阅读说明：本技术 具有光栅化彩色图案的基板的制备方法 (Method for preparing substrate with raster colorful pattern ) 是由 陈旭东 洪炜 朱永祥 于 2020-04-29 设计创作，主要内容包括：本发明属于光栅化二维结构制备领域,公开了一种具有光栅化彩色图案的基板的制备方法,是取附着有光敏性聚合物的基板经紫外将光栅格式化图案曝光至光敏性聚合物表面,再浸入含金属离子的显影剂中显影后,即得。本发明采用光敏性聚合物作为基板的涂层,无需金属镀膜,节省了材料,降低了生产成本；同时,由于采用紫外曝光技术,制备光栅图案时,无需频繁更换母板,进一步降低了生产成本,解决了制备光栅状二维结构成本高的问题。本发明制备的具有光栅化彩色图案的基板适用于产品外包装,其能够有效提升产品的档次及观赏度。(The invention belongs to the field of preparation of a rasterized two-dimensional structure, and discloses a preparation method of a substrate with a rasterized color pattern. The invention adopts the photosensitive polymer as the coating of the substrate, does not need metal coating, saves materials and reduces the production cost; meanwhile, due to the adoption of the ultraviolet exposure technology, a mother board does not need to be frequently replaced when the grating pattern is prepared, the production cost is further reduced, and the problem of high cost in preparing the grating-shaped two-dimensional structure is solved. The substrate with the rasterized colorful pattern is suitable for product outer packaging, and can effectively improve the grade and the ornamental value of products.)

1. A preparation method of a substrate with a rasterized color pattern is characterized by comprising the following steps of:

1) placing the substrate A attached with the photosensitive polymer under ultraviolet light, and exposing a grating formatted pattern on the surface of the photosensitive polymer to form a two-dimensional grating structure on the surface of the photosensitive polymer to obtain a substrate B;

2) and immersing the substrate B into a developer containing metal ions for developing to obtain the substrate with the rasterized color pattern.

2. The method for preparing a substrate with a rasterized color pattern according to claim 1, characterized in that the prepared substrate with a rasterized color pattern is subjected to a heat treatment;

the color-generating light source of the substrate with the rasterized color pattern is a natural light source.

3. The method as claimed in claim 1, wherein the substrate a having the photosensitive polymer is prepared by coating a photosensitive polymer solution on the substrate C and heating to evaporate the solvent.

4. The method of claim 3, wherein the photosensitive polymer solution is prepared by blending photosensitive material D and polymer E;

the polymer E is at least one of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, polyurethane, polycarbonate, polyamide, polyimide, polyethylene terephthalate, polyformaldehyde, polyphenyl ether and polyphenylene sulfide;

the weight ratio of the photosensitive substance D to the polymer E is 1: 1-100.

5. The method of claim 3, wherein the photosensitive polymer solution is prepared by directly chemically grafting a photosensitive material D and a polymer F;

wherein the polymer F is at least one of a carboxyl group-containing polymer, an acid halide group-containing polymer, a sulfonic acid group-containing polymer, an acid anhydride group-containing polymer, an aldehyde group-containing polymer, and a halogenated alkyl group-containing polymer;

the weight ratio of the photosensitive substance D to the polymer F is 1: 1-100.

6. The method of preparing a substrate having a rasterized color pattern according to claim 3, characterized in that the photosensitive polymer solution is also prepared by successively carrying out the following steps:

a1) preparing a photosensitive diamine monomer H by a chemical grafting method by using a photosensitive substance D and a compound G with diamine groups;

a2) and adding the photosensitive diamine monomer H and the anhydride monomer into a polar organic solvent, and carrying out polycondensation reaction under the protection of an inactive gas to obtain the photosensitive diamine/anhydride/diamine/.

