CN115011278B - 3D colloid photon crystal pressure-sensitive adhesive with bright structural color and preparation method thereof - Google Patents

3D colloid photon crystal pressure-sensitive adhesive with bright structural color and preparation method thereof Download PDF

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CN115011278B
CN115011278B CN202210525020.5A CN202210525020A CN115011278B CN 115011278 B CN115011278 B CN 115011278B CN 202210525020 A CN202210525020 A CN 202210525020A CN 115011278 B CN115011278 B CN 115011278B
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sensitive adhesive
pressure
hard core
layer
soft shell
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CN115011278A (en
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汪长春
赵国伟
李华腾
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Fudan University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/50—Adhesives in the form of films or foils characterised by a primer layer between the carrier and the adhesive
    • 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
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/002—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials
    • G02B1/005—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials made of photonic crystals or photonic band gap materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention belongs to the technical field of photonic crystal materials, and particularly relates to a 3D colloid photonic crystal pressure-sensitive adhesive with vivid structural color and a preparation method thereof. The pressure-sensitive adhesive is of a three-layer structure and sequentially comprises a substrate layer, a 3D colloid photon crystal layer and a pressure-sensitive adhesive layer from bottom to top; the 3D colloid photon crystal layer consists of hard building units and matrix (continuous phase), the building units are orderly arranged in the continuous phase to generate vivid structural color, and the wavelength of the color can be regulated between 380 and 800 nanometers; the continuous phase is composed of polyacrylate functional copolymer, which can improve the adhesion of the photon crystal layer, the substrate layer and the pressure-sensitive adhesive layer. The color of the adhesive tape in the pressure-sensitive adhesive is generated by the action of light and the micro-nano structure of the photonic crystal in the adhesive tape, and is a physical color-generating mechanism, so that the pressure-sensitive adhesive is environment-friendly, nontoxic and harmless, can keep the color for a long time, and has great application potential in the fields of packaging, decoration, anti-counterfeiting and the like.

Description

3D colloid photon crystal pressure-sensitive adhesive with bright structural color and preparation method thereof
Technical Field
The invention relates to the technical field of photonic crystal materials, in particular to a 3D colloid photonic crystal pressure-sensitive adhesive with vivid structural color and a preparation method thereof.
Background
Color plays an extremely important role in our lives, making our lives colorful. At present, the colors seen by us are mainly divided into pigment colors and structural colors, wherein the pigment colors mainly come from dyes and pigments, and the dyes and pigment molecules reflect the light with the rest wavelengths by absorbing the visible light with the specific wavelengths, so that the colors seen by us are formed; the generation of structural color is a physical color-generating mechanism, and its micro-nano structure can reflect visible light with specific wavelength to form color. Dyes and pigments generally consist of heavy metal ions and small organic molecules, which not only produce a great deal of pollution in the production process, but also cause harm to the environment after being discarded, and most importantly, the color of the dye is gradually dull as the substances are oxidized or photobleaching; compared with the prior art, the structural color is greener and environment-friendly, and the structural color is generated in a physical color-generating mode, so that the structural color can be used for replacing pigment color used in daily life, and the harm to the environment is greatly reduced while long-term color development is realized.
Colloidal photonic crystals are a typical representation of a photonic crystal family, which is an ordered structure material formed by periodically arranging materials with different refractive indexes, and a photonic forbidden band is generated by assembling spherical building units in a matrix, so that visible light with specific wavelength can be reflected to generate color. The colloid photon crystal can utilize the chemical assembly mode from bottom to top, has the potential of large-scale production, and is very suitable for being applied to the fields of decoration, display, anti-counterfeiting and the like in daily life.
The pressure sensitive adhesive with different colors is widely applied to daily life of people and plays roles of decoration, encapsulation, warning, electric appliance identification, protection and the like. However, the existing pressure-sensitive adhesive is pigment in color, the color development durability is low, and the production process of the pigment layer of the adhesive tape can pollute the environment.
Disclosure of Invention
Aiming at the defects of the existing pressure-sensitive adhesive materials, the invention aims to develop a 3D colloid photon crystal pressure-sensitive adhesive with vivid structural color. The color of the pressure-sensitive adhesive is mainly derived from structural color generated by the 3D colloid photon crystal, no dye or pigment is needed for generating the color, and the influence of the external environment on the color can be reduced to the greatest extent by virtue of the micro-nano structure and the effect of light, so that the color is kept for a long time. The structural color pressure-sensitive adhesive does not contain heavy metal ions and small organic molecules, is nontoxic and harmless to the environment, and is environment-friendly.
According to the invention, the hard core soft shell microsphere is synthesized through semi-continuous multi-step seed emulsion polymerization, the regularity of the photonic crystal layer is realized by bending induced shearing, and finally, the composition of the substrate layer, the photonic crystal layer and the pressure-sensitive adhesive layer is realized through continuous coating, so that the 3D colloid photonic crystal pressure-sensitive adhesive with bright structural color is obtained. The technical scheme of the invention is as follows.
