CN106433609B - Color-changing product, preparation method and application thereof - Google Patents

Color-changing product, preparation method and application thereof Download PDF

Info

Publication number
CN106433609B
CN106433609B CN201610807924.1A CN201610807924A CN106433609B CN 106433609 B CN106433609 B CN 106433609B CN 201610807924 A CN201610807924 A CN 201610807924A CN 106433609 B CN106433609 B CN 106433609B
Authority
CN
China
Prior art keywords
color
weight
parts
mol
changing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610807924.1A
Other languages
Chinese (zh)
Other versions
CN106433609A (en
Inventor
黄肃明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wenzhou Fuqishi Photoelectric Material Co ltd
Original Assignee
Wenzhou Fuqishi Photoelectric Material Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wenzhou Fuqishi Photoelectric Material Co ltd filed Critical Wenzhou Fuqishi Photoelectric Material Co ltd
Priority to CN201610807924.1A priority Critical patent/CN106433609B/en
Publication of CN106433609A publication Critical patent/CN106433609A/en
Application granted granted Critical
Publication of CN106433609B publication Critical patent/CN106433609B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/20—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/10—Filters, e.g. for facilitating adaptation of the eyes to the dark; Sunglasses
    • G02C7/102—Photochromic filters
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/244—All polymers belonging to those covered by group B32B27/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/12—Mixture of at least two particles made of different materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom

Landscapes

  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Ophthalmology & Optometry (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Theoretical Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to the technical field of optical elements, and particularly discloses a color-changing product, which at least comprises a base material; and a color-changing film; the base material and the color-changing film are connected by melting or by an adhesive; the color-changing film includes at least a base resin and a photochromic compound. The color-changing product of the invention has better weather resistance and longer service life.

Description

Color-changing product, preparation method and application thereof
Technical Field
The invention relates to the technical field of optical elements, in particular to a color-changing product, a preparation method and application thereof.
Background
The color-changing material is a novel optical functional material, can be quickly changed into various colors such as red, green, blue, purple and the like from colorless or light color under the irradiation of sunlight or other light sources, can return to the original state after being irradiated by another light source or shielded from light, and can be repeatedly and reversibly changed. The research of the color-changing material is continuously expanded and deepened in recent years, and the application of the photochromic material is more and more extensive. In recent years, photochromic materials gradually come out of high and new technical fields of optical information storage and the like of traditional application, and brand-new corners are exposed in the civil field, so that the magic efficacy of the photochromic materials is shown.
In recent years, the color-changing products have attracted wide attention at home and abroad, and the interest in various fields is caused by the following reasons: the photochromic material has photochromic photosensitive performance under the irradiation of light with different intensities and wavelengths, and is used as a common decoration and packaging material in industry and also used for protecting the damage of intense light radiation such as a nuclear explosion test and the like to human eyes and human bodies; secondly, because of the reversible cycle change performance under the irradiation of light with different intensities and wavelengths, the optical shutter can be made into various optical shutters, recording media and information storage elements in computers, especially provides various necessary light intensities after laser appears, and further promotes the application of the optical shutter in information data systems; thirdly, the color of the product is sensitive to heat of different degrees, and the product can be used as temperature indication to control chemical polymerization reaction; fourthly, the material has specific color-changing performance and is mainly used as an anti-counterfeiting and counterfeit identification material in recent years.
In addition, the application of the color-changing material in the fields of self-developing photosensitive films, holographic materials, anti-counterfeiting identification technology, military hidden camouflage materials and the like is increasing day by day, and the market prospect is considerable.
The existing color-changing products are generally obtained by directly coating a color-changing coating on the surface of a substrate, and the color-changing film is very unstable and easy to damage, so that technical improvement is needed to obtain a color-changing product with excellent aging resistance for long-term use.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a color-changing article comprising at least,
a substrate; and
a color-changing film;
the base material and the color-changing film are connected by melting or by an adhesive;
the color-changing film includes at least a base resin and a photochromic compound.
In a preferred embodiment, the substrate and the base resin may be the same or different and each is independently selected from at least one of polycarbonate, amorphous copolyester, polyamide, polyethylene terephthalate, copolymer of norbornene and ethylene, cellulose acetate butyrate, cellulose triacetate, polyurethane-based polymer, amino resin-based polymer, and acrylate-based polymer.
In a preferred embodiment, the polyurethane-based polymer includes a polycarbonate polyurethane.
In a preferred embodiment, the adhesive is selected from at least one of a (meth) acrylate-based adhesive, an epoxy-based adhesive, a polyurethane-based adhesive, and a polyimide-based adhesive.