7. The method for preparing a substrate having a rasterized color pattern according to any one of claims 4 to 6, characterized in that the structural formula of the photosensitive substance D is:

。

8. the method of claim 6, wherein the step of forming the substrate having the rasterized color pattern comprises the step of forming a mask having a predetermined pattern,

in the step a1), the compound G with diamino is 3, 3 '-diamino-4, 4' -bis (4-bromobutanol) -biphenyl;

the molar ratio of the photosensitive substance D to the compound G with the diamine group is 2-2.2: 1;

in the step a2), the acid anhydride monomer is at least one of pyromellitic dianhydride, biphenyl dianhydride, diphenyl ether dianhydride, diether dianhydride and thioether dianhydride;

the polar organic solvent is at least one of N, N-dimethylformamide, N-diethylacetamide, N-methylpyrrolidone, tetrahydrofuran, methanol, dimethyl sulfoxide, toluene, p-xylene and benzene;

the molar ratio of the photosensitive diamine monomer H to the acid anhydride monomer is 1: 1-1.1;

the mass ratio of the total mass of the photosensitive diamine monomer H and the acid anhydride monomer to the polar solvent is 1: 3-19;

the polycondensation is carried out at 0-10 ℃ for 20-28 h;

before the polycondensation reaction, when the photosensitive substance C and the anhydride monomer are added into a polar solvent, the temperature of the polar solvent is 0-10 ℃.

9. The method as claimed in claim 1, wherein the raster-formatted pattern is a raster-formatted pattern stored in the system after raster-formatted by a Computer aid Drafting software.

10. The method of claim 1, wherein the step of forming the substrate having the rasterized color pattern comprises the step of forming a mask having a predetermined pattern,

in the step 1), the exposure wavelength is 100-400nm, and the time is 1-1000 ms;

in the step 2), the developing time is 1-60s and the temperature is 20-60 ℃;

the solute in the developer is at least one transition metal salt, and the solvent is at least one of methanol, ethanol, acetone, toluene, dimethyl sulfoxide, N-dimethylformamide, N-diethylacetamide, N-methylpyrrolidone, diethyl ether, pyridine and dioxane;

the concentration of the transition metal salt in the developer is 0.005-0.02 kg/L.

Technical Field

The invention belongs to the field of preparation of a rasterized two-dimensional structure, relates to preparation of rasterized color patterns, and particularly relates to a preparation method of a substrate with rasterized color patterns.

Background

The grating two-dimensional structure can enable the material to show bright rainbow color under the action of transmitted light or reflected light under the condition of no dye color generation, and the structural color formed on the material has the advantages of oxidation resistance, acid and alkali resistance, fastness, wear resistance and the like compared with the dye color. The polymer material containing structural color is widely applied to the outer packaging of daily consumer products such as medicines, foods, washing and protecting products, cigarettes, wines and the like, and the attractive color pattern greatly improves the grade and the appreciation of the products.

However, the traditional method for preparing the photogenerated color grating two-dimensional structure usually uses the processes of nano-imprinting, vapor deposition, laser engraving and the like, and has the defects of high cost, complex operation and the like. The product also tends to make the material almost opaque due to the presence of the underlying metal coating. Moreover, the preparation of the rasterized two-dimensional structure on the surface of the substrate is generally limited by the pattern of the motherboard, and a new motherboard needs to be replaced when a new pattern is replaced, thereby increasing the preparation cost of the product.

Disclosure of Invention

The invention aims to provide a method for preparing a substrate with a rasterized color pattern, which aims to solve the problem of high cost of preparing a rasterized two-dimensional structure in the prior art.

In order to achieve the purpose, the invention adopts the technical scheme that:

a method for preparing a substrate with a rasterized color pattern comprises the following steps which are carried out in sequence:

1) placing a substrate A attached with a photosensitive polymer under ultraviolet light, and exposing a grating formatted pattern on the surface of the photosensitive polymer by adopting a direct writing type or a mask plate covering type, wherein a two-dimensional grating structure is formed on the surface of the photosensitive polymer to obtain a substrate B; the substrate B is attached with a photosensitive polymer of which the surface forms a two-dimensional grating structure, and obvious color patterns cannot be directly observed on the surface of the photosensitive polymer;

2) and after the substrate B is immersed in a developer containing metal ions for development, the metal ions are selectively and precisely deposited in an exposure area in the development process, an obvious iridescent exposure pattern can be observed by the developed polymer under transmitted light or reflected light, and the pattern color has strong angle dependence on the light source incidence angle, so that the substrate with the rasterized color pattern is obtained.