The invention provides a 3D colloid photon crystal pressure-sensitive adhesive with vivid structural color, which has a three-layer structure and sequentially comprises a substrate layer, a 3D colloid photon crystal layer and a pressure-sensitive adhesive layer from bottom to top; the 3D colloid photon crystal layer is formed by arranging hard construction units in soft continuous phase matrix in sequence, so as to form photon forbidden band, thereby reflecting visible light with specific wavelength and enabling the pressure sensitive adhesive to have bright color;
the 3D colloid photon crystal layer is prepared by synthesizing hard core soft shell microspheres and regularly arranging the shear-induced core microspheres in a film formed by a matrix; the hard core soft shell microsphere consists of a hard core microsphere and a soft shell layer; the hard core microspheres can maintain the shape when regularly sheared, thereby being used as a construction unit; the polymer selected for the soft shell layer is not crosslinked, and the uncrosslinked shell layers can be mutually fused to form a continuous phase matrix during processing. The color of the colloid photon crystal layer can be adjusted by changing the crystal face distance formed by the hard construction unit, so that the structural color pressure-sensitive adhesive with different appearance colors can be obtained.
In the invention, the average particle size of the hard core soft shell microsphere is 50-1000 nanometers, and the particle size distribution coefficient is less than 0.1. Wherein, the average grain diameter of the hard core microsphere is 25-500 nanometers, and the thickness of the soft shell layer is 12.5-250 nanometers.
In the invention, the hard core microsphere accounts for 30% -60% of the total mass of the hard core soft shell microsphere, and the soft shell layer is coated around the core microsphere in a covalent bond form and accounts for 40% -70% of the total mass of the hard core soft shell microsphere.
In the invention, the material composing the hard core microsphere is mainly a polymer with high glass transition temperature (Tg >110 ℃) and one or a mixture of a plurality of organic-inorganic or inorganic materials, and can be one or a mixture of a plurality of polystyrene, polymethyl methacrylate, polyacrylonitrile, silicon dioxide and cadmium sulfide.
In the invention, the soft shell layer mainly comprises polyacrylate copolymer with lower glass transition temperature, so that stronger binding force to the substrate layer and the pressure-sensitive adhesive layer can be generated. Monomers which may be used are methyl acrylate, methyl methacrylate, ethyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, N-butyl methacrylate, isobutyl methacrylate, isobornyl acrylate, isobornyl methacrylate, lauryl acrylate, lauryl methacrylate, 2-phenoxyethyl acrylate, vinyl acetate, styrene, butyl acrylate, ethyl acrylate, N-octyl acrylate, isooctyl methacrylate, isononyl acrylate, isononyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, acrylonitrile, 1, 4-butanediol diacrylate, acrylic acid, methacrylic acid, acrylamide, N-methylolacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate, glycidyl acrylate, diethylene glycol methacrylate, methyl acrylate, di-tert-butyl methacrylate, glycidyl methacrylate, tri-butyl methacrylate; preferably, the acrylic acid is more than two of styrene, 1, 4-butanediol diacrylate, allyl methacrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate and acrylic acid; wherein, the mass fraction of the acrylic monomer containing hydroxyl accounts for more than 10 percent of the mass fraction of the hard core soft shell microsphere.
In the invention, the base material layer is made of one of polyethylene terephthalate film (PET), low-density polyethylene film (LDPE), high-density polyethylene film (HDPE), biaxially oriented polypropylene film (BOPP), nylon film (PA) or polyurethane film (PU); preferably, it is a polyethylene terephthalate film (PET).
In the invention, the pressure-sensitive adhesive layer is formed by coating and drying polyacrylate pressure-sensitive adhesive emulsion.
In the invention, the thickness of the colloid photon crystal pressure-sensitive adhesive is 100-300 micrometers; wherein the thickness of the base material is 70-200 micrometers, the thickness of the 3D colloid photon crystal layer is 5-40 micrometers, and the thickness of the pressure-sensitive adhesive layer is 5-60 micrometers.
The invention also provides a 3D colloid photon crystal pressure-sensitive adhesive with vivid structural color, which comprises the following specific preparation steps:
s1, synthesizing hard core soft shell microspheres: preparing hard core soft shell microsphere by semi-continuous multi-step emulsion polymerization, wherein the reaction temperature is 70-95 ℃ and the reaction time is 12-20 hours;
s2, preparation of a coating liquid: uniformly mixing the obtained hard core soft shell microsphere emulsion with a functional monomer, a cross-linking agent and an auxiliary agent;
s3 3D regularity of colloidal photonic crystal layer: coating the coating liquid on a substrate, and then coating a release film after drying; the composite film is subjected to continuous bending and induced shearing, so that hard construction units are regularly arranged in a matrix, and then the construction elements are regularly arranged through thermal crosslinking and photo crosslinking;
s4, coating a pressure-sensitive adhesive layer: tearing off the surface release film from the regular film, coating pressure-sensitive adhesive emulsion, and drying to obtain the photonic crystal pressure-sensitive adhesive.
