrile is 5: 2: 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 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 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:
the mass of the solvent is 5 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 and azobisisobutyronitrile into a 500mL reaction bottle containing a toluene solvent according to a certain proportion, reacting for 4h at 60 ℃ under the protection of nitrogen to obtain a product, dissolving the obtained product in acetone, precipitating and washing in water, and then drying in vacuum to obtain the acrylic resin. Wherein, the mol ratio of the methyl methacrylate, the methacrylic acid and the azobisisobutyronitrile is 5: 2: 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 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 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:
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 and azobisisobutyronitrile into a 500mL reaction bottle containing a toluene solvent according to a certain proportion, reacting for 4h at 60 ℃ under the protection of nitrogen to obtain a product, dissolving the obtained product in acetone, precipitating and washing in water, and then drying in vacuum to obtain the acrylic resin. Wherein, the mol ratio of the methyl methacrylate, the methacrylic acid and the azobisisobutyronitrile is 5: 2: 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 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 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:
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 and azobisisobutyronitrile into a 500mL reaction bottle containing a toluene solvent according to a certain proportion, reacting for 4h at 60 ℃ under the protection of nitrogen to obtain a product, dissolving the obtained product in acetone, precipitating and washing in water, and then drying in vacuum to obtain the acrylic resin. Wherein, the mol ratio of methyl methacrylate, methacrylic acid and azodiisobutyronitrile is 8: 3: 0.15.
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 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 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:
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 and azobisisobutyronitrile into a 500mL reaction bottle containing a toluene solvent according to a certain proportion, reacting for 4h at 60 ℃ under the protection of nitrogen to obtain a product, dissolving the obtained product in acetone, precipitating and washing in water, and then drying in vacuum to obtain the acrylic resin. Wherein, the mol ratio of methyl methacrylate, methacrylic acid and azodiisobutyronitrile is 6: 3: 0.12.
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 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 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:
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 and azobisisobutyronitrile into a 500mL reaction bottle containing a toluene solvent according to a certain proportion, reacting for 4h at 60 ℃ under the protection of nitrogen to obtain a product, dissolving the obtained product in acetone, precipitating and washing in water, and then drying in vacuum to obtain the acrylic resin. Wherein, the mol ratio of methyl methacrylate, methacrylic acid and azodiisobutyronitrile is 6: 3: 0.12.
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 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 the molar ratio between methyl methacrylate and methacrylic acid was changed to 1: 1.
comparative example 4:
comparative example 4 is the same as example 1 except that methacrylic acid was replaced with acrylic acid.
Comparative example 5:
comparative example 5 is the same as example 1 except that methyl methacrylate was replaced with acrylic acid.
Comparative example 6:
comparative example 6 is the same as example 1 except that methyl methacrylate was replaced with ethyl 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
In addition, the release layer of the pigment foil obtained by the method has a good release effect, and has no quality problems such as color floating and the like.