As a limitation, the prepared substrate having the rasterized color pattern is subjected to a heat treatment;

the temperature of the heating treatment is 150-;

the color-generating light source of the substrate with the rasterized color pattern is a natural light source.

As a second limitation, the substrate a with the photosensitive polymer attached is prepared by coating a photosensitive polymer solution on a substrate C, and heating to evaporate the solvent;

the thickness of the photosensitive polymer on the substrate A to which the photosensitive polymer is attached is 3 to 3000 μm.

By way of further limitation, the photosensitive polymer is prepared by blending a photosensitive substance D and a polymer E;

the polymer E is at least one of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, polyurethane, polycarbonate, polyamide, polyimide, polyethylene terephthalate, polyformaldehyde, polyphenyl ether and polyphenylene sulfide;

the weight ratio of the photosensitive substance D to the polymer E is 1: 1-100;

the blending method is prepared by dissolving in a polar solvent at 25-80 ℃;

the weight ratio of the photosensitive substance D to the polar solvent is 1: 16-519.

As a further limitation, the photosensitive polymer can also be prepared by directly carrying out a chemical grafting method on a photosensitive substance D and a polymer F;

wherein the polymer F is at least one of a carboxyl group-containing polymer, an acid halide group-containing polymer, a sulfonic acid group-containing polymer, an acid anhydride group-containing polymer, an aldehyde group-containing polymer, and a halogenated alkyl group-containing polymer;

the weight ratio of the photosensitive substance D to the polymer F is 1: 1-100;

the chemical grafting method is to react for 6 to 10 hours in a polar organic solvent;

a basic catalyst is also needed when the photosensitive substance and the polymer containing aldehyde groups or the polymer containing alkyl halide groups carry out chemical grafting reaction;

the alkaline catalyst is sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride or calcium hydride;

the weight ratio of the photosensitive substance D to the alkaline catalyst is 1: 0.02-1.

By way of further limitation, the photosensitive polymer may also be prepared by sequentially performing the following steps:

a1) preparing a photosensitive diamine monomer H by a chemical grafting method by using a photosensitive substance D and a compound G with diamine groups;

a2) and adding the photosensitive diamine monomer H and the anhydride monomer into a polar organic solvent, and carrying out polycondensation reaction under the protection of an inactive gas to obtain the photosensitive diamine/anhydride/diamine/.

As a still further limitation, the photosensitive material D has a structural formula:

wherein, the photosensitive structure D' in the photosensitive substance D is:

the photosensitive structure D' is changed into a photosensitive structure I after exposure reaction, and the structural formula of the photosensitive structure I is as follows:

namely, the photosensitive polymer of which the surface forms a two-dimensional grating structure contains the photosensitive structure I.

As a further limitation, in step a1), the compound G having a diamine group is 3, 3 '-diamine-4, 4' -bis (4-bromobutanediol) -biphenyl;

the molar ratio of the photosensitive substance D to the compound G with the diamine group is 2-2.2: 1;

in the step a2), the acid anhydride monomer is at least one of pyromellitic dianhydride, biphenyl dianhydride, diphenyl ether dianhydride, diether dianhydride and thioether dianhydride;

the polar organic solvent is at least one of N, N-dimethylformamide, N-diethylacetamide, N-methylpyrrolidone, tetrahydrofuran, methanol, dimethyl sulfoxide, toluene, p-xylene and benzene;

the molar ratio of the photosensitive diamine monomer H to the acid anhydride monomer is 1: 1-1.1;

the mass ratio of the total mass of the photosensitive diamine monomer H and the acid anhydride monomer to the polar solvent is 1: 3-19;

the polycondensation is carried out at 0-10 ℃ for 20-28 h;

before the polycondensation reaction, when the photosensitive substance C and the anhydride monomer are added into a polar solvent, the temperature of the polar solvent is 0-10 ℃.