In a preferred embodiment, the adhesive is an acrylate adhesive, and the acrylate adhesive is prepared from the following raw materials:
100 parts by weight of an acrylate copolymer;
0.01 to 20 parts by weight of an ester plasticizer;
0.001 to 7 parts by weight of an alkali metal salt;
0.01-10 parts by weight of aminosilane-modified beta-cyclodextrin-graphene oxide-polybenzimidazole compound and
0.01-10 parts by weight of epoxy-terminated polyetheramine.
In a preferred embodiment, the color-changing film comprises at least
100 parts by weight of a base resin; and
0.1-30 parts by weight of photochromic compound.
In a preferred embodiment, the photochromic compound is selected from: any one of naphthopyrans, benzopyrans, indolopyrans, phenanthropyrans and spiropyrans.
The second aspect of the present invention provides a method for preparing the color-changing article, comprising the following steps:
providing a substrate and a color-changing film;
wherein the base material and the base resin are the same;
and (3) bonding the base material and the color-changing film in a melting mode.
In a third aspect, the present invention provides a method for preparing the color-changing article, comprising the steps of:
providing a substrate and a color-changing film;
wherein, the base material and the base resin are different;
and at least partially covering the upper surface of the base material with an adhesive to ensure that the base material is attached with the color-changing film.
A fourth aspect of the present invention provides use of the color changing film in eyeglasses, a display device or a communication device.
The above-described and other features, aspects, and advantages of the present application will become more apparent with reference to the following detailed description.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1: example 1 a schematic representation of the resulting color-changing article is obtained,
wherein, 1 represents a color-changing film, and 2 represents a substrate;
FIG. 2: a schematic representation of the color-changing article obtained in example 10,
wherein, 3 represents a color-changing film, and 4 represents an adhesive; and 5 represents a substrate.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. In the following specification and claims, reference will be made to a number of terms which shall be defined to have the following meanings.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.
"optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
The expression a range includes all integers within the range as well as fractions thereof. The expression a range also includes the endpoints of the range, regardless of whether the range indicates a value that is "within" or "between" or "the" some of the stated values. Ranges stated in this disclosure and the claims are intended to specifically include the full range and not just one or more endpoints. For example, a stated range of 0 to 10 is intended to disclose all integers between 0 and 10, e.g., 1,2, 3, 4, etc., all fractions between 0 and 10, e.g., 1.5, 2.3, 4.57, 6.1113, etc., and the endpoints 0 and 10.
As used herein, the term "photochromic" and similar terms, such as "photochromic compound," mean having an absorption spectrum for at least visible light that changes in response to the absorption of at least actinic radiation. Furthermore, as used herein, the term "photochromic material" means any substance that is suitable to exhibit photochromic properties (i.e., that is suitable to have an absorption spectrum for at least visible light that is variable in response to at least the absorption of actinic radiation) and that comprises at least one photochromic compound.
As used herein, the term "photochromic compound" includes both thermally reversible photochromic compounds and non-thermally reversible photochromic compounds. As used herein, the term "thermally reversible photochromic compound/material" refers to a compound/material that is capable of transforming from a first state, e.g., "clear state", to a second state, e.g., "colored state", in response to actinic radiation, and reverting back to the first state in response to thermal energy. As used herein, the term "non-thermally reversible photochromic compound/material" means a compound/material that is capable of converting from a first state, e.g., "clear state," to a second state, e.g., "colored state," in response to actinic radiation, and reverts back to the first state (e.g., ceases exposure to such actinic radiation) in response to actinic radiation of substantially the same wavelength as the absorption of the colored state.
As used herein, the term "sheet" means a preformed film having a generally uniform thickness and being capable of being self-sustaining.
As used herein, the term "polymer" means homopolymers (e.g., prepared from a single monomeric species), copolymers (e.g., prepared from at least two monomeric species), and graft polymers.
As used herein, the term "(meth) acrylate" and similar terms such as "(meth) acrylate" refer to methacrylates and/or acrylates. As used herein, the term "(meth) acrylic" means methacrylic and/or acrylic.
As used herein, the term "copolyester" is understood to mean a synthetic polymer prepared by the polycondensation of one or more difunctional carboxylic acids with two more difunctional hydroxyl compounds. Typically, the difunctional carboxylic acid is a dicarboxylic acid and the difunctional hydroxyl compound is a diol, such as, for example, glycols and diols.
As used herein, the term "residue" refers to any organic structure introduced into a polymer by a polycondensation reaction involving the corresponding monomer. As used herein, the term "repeating unit" denotes an organic structure having a dicarboxylic acid residue and a diol residue bonded via a carbonyloxy group. Thus, the dicarboxylic acid residues may be derived from acid halides, esters, salts, anhydrides, or mixtures thereof of dicarboxylic acid monomers or combinations thereof. Thus, as used herein, the term dicarboxylic acid is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, in combination, that can be used in a polycondensation process with a diol to produce a high molecular weight copolyester.