In the invention, in step S2, in order to further enhance the binding force of the 3D colloid photon crystal layer, the base material and the pressure-sensitive adhesive layer, a certain proportion of functional monomers, cross-linking agents and auxiliary agents are added in the preparation of the coating liquid; the functional monomer is mainly acrylic ester monomer, and can be selected from more than two of acrylic acid, methacrylic acid, acrylamide, N-methylolacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl methacrylate, hydroxypropyl methacrylate, glycidyl acrylate, diethylene glycol methyl ether methacrylate, diethylene glycol dimethacrylate, glycidyl methacrylate, glycidyl dimethacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, allyl methacrylate, 4-tert-butylcyclohexyl acrylate and acryloylmorpholine; the cross-linking agent is a mixed cross-linking agent of thermal cross-linking and photo-cross-linking, wherein the thermal cross-linking agent is one or a mixture of more than two of divinylbenzene, 1, 4-butanediol diacrylate, 1, 6-hexanediol dimethacrylate and allyl methacrylate, and the photo-cross-linking agent is a mixture of more than two of benzoin ethers, acetophenones, acyl phosphine oxides, benzophenones, hexaxanthones and coumarin ketones; the auxiliary agent is mainly wetting agent and leveling agent.
In the invention, in the step S2, the hard core soft shell microsphere emulsion is prepared from the following components in parts by weight: 45-75 parts; functional monomer: 10-20 parts; auxiliary agent: 0.5-2.5 parts; crosslinking agent: 0.5-2.5 parts.
In the present invention, in the steps S3 and S4, the coating methods that may be used include brushing, knife coating, roll coating, spray coating, dip coating, slit coating, or micro-gravure coating.
In the present invention, in step S3, the bending-induced shearing used for the 3D colloidal photonic crystal layer may be performed on a common polymer processing apparatus, such as uniaxial pressing, calendaring, lamination, continuous roll passing, and the like.
In the present invention, in step S3, the thermal crosslinking temperature is 60 to 75 ℃.
In the invention, in the step S4, the pressure-sensitive adhesive emulsion is polyacrylate pressure-sensitive adhesive emulsion.
The 3D colloid photon crystal pressure-sensitive adhesive with vivid structural color prepared by the invention has the color from the reflection of the micro-nano structure of the adhesive tape to visible light with specific wavelength, and is a pure physical color-generating mode, so compared with the pressure-sensitive adhesive sold in the market at present, the 3D colloid photon crystal pressure-sensitive adhesive has the advantages that:
(1) The color can be kept permanently
The pressure sensitive adhesive has a structural color, and the color is always kept as long as the colloid photon crystal layer structure of the adhesive tape is not changed compared with the pigment color formed by dye and pigment, so that the photo-bleaching and the oxidation of oxygen in the air do not need to be worried about.
(2) Green environmental protection
The pressure-sensitive adhesive with various colors is commercially available, the colors mainly come from pigment colors formed by dyes and pigments, the main components of the substances are heavy metal ions and organic conjugated small molecules, a large amount of three wastes are generated in the production and preparation process, and the environment is polluted. Compared with the 3D colloid photon crystal pressure sensitive adhesive with structural color developed by the invention, the color is not generated by using any dye or pigment, so the pressure sensitive adhesive is a more green and environment-friendly material.
Drawings
Fig. 1 is a schematic structural diagram of a 3D colloidal photonic crystal pressure sensitive adhesive having a structural color.
Fig. 2 is a photograph of the appearance of the 3d colloidal photonic crystal pressure sensitive adhesive.
Fig. 3d shows transmission spectra of the colloidal photonic crystal pressure sensitive adhesive at different angles.
Fig. 4 3d colloidal photonic crystal viscosity display.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments, so that those skilled in the art will more fully understand the present invention. The described embodiments are only some embodiments of the invention, and not all embodiments, and it should be noted that it should not be construed as limiting the scope of the invention, and that modifications and variations can be made by persons skilled in the art without departing from the principles of the invention, which are intended to be covered by the scope of the embodiments of the invention.