As a third limitation, the raster-formatted pattern is a raster-formatted pattern stored in the system after being raster-formatted by a common pattern through Computer aideddrawing software;

wherein, the width of the exposure line in the grating formatting pattern is 50-2000nm, and the grating period is 100-4000 nm.

As a fourth limitation, in the step 1), the wavelength of the ultraviolet exposure is 100-400nm, and the time is 1-1000 ms;

the exposure is carried out in an ultraviolet exposure machine, and the power of the ultraviolet exposure machine is 10-1000W;

in the step 2), the developing time is 1-60s and the temperature is 20-60 ℃.

As a fifth limitation, the solute in the developer is at least one transition metal salt, and the solvent is at least one of methanol, ethanol, acetone, toluene, dimethyl sulfoxide, N-dimethylformamide, N-diethylacetamide, N-methylpyrrolidone, diethyl ether, pyridine, dioxane;

the concentration of the transition metal salt in the developer is 0.005-0.02 kg/L;

the transition metal salt is gold salt, silver salt, palladium salt, platinum salt, copper salt, cobalt salt, nickel salt or zinc-gold salt.

The substrate with the rasterized color pattern has a two-dimensional grating structure on the surface of a photosensitive polymer after being developed in a developer containing metal ions, when incident light irradiates on the two-dimensional grating structure on the surface of the polymer, the incident light can generate diffraction of different orders on the concave-convex structure part and be split, when the optical path difference of the diffracted light with different wavelengths is the positive integer multiple of the wavelength, coherence or resonance enhancement can be generated, and the two-dimensional grating structure on the surface of the polymer can generate color patterns with different colors under illumination. The structural color of the two-dimensional grating structure under illumination has strong angle dependence, and the principle of the two-dimensional grating structure can be illustrated by the following basic grating equation:

sinα+sinβ＝10^-6knλ，

where α is an incident angle, β is a diffraction angle, k is a diffraction order (positive integer), n is a reticle density, and λ is an incident light wavelength. Thus, for a rasterized pattern having a fixed reticle density, natural light having different wavelengths λ incident on the two-dimensional grating structure will result in different diffraction angles at the same diffraction order when the angle of incidence α is fixed. For the same incident light wavelength, corresponding diffracted light can be observed under corresponding diffraction angles under different diffraction orders, and equivalently, when the receiving angle is not changed, the same effect can be obtained by changing the incident angle of the incident light, so that the structural color of the two-dimensional grating structure under illumination has strong angle dependence.

Due to the adoption of the technical scheme, compared with the prior art, the invention has the technical progress that:

the invention adopts the photosensitive polymer as the coating of the substrate, does not need metal coating, saves materials and reduces the production cost; because the ultraviolet exposure technology is adopted, the mother board does not need to be frequently replaced when the grating pattern is prepared, and the production cost is further reduced; moreover, the invention has simple process route and convenient operation;

meanwhile, the obviously-developed rasterized colorful pattern has high goodness of fit with the designed pattern, short development time, high resolution and obvious pattern visual effect, and is very suitable for large-scale continuous production.

The substrate with the rasterized colorful pattern is suitable for product outer packaging, and can effectively improve the grade and the ornamental value of products.

Drawings

FIG. 1 shows a substrate N in example 1 of the present invention₁The principle schematic diagram of the structural color of the rasterized color pattern on the surface under the illumination condition is shown, wherein diffracted light a is purple light, diffracted light b is blue light, diffracted light c is green light, and diffracted light d is red light;

fig. 2 is a schematic diagram of optical rasterization in embodiment 1 of the present invention, wherein fig. 2(a) is a normal pattern, fig. 2(b) is a raster formatting pattern, and fig. 2(c) is a partial detail view of the raster formatting pattern;

FIG. 3 shows a substrate N in example 1 of the present invention₁A physical effect map of the rasterized color pattern on the surface;

FIG. 4 shows a substrate N in example 1 of the present invention₁Local electron micrographs of the rasterized color pattern on the surface.

Detailed Description

The present invention is further illustrated by the following specific examples, which are to be construed as merely illustrative, and not limitative of the remainder of the disclosure.