In the present invention, the "color-changing article" can be made into films, sheets, blocks, coatings, and the like.
In order to solve the above problems, a first aspect of the present invention provides a color-changing article comprising at least,
a substrate; and
a color-changing film;
the base material and the color-changing film are connected by melting or by an adhesive;
the color-changing film includes at least a base resin and a photochromic compound.
Base material and base resin
In the present invention, the plastic used for forming the substrate of the present application is not particularly limited, and may be commercially available or experimentally synthesized.
The substrate and the base resin may be the same or different and each is independently selected from at least one of polycarbonate, amorphous copolyester, polyamide, polyethylene terephthalate, copolymer of norbornene and ethylene, cellulose acetate butyrate, cellulose triacetate, polyurethane-based polymer, amino resin-based polymer, and acrylate-based polymer.
The amorphous copolyester of the present invention means that the polyester substantially comprises disordered regions of the polymer. Amorphous copolyesters generally have no melting point.
The amorphous copolyesters of the invention exhibit a glass transition temperature (abbreviated herein as "Tg") of at least 90 ℃ as measured by well-known techniques, such as, for example, differential scanning calorimetry ("DSC"), using TA DSC 2920 from TA Instruments at a scan rate of 20 ℃/min.
Desirably, the Tg of the amorphous copolyester exhibits a Tg of at least 92 ℃, or at least 94 ℃, or at least 96 ℃, or at least 98 ℃, or at least 100 ℃, or at least 102 ℃, or at least 104 ℃, or at least 106 ℃, or at least 108 ℃, or at least 110 ℃, or at least 112 ℃, or at least 144 ℃, or at least 116 ℃, or at least 118 ℃, or at least 120, and at most 185 ℃, or at most less than 170 ℃, or at most 160 ℃, or less than 150 ℃, or less than 140 ℃, or less than 138 ℃, or less than 136 ℃, or less than 134 ℃, or less than 132 ℃, or less than 130 ℃, or less than 128 ℃, or less than 126 ℃, or less than 124 ℃, or less than 122 ℃, or less than 120 ℃, or less than 118 ℃, or less than 116 ℃.
Examples of ranges include from 90 to 185 ℃; 90 to 180 ℃; 90 to 170 ℃; 90 to 160 ℃; 90 to 155 ℃; 90 to 150 ℃; from 90 to 145 ℃; from 90 to 140 ℃; 90 to 138 ℃; 90 to 135 ℃; 90 to 130 ℃; 90 to 125 ℃; 90 to 120 ℃; from 90 to 115 ℃; from 90 to 110 ℃; from 90 to 105 ℃; 90 to 100 ℃; 90 to 95 ℃; from 92 to 185 ℃; 92 to 180 ℃; 92 to 170 ℃; 92 to 160 ℃; 92 to 155 ℃; 92 to 150 ℃; from 92 to 145 ℃; 92 to 140 ℃; 92 to 138 ℃; from 92 to 136 ℃; 92 to 134 ℃; from 92 to 132 ℃; 92 to 130 ℃; from 92 to 128 ℃; 92 to 126 ℃; 92 to 124 ℃; 100 to 185 ℃; 100 to 160 ℃; 100 to 150 ℃; 100 to 145 ℃; 100 to 140 ℃; 100 to 138 ℃; 100 to 136 ℃; 100 to 134 ℃; 100 to 132 ℃; 100 to 130 ℃; 100 to 128 ℃; 100 to 126 ℃; 105 to 185 ℃; 105 to 160 ℃; 105 to 150 ℃; 105 to 145 ℃; 105 to 140 ℃; 105 to 136 ℃; 105 to 132 ℃; 105 to 128 ℃; 110 to 185 ℃; 110 to 160 ℃; 110 to 150 ℃; 110 to 145 ℃; 110 to 140 ℃; 110 to 136 ℃; 110 to 132 ℃; and a Tg in the range of 110 to 128 ℃.
Preferably, the amorphous copolyester polymer of the present invention contains alkylene terephthalate repeat units in the polymer chain.
The amorphous copolyester may be prepared by reacting NPG and TACD with terephthalic acid C1-C4Dialkyl esters are reacted to produce ester monomers and/or oligomers, which are then polycondensed to produce copolyesters. More than one compound containing one or more carboxylic acid groups or one or more derivatives thereof may be reacted during the process. All compounds containing one or more carboxylic acid groups or one or more derivatives thereof entering the process that become part of the copolyester product constitute the "acid component". The "residue" of the one or more compounds containing one or more carboxylic acid groups or one or more derivatives thereof means the portion of the one or more compounds remaining in the copolyester product after all of the compounds have condensed and polycondensed to form copolyester polymer chains of varying lengths.