Example 1
The embodiment illustrates a preparation method of a blue-violet structural color pressure-sensitive adhesive based on a colloid photon crystal structure, wherein the thickness of a 3D colloid photon crystal layer of an intermediate layer is 15 microns, and the specific implementation process comprises the following steps:
1. synthesis of hard core soft shell microsphere
The 1T reaction kettle is heated to 85 ℃ and kept at constant temperature for 30 minutes, and meanwhile, condensed water is introduced. Adding 1 part by weight of sodium dodecyl sulfate, 18 parts by weight of styrene, 2 parts by weight of 1, 4-butanediol diacrylate and 990 parts by weight of deionized water into a reaction kettle, starting stirring, stirring for 5 minutes at a motor frequency of 18 Hz, adding 1 part by weight of sodium persulfate and 12.5 parts by weight of deionized water into the reaction kettle, and flushing a charging pipeline with 10 parts by weight of deionized water after adding. Keeping the temperature at 85 ℃ for 60 minutes, cooling to room temperature, filtering by filter cloth, and then finishing the preparation of the polystyrene seeds, and placing the polystyrene seeds in a charging barrel for later use.
0.16 weight part of sodium dodecyl sulfate, 0.64 weight part of sodium bicarbonate, 104 weight parts of deionized water, 225 weight parts of styrene, 10 weight parts of allyl methacrylate, 25 weight parts of 1, 4-butanediol diacrylate and 0.48 weight part of sodium persulfate are weighed and added into a pre-emulsification kettle, and the stirring motor frequency is 50 Hz, and stirring is carried out for 30 minutes to complete pre-emulsification. Adding 200 parts by weight of seed emulsion and 100 parts by weight of deionized water into a 1T reaction kettle, heating to 85 ℃, stirring at the motor frequency of 18 Hz, dripping the pre-emulsion into the reaction kettle within 150 minutes, and stirring for 30 minutes at the temperature of the dripping completion to obtain the polystyrene hard core microsphere emulsion.
2 parts by weight of sodium dodecyl sulfate, 160 parts by weight of deionized water, 250 parts by weight of butyl acrylate, 25 parts by weight of hydroxyethyl acrylate and 8 parts by weight of acrylic acid are added into a pre-emulsification reaction kettle, and the stirring motor frequency is 50 and Hz, and stirring is carried out for 30 minutes to complete pre-emulsification. The reaction kettle in the previous step 1, T, is cooled to 75 ℃, and the pre-emulsion is dripped within 180 minutes, and meanwhile, 0.25 weight part of sodium bisulphite and 4 weight parts of deionized water are added. After the dripping is finished, the reaction is continued for 30 minutes under the condition of heat preservation, the mixture is cooled to the room temperature, and the mixture is filtered by filter cloth, so that the preparation of the hard core soft shell microsphere emulsion with the solid content of 47 percent can be completed.
2. Preparation of coating liquid
100 parts by weight of hard core soft shell microsphere emulsion, 12.5 parts by weight of diethylene glycol dimethacrylate, 12.5 parts by weight of hydroxybutyl acrylate, 0.2 part by weight of trimethylolpropane triacrylate, 0.2 part by weight of acryloylmorpholine, 0.2 part by weight of 1, 4-butanediol diacrylate, 0.63 part by weight of benzophenone and 0.63 part by weight of EDAP are fully stirred, a leveling agent and a wetting agent are added while stirring, 30 parts by weight of deionized water is supplemented, and the preparation of the coating liquid is completed after fully stirring for 30 minutes.
3.3 regularity of colloidal photonic crystal layer
By gravure coating, the relevant parameters were 1300 mm,45 ° diagonal, 70 mesh, speed ratio 1.3. The prepared coating liquid is quantitatively transferred onto a release PET film through micro-concave coating, and after being dried by a 60 ℃ oven, a layer of polyethylene terephthalate (PET) film is covered, and the release PET film passes through bending induction shearing equipment at the speed of 1.5 m/min, and the relative sliding of the PET layer is generated, so that the soft substrate is driven to move, and the shearing hard microspheres are regularly arranged. And (3) performing ultraviolet crosslinking for 3 minutes, and performing thermal crosslinking at 75 ℃ for 3 minutes to finish the regulation and preparation of the 3D colloid photon crystal layer.
4. Coating of pressure sensitive adhesive layer
(1) Preparation of polyacrylate pressure-sensitive adhesive emulsion
495 parts by weight of isooctyl acrylate, 5 parts by weight of acrylic acid, 1 part by weight of sodium bicarbonate, 4.3 parts by weight of sodium dodecyl sulfate and 180 parts by weight of deionized water are fully emulsified to obtain a pre-emulsion. The reaction kettle bottom is heated to 85 ℃, 15 parts by weight of pre-emulsion, 185 parts by weight of deionized water and 0.5 part by weight of sodium bicarbonate are added, after the temperature is stabilized, 0.5 part by weight of sodium persulfate is added into the pre-emulsion, and the pre-emulsion is added into the reaction kettle within 3.5 hours. After the dripping is finished, the material pipe is washed by 50 parts by weight of deionized water, the temperature is reduced to room temperature after the heat preservation is carried out for 30 minutes, and then ammonia water is added to adjust the pH value to 7-8, thus the preparation of the pressure-sensitive adhesive emulsion is completed.