More than one compound containing one or more hydroxyl groups or derivatives thereof may become part of one or more copolyester polymer products. All compounds containing one or more hydroxyl groups or derivatives thereof that become part of the process of the one or more copolyester products constitute the hydroxyl component. The residue of the one or more hydroxy-functional compounds or derivatives thereof which becomes part of the copolyester product represents the portion of the one or more compounds remaining in the copolyester product after condensation with the one or more compounds containing one or more carboxylic acid groups or one or more derivatives thereof and further polycondensation to form copolyester polymer chains of different lengths.
The mol% of hydroxyl residues and carboxylic acid residues in the one or more products can be determined by proton NMR or gas chromatography.
Preferably, the amorphous copolyester polymer comprises:
(a) an acid component comprising at least 80 mole%, or at least 85 mole%, or at least 90 mole%, or at least 92 mole%, or at least 96 mole% of terephthalic acid, or desirably the C of terephthalic acid1-C4A residue of a dialkyl ester, or in any event at least 85 mol%, or at least 90 mol%, or at least 92 mol%, or at least 96 mol% of terephthalate units comprising a-c (O) O-group bonded to an aromatic ring; and
(b) a hydroxyl component comprising at least 85 mol%, or at least 90 mol%, or at least 92 mol%, or at least 96 mol% of the residues of TACD and NPG;
based on 100 mole% of acid component residues and 100 mole% of hydroxyl component residues in the copolyester polymer.
The reaction of the acid component with the hydroxyl component to prepare the copolyester polymer is not limited to the mole percentages, as an excess of the hydroxyl component may be added during manufacture. However, the copolyester polymer produced by the reaction will contain the stated amounts of acid component and hydroxyl component.
Derivatives of terephthalic acid include terephthalic acid C1-C4Dialkyl esters, such as dimethyl terephthalate. Desirably, the amount of acid component is C of terephthalic acid1-C4Dialkyl esters, or dimethyl terephthalate.
C for removing terephthalic acid and terephthalic acid1-C4In addition to dialkyl esters, TACD and NPG, other acid components and hydroxyl components may be used as modifiers, as long as the Tg of the polymer is maintained at a level of at least 90 ℃.
Examples of acid modifiers include aromatic dicarboxylic acids, preferably having 8 to 14 carbon atoms, aliphatic dicarboxylic acids, preferably having 4 to 12 carbon atoms, or cycloaliphatic dicarboxylic acids, preferably having 8 to 12 carbon atoms. More specific examples of dicarboxylic acids that can be used as modifiers for the one or more acid components are phthalic acid, isophthalic acid, naphthalene-2, 6-dicarboxylic acid, cyclohexane-1, 4-dicarboxylic acid, cyclohexanediacetic acid, diphenyl-4, 4' -dicarboxylic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, sulfoisophthalic acid, fumaric acid, maleic acid, itaconic acid, 1, 3-cyclohexanedicarboxylic acid, diglycolic acid, 2, 5-norbornanedicarboxylic acid, bibenzoic acid, 4' -oxydibenzoic acid, 4' -sulfonyldibenzoic acid, mixtures thereof, and the like. It is understood that the corresponding anhydrides, esters, and acid chlorides using these acids are included in the term "carboxylic acid". Tricarboxylic compounds and compounds with a higher carboxylic acid group number can likewise modify the copolyester.
In addition to the hydroxyl components comprising NPG and TACD, the hydroxyl component of the copolyester of the present invention may include a modifier. The hydroxyl modifier is any hydroxyl bearing compound other than NPG and TACD. Hydroxyl modifiers include monoalcohols, diols, or compounds with higher hydroxyl numbers as branching monomers. Examples of modifier hydroxy compounds include cycloaliphatic diols, preferably having 6 to 20 carbon atoms and/or aliphatic diols, preferably having 2 to 20 carbon atoms. More specific examples of such glycols include ethylene glycol, diethylene glycol; triethylene glycol; 1, 2-cyclohexanedimethanol; 1, 3-cyclohexanedimethanol; 1, 4-cyclohexanedimethanol; 1, 2-propanediol; 1, 3-propanediol; 1, 4-butanediol; 1, 5-pentanediol; 1, 6-hexanediol; 3-methyl-2, 4-pentanediol; 2-methyl-1, 4-pentanediol; 2,2, 4-trimethylpentane-1, 3-diol; 2, 5-ethylhexane-1, 3-diol; 2, 2-diethyl-1, 3-propanediol; 1, 3-hexanediol; 1, 4-bis- (hydroxyethoxy) -benzene; 2, 2-bis- (4-hydroxycyclohexyl) -propane; 2, 4-dihydroxy-1, 1,3, 3-tetramethyl-cyclobutane; 2, 2-bis- (3-hydroxyethoxyphenyl) -propane; 2, 2-bis- (4-hydroxypropoxyphenyl) -propane; 2-butyl-2-ethyl-1, 3-propanediol, 2-ethyl-2-isobutyl-1, 3-propanediol, 2,2,4, 4-tetramethyl-1, 6-hexanediol, 1, 10-decanediol, 1, 4-benzenedimethanol, hydrogenated bisphenol A, isosorbide isohydrated sorbitol, propylene glycol, dipropylene glycol, polytetramethylene glycol, tetraethylene glycol, polyethylene glycols, and higher functional hydroxyl compounds that can be used as branching compounds, including 1,1, 1-trimethylolpropane, 1,1, 1-trimethylolethane, glycerol, pentaerythritol, erythritol, threitol, dipentaerythritol, sorbitol, mixtures thereof, and the like.
One example of a modifier includes isophthalic acid or naphthalene dicarboxylic acid added as an acid modifier, and cyclohexanedimethanol, ethylene glycol, or diethylene glycol added as a hydroxyl modifier.
In addition to NPG and TACD, the hydroxyl-bearing modifier may be added in an amount of less than 40 mol%, or less than 20 mol%, or less than 10 mol%, or less than 8 mol%, or less than 5 mol%, or less than 3 mol%, or less than 2 mol%, or less than 1 mol%, or less than 0.5 mol%, or less than 0.25 mol%, and desirably not added at all, based on 100 mol% of its individual components, acid or hydroxyl groups, in the polymer. In addition to NPG and TACD, the hydroxyl-containing modifier is desirably present in the polymer in an amount of less than 20 mole%, or less than 10 mole%, or less than 5 mole%, or less than 4 mole%, or less than 2 mole%, or less than 1 mole%, or less than 0.5 mole%, based on the moles of all residues in the copolyester (which by definition includes the residues of the hydroxyl and acid components).
Desirably, all moieties present in the copolyester, except for terephthalate, NGP and TACD moieties, including those due to added modifiers and those formed in situ during melt phase polymerization, are in amounts of less than 12 mol%, or no more than 10 mol%, or no more than 8 mol%, or no more than 6 mol%, or no more than or less than 5 mol%, or no more than 4 mol%, or no more than 2 mol%, or no more than 1 mol%, or no more than less than 0.5 mol%, or no more than or less than 0.25 mol%, or no more than or less than 0.1 mol%, or 0 mol%, based on the moles of all residues in the copolyester.
Desirably, the copolyesters of the invention comprise less than 5 mole%, or less than 4 mole%, or less than 3 mole%, or less than 2 mole%, or less than 1 mole% of ethylene glycol residues, based on the moles of all residues in the copolyester. Ideally, ethylene glycol is not added unless it is added as a support for the catalyst metal compound. Optionally, no ethylene glycol is added.
The polyester of the present invention may comprise at least one chain extender. Suitable chain extenders include, but are not limited to, polyfunctional (including, but not limited to, difunctional) isocyanates, polyfunctional epoxides including, for example, epoxidized novolacs, and phenoxy resins. In certain embodiments, the chain extender may be added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, the chain extender may be introduced during the conversion process (e.g., injection molding or extrusion) by compounding or by addition. The amount of chain extender used can vary depending on the particular monomer composition used and the physical properties desired, but is generally from about 0.1 to about 10 weight percent, for example from about 0.1 to about 5 weight percent, based on the total weight of the polyester.
In one embodiment, the amorphous copolyester wherein the residues of 2,2,4, 4-tetraalkyl-1, 3-cyclobutanediol comprise residues of compounds represented by the following structure:
Figure BDA0001110701080000081
wherein R is1，R2，R3And R4Each independently represents an alkyl group having 1 to 8 carbon atoms. The alkyl group may be linear, branched, or a combination of linear and branched alkyl groups, desirably, R1，R2，R3And R4At least one of (A) is methyl, preferably R1，R2，R3And R4Each of which is methyl.
Corresponding 2,2,4, 4-tetraalkyl-1, 3-cyclobutanediol that can be used as a TACD compound include 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol ("TMCD"), 2,2,4, 4-tetraethyl-1, 3-cyclobutanediol, 2,2,4, 4-tetra-n-propyl-1, 3-cyclobutanediol, 2,2,4, 4-tetra-n-butyl-1, 3-cyclobutanediol, 2,2,4, 4-tetra-n-pentyl-1, 3-cyclobutanediol, 2,2,4, 4-tetra-n-hexyl-1, 3-cyclobutanediol, 2,2,4, 4-tetra-n-heptyl-1, 3-cyclobutanediol, 2,2,4, 4-tetra-n-octyl-1, 3-cyclobutanediol, 2, 2-dimethyl-4, 4-diethyl-1, 3-cyclobutanediol, 2-ethyl-2, 4, 4-trimethyl-1, 3-cyclobutanediol, 2, 4-dimethyl-2, 4-diethyl-1, 3-cyclobutanediol, 2, 4-dimethyl-2, 4-di-n-propyl-1, 3-cyclobutanediol, 2, 4-n-dibutyl-2, 4-diethyl-1, 3-cyclobutanediol, 2, 4-dimethyl-2, 4-diisobutyl-1, 3-cyclobutanediol, and 2, 4-diethyl-2, 4-diisoamyl-1, 3-cyclobutanediol. Desirably, the TACD compound comprises 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol.