(2) Coating of polyacrylate pressure sensitive adhesive emulsion
Tearing off a layer of PET film on the surface layer of the composite film prepared in the third step, then coating by micro-concave (the related parameters are 1300 mm,45 DEG twill, 70 meshes and the speed ratio is 1.3), transferring the pressure-sensitive adhesive emulsion onto the 3D colloid photon crystal layer, and drying by a baking oven at the temperature of 45 ℃ to prepare the 3D colloid photon crystal pressure-sensitive adhesive.
The structure of the prepared colloidal photonic crystal pressure-sensitive adhesive is shown in figure 1; as shown in fig. 2, the appearance color is bluish violet; according to transmission spectrum tests of different angles, the colloid photon crystal pressure-sensitive adhesive has an effect of changing color with angle; the tackiness of such a pressure-sensitive adhesive is shown in fig. 4.
The prepared photonic crystal pressure-sensitive adhesive adopts a rolling ball method to test initial adhesion, and the initial adhesion is 14#; 180 DEG stripping is tested by adopting a tensile machine, and the stripping force is 200 g; the retention force is 10 h by using a 1 kg weight test; can be used as a protective film and a warning film.
Example 2
The embodiment illustrates a preparation method of a blue-violet structural color pressure-sensitive adhesive based on a colloidal photonic crystal structure, wherein the thickness of a 3D colloidal photonic crystal layer of an intermediate layer is 15 micrometers, and in the preparation of a coating liquid, the adopted method is as follows:
100 parts by weight of hard core soft shell microsphere emulsion, 12.5 parts by weight of diethylene glycol dimethacrylate, 10 parts by weight of hydroxypropyl methacrylate, 2.5 parts by weight of methacrylic acid, 0.2 part by weight of trimethylolpropane triacrylate, 0.2 part by weight of 4-tert-butylcyclohexyl acrylate, 0.2 part by weight of divinylbenzene, 0.63 part by weight of diphenoxybenzophenone and 0.63 part by weight of alpha-hydroxyacetophenone are fully stirred, a leveling agent and a wetting agent are added while stirring, 30 parts by weight of deionized water is supplemented, and the preparation of the coating liquid is completed after fully stirring for 30 minutes. The rest of the preparation method is the same as in example 1.
The prepared photonic crystal pressure-sensitive adhesive adopts a rolling ball method to test initial adhesion, and the initial adhesion is 14#; 180 DEG stripping is tested by adopting a tensile machine, and the stripping force is 200 g; the retention force is measured by a 1 kg weight, and the retention force is 12 h; can be used as a protective film and a warning film.
Example 3
The embodiment illustrates a preparation method of a green structural color pressure-sensitive adhesive based on a colloid photon crystal structure, wherein the thickness of a 3D colloid photon crystal layer in an intermediate layer is 15 microns, and in the synthesis step of hard core soft shell microspheres, when the polystyrene hard microspheres are synthesized, the adopted method is as follows:
0.16 weight part of sodium dodecyl sulfate, 0.64 weight part of sodium bicarbonate, 104 weight parts of deionized water, 225 weight parts of styrene, 35 weight parts of 1, 4-butanediol diacrylate and 0.48 weight part of sodium persulfate are weighed and added into a pre-emulsification kettle, the frequency of a stirring motor is 50 and Hz, and the stirring is carried out for 30 minutes to complete pre-emulsification. Firstly adding 140 parts by weight of seed emulsion and 100 parts by weight of deionized water into a 1T reaction kettle, heating to 85 ℃, stirring at the motor frequency of 18 Hz, dripping the pre-emulsion into the reaction kettle within 150 minutes, and after dripping, preserving heat and stirring for 30 minutes to obtain the polystyrene hard core microsphere emulsion.
The rest of the preparation method is the same as in example 1. The pressure sensitive adhesive performance test index was the same as in example 1.
Example 4
The embodiment illustrates a preparation method of a red structural color pressure-sensitive adhesive based on a colloid photon crystal structure, wherein the thickness of a 3D colloid photon crystal layer in an intermediate layer is 15 microns, and in the synthesis step of hard core soft shell microspheres, when the polystyrene hard microspheres are synthesized, the adopted method is as follows:
0.2 weight part of sodium dodecyl sulfate, 0.7 weight part of sodium bicarbonate, 104 weight parts of deionized water, 225 weight parts of styrene, 18 weight parts of allyl methacrylate, 18 weight parts of 1, 4-butanediol diacrylate and 0.48 weight part of sodium persulfate are weighed and added into a pre-emulsification kettle, and the stirring motor frequency is 50 Hz, and stirring is carried out for 30 minutes to complete pre-emulsification. 120 parts by weight of seed emulsion and 100 parts by weight of deionized water are firstly added into a reaction kettle of 1T, the temperature is raised to 85 ℃, the frequency of a stirring motor is 18 Hz, the pre-emulsion is dripped into the reaction kettle within 150 minutes, and the temperature is kept and the stirring is carried out for 30 minutes after the dripping is finished, so that the polystyrene hard core microsphere emulsion can be obtained.