The moles of TACD residues may be at least 20 mol%, or at least 30 mol%, or at least 40 mol%, or at least 50 mol%, or at least 60 mol%, or at least 70 mol%, or at least 80 mol%, and less than 90 mol%, or less than 85 mol%, or less than 80 mol%, or less than 75 mol%, or less than 70 mol%, or less than 65 mol%, based on 100 mol% of the hydroxyl components, based on the total moles of added hydroxyl components. Suitable ranges include from 20 to 90, or from 20 to 85, or from 20 to 80, or from 20 to 75, or from 20 to 70, or from 20 to 65, or from 30 to 90, or from 30 to 85, or from 30 to 80, or from 30 to 75, or from 30 to 70, or from 30 to 65, or from 30 to 60, or from 40 to 90, or from 40 to 85, or from 40 to 80, or from 40 to 75, or from 40 to 70, or from 40 to 65, or from 40 to 60, or from 50 to 90, or from 50 to 85, or from 50 to 80, or from 50 to 70, or from 50 to 65, or from 50 to 60, or from 60 to 90, or from 60 to 85, or from 60 to 80, or from 60 to 75, or from 60 to 70, or from 60 to 65, or from 70 to 90, or from 70 to 85, or from 70 to 80, or from 70 to 75, or from 80 to 90, or from 80 to 85, in each case in the form of mol%, based on the moles of hydroxyl components.
The mole% of TACD residues present in the copolyester may be at least 10 mole%, or at least 15 mole%, or at least 20 mole%, or at least 25 mole%, or at least 30 mole%, or at least 35 mole%, or at least 40 mole%, and less than 45 mole%, or less than 40 mole%, or less than 35 mole%, or less than 30 mole%, based on the moles of all residues in the copolyester. Suitable ranges include from 10 to 45, or from 15 to 45, or from 20 to 45, or from 25 to 45, or from 30 to 45, or from 35 to 45, or from 40 to 45, or from 10 to 40, or from 15 to 40, or from 20 to 40, or from 25 to 40, or from 30 to 40, or from 35 to 40, or from 10 to 35, or from 15 to 35, or from 20 to 35, or from 25 to 35, or from 30 to 35, or from 10 to 30, or from 15 to 30, or from 20 to 30, or from 25 to 30, or from 10 to 25, or from 15 to 25, or from 20 to 25, or from 15 to 20, in each case based on the moles of all residues in the copolyester.
The copolyester also contains residues of neopentyl glycol (or 2, 2-dimethyl-1, 3-propanediol) ("NPG"). The amount of NPG added is at least 10 mol%, or at least 15 mol%, or at least 20 mol%, or at least 30 mol%, or at least 40 mol%, or at least 50 mol%, or at least 60 mol%, or at least 70 mol%, and less than 80 mol%, or less than 75 mol%, or less than 70 mol%, or less than 65 mol%, or less than 60 mol%, or less than 55 mol%, or less than 50 mol%, or less than 45 mol%, based on 100 mol% of the amount of hydroxyl component. Suitable ranges include 10 to 80, or 10 to 75, or 10 to 70, or 10 to 65, or 10 to 60, or 10 to 55, or 10 to 50, or 10 to 45, or 20 to 80, or 20 to 75, or 20 to 70, or 20 to 65, or 20 to 60, or 20 to 55, or 20 to 50, or 20 to 45, or 30 to 80, or 30 to 75, or 30 to 70, or 30 to 65, or 30 to 60, or 30 to 55, or 30 to 50, or 3045, or 40 to 80, or 40 to 75, or 40 to 70, or 40 to 65, or 40 to 60, 40 to 55, or 40 to 50, or 4045, or 50 to 80, or 50 to 75, or 50 to 70, or from 50 to 65, or from 50 to 60, or from 60 to 80, or from 60 to 75, or from 60 to 70, or from 60 to 65, or from 70 to 80, or from 70 to 75, or from 80 to 90, or from 80 to 85, in each case in the form of mol% based on the moles of hydroxyl components.