The rest of the preparation method is the same as in example 1. The pressure sensitive adhesive performance test index was the same as in example 1.
Example 5
The embodiment illustrates a preparation method of a blue-violet structural color pressure-sensitive adhesive based on a colloidal photonic crystal structure, wherein the thickness of a 3D colloidal photonic crystal layer of an intermediate layer is 18 microns, and in the preparation process of a coating liquid, the adopted method is as follows:
115 parts by weight of hard core soft shell microsphere emulsion, 12.5 parts by weight of diethylene glycol dimethacrylate, 12.5 parts by weight of hydroxybutyl acrylate, 0.2 part by weight of trimethylolpropane triacrylate, 0.2 part by weight of acryloylmorpholine, 0.2 part by weight of 1, 4-butanediol diacrylate, 0.63 part by weight of benzophenone and 0.63 part by weight of EDAP are fully stirred, a leveling agent and a wetting agent are added while stirring, 15 parts by weight of deionized water is supplemented, and the mixture is fully stirred for 30 minutes, so that the preparation of the coating liquid is completed.
The rest of the preparation method is the same as in example 1.
The prepared photonic crystal pressure-sensitive adhesive adopts a rolling ball method to test initial adhesion, and the initial adhesion is 14#; 180 DEG stripping is tested by adopting a tensile machine, and the stripping force is 300 g; the retention force is measured by a 1 kg weight, and the retention force is 18 h; can be used as a process protective film with large adhesive force and cohesion.
Example 6
The embodiment illustrates a preparation method of a blue-violet structural color pressure-sensitive adhesive based on a colloidal photonic crystal structure, wherein the thickness of a 3D colloidal photonic crystal layer of an intermediate layer is 7 microns, and in the preparation process of a coating liquid, the adopted method is as follows:
100 parts by weight of hard core soft shell microsphere emulsion, 12.5 parts by weight of diethylene glycol dimethacrylate, 12.5 parts by weight of hydroxybutyl acrylate, 0.2 part by weight of trimethylolpropane triacrylate, 0.2 part by weight of acryloylmorpholine, 0.2 part by weight of 1, 4-butanediol diacrylate, 0.63 part by weight of benzophenone and 0.63 part by weight of EDAP are fully stirred, a leveling agent and a wetting agent are added while stirring, 60 parts by weight of deionized water is supplemented, and the mixture is fully stirred for 30 minutes, so that the preparation of a coating liquid is completed.
The rest of the preparation method is the same as in example 1.
The prepared photonic crystal pressure-sensitive adhesive adopts a rolling ball method to test initial adhesion, and the initial adhesion is 14#; 180-degree stripping is tested by adopting a tensile machine, and the stripping force is 150-200 g; the retention force is measured by a 1 kg weight, and the retention force is 6 h; can be used as a protective film and a warning film.
Comparative example 1
The method for preparing the colloidal photonic crystal pressure-sensitive adhesive according to the comparative example was identical to that of example 1 in the regulation of the colloidal photonic crystal layer and the coating of the pressure-sensitive adhesive layer, except that the method used in the synthesis of the hard core soft shell microsphere emulsion was: the 1T reaction kettle is heated to 85 ℃ and kept at constant temperature for 30 minutes, and meanwhile, condensed water is introduced. 1 part by weight of sodium dodecyl sulfate, 18 parts by weight of styrene, 2 parts by weight of divinylbenzene, 990 parts by weight of deionized water are added into a reaction kettle, stirring is started, the motor frequency is 18 and Hz, after stirring for 5 minutes, 1 part by weight of sodium persulfate and 12.5 parts by weight of deionized water are added into the reaction kettle, and after the addition, the addition pipeline is flushed with 10 parts by weight of deionized water. Keeping the temperature at 85 ℃ for 60 minutes, cooling to room temperature, filtering by filter cloth, and then finishing the preparation of the polystyrene seeds, and placing the polystyrene seeds in a charging barrel for later use. 0.16 weight part of sodium dodecyl sulfate, 0.64 weight part of sodium bicarbonate, 104 weight parts of deionized water, 225 weight parts of styrene, 35 weight parts of divinylbenzene and 0.48 weight part of sodium persulfate are weighed and added into a pre-emulsification kettle, and the stirring motor frequency is 50 and Hz, and stirring is carried out for 30 minutes to complete pre-emulsification. 160 parts by weight of seed emulsion and 100 parts by weight of deionized water are firstly added into a 1T reaction kettle, the temperature is raised to 85 ℃, the frequency of a stirring motor is 18 Hz, the pre-emulsion is dripped into the reaction kettle within 150 minutes, and the temperature is kept and the stirring is carried out for 30 minutes after the dripping is finished, so that the polystyrene hard core microsphere emulsion can be prepared.