The mol% of NPG residues present in the copolyester may be at least 5 mol%, or at least 7 mol%, or at least 8 mol%, or at least 10 mol%, or at least 15 mol%, or at least 20 mol%, or at least 25 mol%, or at least 30 mol%, or at least 35 mol%, or at least 40 mol%, and less than 40 mol%, or less than 35 mol%, or less than 30 mol%, based on the moles of all residues in the copolyester. Suitable ranges include 5 to 40, or 7 to 40, or 8 to 40, or 10 to 40, or 15-40, or 20-40, or 25-40, or 30-40, or 35-40, 5-35, or 7-35, or 8-35, or 10-35, or 15-35, or 20-35, or 25-35, or 30-35, or 5 to 30, or 7 to 30, or 8 to 30, or 10-30, or 15-30, or 20-30, or 25-30, or 5-25, or 7-25, or 8-25, or 10-25, or 15-25, or 20-25, or from 5 to 20, or from 7 to 20, or from 8 to 20, or from 15 to 20, in each case in the form of mol%, based on the moles of all residues in the copolyester.
In one embodiment, the amorphous copolyester has one or more of the following characteristics:
(1) light transmittance is greater than 90%, haze is less than 1%;
(2) the low-pressure heat distortion temperature (HDT @0.455MPa) is between 94 ℃ and 109 ℃;
(3) the test conditions are that under the conditions of 2.16kgf pressure and 280 ℃ melt temperature, the Melt Index (MI) is between 15.3 and 29.5;
(4) a glass transition temperature of at least 90 ℃.
In a preferred embodiment, the polyurethane polymer comprises polycarbonate polyurethane.
Polycarbonate urethane contains a reaction product of polycarbonate polyol and polyisocyanate because the urethane resin has a skeleton derived from polycarbonate. As the polycarbonate polyol, known polycarbonate polyols can be used without limitation, and poly (alkylene carbonate) such as poly (hexamethylene carbonate) and the like can be exemplified.
Usually, as the polyol constituting the polyurethane resin, a polyalkylene glycol, a polyester polyol, a polyether polyol, and the like can also be used.
Further, as the urethane resin used in the present invention, a urethane resin having a crosslinked structure is preferably used. When a coating composition for forming a hard coat layer is applied onto a primer coating layer by using a polyurethane resin having a crosslinked structure in the molecule, the resistance of the primer coating layer to the dissolution of the coating composition can be enhanced to shorten the production time of a laminate. Also, the laminate thus obtained is excellent in appearance and impact resistance.
Adhesive agent
In the present invention, the adhesive is selected from: at least one of (meth) acrylate adhesives, epoxy resin adhesives, polyurethane adhesives, and polyimide adhesives.
The adhesive layer is arranged between the base material and the color-changing film, so that the base material is attached to the color-changing film.
In a preferred embodiment, the adhesive used in the adhesive layer is an acrylate adhesive, and the acrylate adhesive is prepared from the following raw materials:
100 parts by weight of an acrylate copolymer;
0.01 to 20 parts by weight of an ester plasticizer;
0.001 to 7 parts by weight of an alkali metal salt;
0.01-10 parts by weight of aminosilane-modified beta-cyclodextrin-graphene oxide-polybenzimidazole compound and
0.01-10 parts by weight of epoxy terminated polyetheramine;
the weight average molecular weight Mw of the acrylate copolymer is 100000-2000000, and the dispersity Mw/Mn is 4-20;
the ester plasticizer is selected from any one or more of diethylene glycol-di-2-ethylhexanoate, tetraethylene glycol-di-2-ethylhexanoate, polyethylene glycol di-2-ethylhexanoate, triethylene glycol diethylbutyrate, polyethylene glycol diethylbutyrate, polypropylene glycol diethylhexanoate, triethylene glycol dibenzoate, polyethylene glycol dibenzoate, polypropylene glycol dibenzoate and polyethylene glycol-2-ethylhexanoate benzoate;
the alkali metal salt is selected from any one or more of lithium perchlorate, lithium trifluoromethanesulfonate and sodium perchlorate.
In one embodiment, the acrylate copolymer is obtained by solution polymerization of a comonomer initiated by a free radical initiator; the initiator is one of azodiisobutyronitrile or dibenzoyl peroxide, and the total weight of the initiator is 0.03-0.6% of the total weight of the monomers; the copolymerization temperature is 50-100 ℃; copolymerization process using N2Protection; the solvent adopted in the solution polymerization is an organic solvent and is one or a mixture of several of aromatic hydrocarbons, esters, alcohols and ketones.
In one embodiment, the aminosilane-modified β -cyclodextrin-graphene oxide-polybenzimidazole complex is prepared by the following method:
1) dissolving 0.16 mol of 3,3 ', 4,4' -tetraaminodiphenylsulfone in 1000 g of polyphosphoric acid containing 85 wt% of phosphorus pentoxide, then adding 0.1mol of 1,3, 5-m-trimellitic acid into the reaction solution, reacting at 200 ℃ for 20 hours, cooling to room temperature, precipitating into water, neutralizing with ammonia water, filtering, and drying in vacuum at 100 ℃ to obtain amino-terminated hyperbranched polybenzimidazole;
2) fully dissolving 10 g of beta-cyclodextrin in an acetic acid solution, adding 10 g of the amino-terminated hyperbranched polybenzimidazole obtained in the step 1), 3g of graphene oxide, 3g of an aminosilane coupling agent KH-550, 2g of glutaraldehyde and 2g of 1, 3-dibromopropane, and performing ultrasonic dispersion to adjust the pH value of the solution to be 8.0-9.0; stirring for 1.5-2.5 h at 55-65 ℃ to obtain a precipitate, cleaning to be neutral, and drying to obtain the aminosilane-modified beta-cyclodextrin-graphene oxide-polybenzimidazole compound.