In the preparation of the coating liquid, the method adopted is as follows: 100 parts by weight of hard core soft shell microsphere emulsion, 0.63 part by weight of benzophenone and 0.63 part by weight of EDAP are fully stirred, a leveling agent and a wetting agent are added while stirring, 30 parts by weight of deionized water is supplemented, and the fully stirred is carried out for 30 minutes, so that the preparation of the coating liquid is completed.
Compared with the embodiment 1, the colloid photon crystal pressure-sensitive adhesive prepared by the method is different in that more residues appear in the process of coating, the colloid photon crystal layer cannot form a film, the color development degree is extremely poor, more defects appear, and the pressure-sensitive adhesive is difficult to use.
Comparative example 2
The method for preparing the colloidal photonic crystal pressure-sensitive adhesive according to the comparative example was carried out in the synthesis of hard core soft shell microspheres, and the regularity of the colloidal photonic crystal layer and the coating of the pressure-sensitive adhesive layer were the same as those of example 1, except that the acrylate functional monomer was not added in the preparation of the coating liquid.
Compared with comparative example 1, the colloid photon crystal pressure sensitive adhesive prepared by the method has improved film forming property, but compared with example 1, more shrinkage cavities still appear, and the actual use is affected.
Comparative example 3
The method for preparing the colloidal photonic crystal pressure-sensitive adhesive according to the comparative example was carried out in the synthesis of hard core soft shell microspheres, the regularity of the colloidal photonic crystal layer and the coating of the pressure-sensitive adhesive layer were the same as those of example 1, except that thermal crosslinking and ultraviolet crosslinking were not carried out at the time of preparation of the coating liquid.
The colloidal photonic crystal pressure-sensitive adhesive prepared according to the method is different from example 1 in that the strength of the colloidal photonic crystal layer of the pressure-sensitive adhesive is poor.

Claims (9)

1. The 3D colloid photon crystal pressure-sensitive adhesive with vivid structural color is characterized by comprising a three-layer structure, a substrate layer, a 3D colloid photon crystal layer and a pressure-sensitive adhesive layer from bottom to top; wherein:
in the 3D colloid photon crystal layer, hard construction units are orderly arranged in a continuous phase matrix, and a bright structural color is generated by forming a photon forbidden band to reflect visible light with specific wavelength;
the 3D colloid photon crystal layer is prepared by firstly synthesizing hard core and soft shell microspheres composed of hard core microspheres and soft shell layers, and then regularly arranging the hard core microspheres in a continuous phase matrix formed by melting the soft shell layers through regular shearing induction; the hard core microsphere is used as a hard construction unit, and the material of the hard core microsphere is one or a mixture of a plurality of crosslinked polymers, organic-inorganic or inorganic materials with glass transition temperature Tg of more than 110 ℃; the soft shell layer is made of uncrosslinked polymer and is composed of polyacrylate functional copolymer, so that the binding force of the 3D colloid photon crystal layer, the substrate layer and the pressure-sensitive adhesive layer is improved; wherein: the monomer adopted in the synthesis of the soft shell layer is more than two of styrene, 1, 4-butanediol diacrylate, allyl methacrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, acrylic acid, diethylene glycol dimethacrylate and hydroxybutyl acrylate, wherein the mass fraction of the hydroxyl-containing acrylic ester monomer accounts for more than 10% of the mass fraction of the hard core soft shell microsphere;
the pressure-sensitive adhesive layer is formed by coating and drying polyacrylate pressure-sensitive adhesive emulsion;
the specific preparation steps of the 3D colloid photon crystal pressure-sensitive adhesive with vivid structural color are as follows:
s1, preparing hard core soft shell microspheres by adopting semi-continuous multi-step seed emulsion polymerization, wherein the reaction temperature is 70-95 ℃ and the reaction time is 5-20 hours;
s2, mixing the hard core soft shell microsphere emulsion with a functional monomer, a cross-linking agent, an auxiliary agent and deionized water to obtain a coating liquid;
s3, coating the coating liquid on a substrate, drying, then covering a release film, and continuously bending and inducing shearing the obtained composite film to enable the hard construction units to be regularly arranged in a matrix, and fixing the arrangement of the construction units through thermal crosslinking and photo crosslinking;
s4, tearing off the surface release film from the regular film, coating pressure-sensitive adhesive emulsion, and drying to obtain photonic crystal pressure-sensitive adhesive; wherein:
in the step S2, the adopted functional monomer is selected from more than two of 1, 4-butanediol diacrylate, allyl methacrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, acrylic acid, diethylene glycol dimethacrylate, hydroxybutyl acrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, 4-tert-butylcyclohexyl acrylate and acryloylmorpholine, wherein the mass fraction of the hydroxyl-containing acrylate monomer accounts for more than 10% of the mass fraction of the hard core-shell microsphere;
in the step S2, the cross-linking agent is a mixed cross-linking agent of thermal cross-linking and photo-cross-linking, wherein the thermal cross-linking agent is one or a mixture of more than two of divinylbenzene, 1, 4-butanediol diacrylate, 1, 6-hexanediol dimethacrylate and allyl methacrylate, and the photo-cross-linking agent is a mixture of more than two of benzoin ethers, acetophenones, acyl phosphine oxides, benzophenones, hexaxanthones and coumarin; the hard core soft shell microsphere emulsion comprises the following raw materials in parts by weight: 45-75 parts; functional monomer: 10-20 parts of a lubricant; auxiliary agent: 0.5-2.5 parts; crosslinking agent: 0.5-2.5 parts;
in the step S4, the pressure-sensitive adhesive emulsion is polyacrylate pressure-sensitive adhesive emulsion.
2. The 3D colloidal photonic crystal pressure sensitive adhesive according to claim 1, wherein the hard core microspheres are made of one or more of polystyrene, polymethyl methacrylate, polyacrylonitrile, silica, and cadmium sulfide.
3. The 3D colloidal photonic crystal pressure sensitive adhesive according to claim 1, wherein the average particle size of the hard core soft shell microspheres is 50 to 1000 nanometers, and the particle size distribution coefficient is less than 0.1.
4. The 3D colloidal photonic crystal pressure-sensitive adhesive according to claim 1, wherein in the hard core and soft shell microspheres, the hard core microspheres account for 30% -60% of the total mass of the hard core and soft shell microspheres, and the soft shell layer is stably coated around the hard core microspheres in a covalent bond form and accounts for 40% -70% of the total mass of the hard core and soft shell microspheres.
5. The 3D colloidal photonic crystal pressure sensitive adhesive according to claim 1, wherein the substrate layer is made of one of polyethylene terephthalate film PET, low density polyethylene film LDPE, high density polyethylene film HDPE, biaxially oriented polypropylene film BOPP, nylon film PA or polyurethane film PU.
6. The 3D colloidal photonic crystal pressure sensitive adhesive according to claim 1, wherein the thickness thereof is 100 to 300 μm; wherein the thickness of the substrate layer is 70-200 micrometers, the thickness of the 3D colloid photon crystal layer is 5-40 micrometers, and the thickness of the pressure-sensitive adhesive layer is 5-60 micrometers.
7. The method for preparing the 3D colloidal photonic crystal pressure-sensitive adhesive according to claim 1, wherein the specific preparation steps are as follows:
s1, preparing hard core soft shell microspheres by adopting semi-continuous multi-step seed emulsion polymerization, wherein the reaction temperature is 70-95 ℃ and the reaction time is 5-20 hours;
s2, mixing the hard core soft shell microsphere emulsion with a functional monomer, a cross-linking agent, an auxiliary agent and deionized water to obtain a coating liquid;
s3, coating the coating liquid on a substrate, drying, then covering a release film, and continuously bending and inducing shearing the obtained composite film to enable the hard construction units to be regularly arranged in a matrix, and fixing the arrangement of the construction units through thermal crosslinking and photo crosslinking;
s4, tearing off the surface release film from the regular film, coating pressure-sensitive adhesive emulsion, and drying to obtain photonic crystal pressure-sensitive adhesive; wherein:
in the step S2, the adopted functional monomer is selected from more than two of 1, 4-butanediol diacrylate, allyl methacrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, acrylic acid, diethylene glycol dimethacrylate, hydroxybutyl acrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, 4-tert-butylcyclohexyl acrylate and acryloylmorpholine, wherein the mass fraction of the hydroxyl-containing acrylate monomer accounts for more than 10% of the mass fraction of the hard core-shell microsphere;
in the step S2, the cross-linking agent is a mixed cross-linking agent of thermal cross-linking and photo-cross-linking, wherein the thermal cross-linking agent is one or a mixture of more than two of divinylbenzene, 1, 4-butanediol diacrylate, 1, 6-hexanediol dimethacrylate and allyl methacrylate, and the photo-cross-linking agent is a mixture of more than two of benzoin ethers, acetophenones, acyl phosphine oxides, benzophenones, hexaxanthones and coumarin; the hard core soft shell microsphere emulsion comprises the following raw materials in parts by weight: 45-75 parts; functional monomer: 10-20 parts of a lubricant; auxiliary agent: 0.5-2.5 parts; crosslinking agent: 0.5-2.5 parts;
in the step S4, the pressure-sensitive adhesive emulsion is polyacrylate pressure-sensitive adhesive emulsion.
8. The method for preparing the 3D colloid photon crystal pressure sensitive adhesive according to claim 7, wherein the used auxiliary agent comprises wetting agent and leveling agent.
9. The method for preparing a 3D colloidal photonic crystal pressure-sensitive adhesive according to claim 7, wherein in the step S3, the thermal crosslinking temperature is 60 to 75 ℃.
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