In one embodiment, the epoxy-terminated polyetheramine is prepared by the following process:
dissolving 100 g of epoxy resin E51 and 0.23 mol of benzylamine in 2000 g of propylene glycol methyl ether, reacting for 4 hours at 100 ℃ under the protection of nitrogen, cooling to room temperature, repeatedly washing the product with deionized water, and drying for 5 hours at 50 ℃ in a vacuum oven to obtain the epoxy terminated polyetheramine.
Color-changing film
In a preferred embodiment, the color-changing film comprises at least
100 parts by weight of a base resin; and
0.1-30 parts by weight of photochromic compound.
In a preferred embodiment, the photochromic compound is selected from: any one of naphthopyrans, benzopyrans, indolopyrans, phenanthropyrans and spiropyrans.
The term "photochromic compound", photochromic compound is not particularly limited, and known compounds may be used. For example, photochromic compounds described in the following documents may be used: japanese patent application publication (Toku-kai-Hei)2-28165, Japanese patent application publication (Toku-kai-Sho)62-288830, International publication WO94/22850 pamphlet, International publication WO96/14596 pamphlet, International publication WO01/60811 pamphlet, U.S. Pat. No. 4913544 and U.S. Pat. No. 5623005. The amount of the photochromic compound may be appropriately determined depending on the use of the photochromic coating agent or the cast curable composition.
In one embodiment, a non-limiting example of the photochromic compound is an organic photochromic compound having a desired chromatic color. They typically have at least one activated absorption peak in the range of about 400-700 nm. They may be used alone or in combination with photochromic compounds that complement their activated color.
In one non-limiting embodiment, the photochromic compounds include chromenes such as naphthopyrans, benzopyrans, indolocaphthopyrans, and phenanthropyrans; spiropyrans, such as spiro (benzindoline) naphthopyrans, spiro (indoline) benzopyrans, spiro (indoline) naphthopyrans, spiro (indoline) quinropyrans and spiro (indoline) pyrans; mercury salts of dithizone, fulgides, fulgimides, and mixtures of these photochromic compounds. These photochromic compounds are described in U.S. Pat. Nos. 5,645,767, 6,153,126 and US6,296,785B1 at column 30, line 44 to column 31, line 5.
In a preferred embodiment, the raw materials for preparing the color-changing film further comprise: 1 to 20 parts by weight of a hydrolyzable group-containing organosilicon compound and 10 to 200 parts by weight of inorganic oxide fine particles.
Illustrative examples of preferred organosilicon compounds containing hydrolyzable groups include gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, gamma-glycidoxypropyltriethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, 1, 6-bistrimethoxysilane, 3-ureidopropyltriethoxysilane, bis [3- (diethoxymethylsilyl) propyl ] carbonate, trifluoropropyltrimethoxysilane, perfluorooctylethyltriethoxysilane, gamma-chloropropyltrimethoxysilane, vinyltris (beta-methoxy-ethoxy) silane, allyltrimethoxysilane, gamma-acryloyloxypropyltrimethoxysilane, gamma-acryloyloxypropyltriethoxysilane, gamma-methacryloyloxypropyltrimethoxysilane, gamma-methacryloyloxypropyltriethoxysilane, gamma-methacryloyloxypropyldimethoxymethylsilane, a salt thereof, a base, a polymer, Gamma-mercaptopropyltrialkoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylene) propylamine, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, p-styryltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc., and partial or total hydrolysates or partial condensates thereof. Among them, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, gamma-acryloxypropyltrimethoxysilane, gamma-acryloxypropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane and the like are preferable.
In a preferred embodiment, inorganic oxide fine particles may be further added to the color-changing film, and the inorganic oxide fine particles may improve the refractive index of the color-changing film and may further improve the scratch resistance of the color-changing film. The inorganic oxide fine particles may be used together with the above-mentioned hydrolyzable group-containing organosilicon compound or alone.
Specifically, silica can be used as the inorganic oxide fine particles. When inorganic oxide fine particles are added for increasing the refractive index, fine particles of an inorganic oxide or a composite inorganic oxide containing at least one element selected from the group consisting of Si, Al, Ti, Fe, In, Zr, Ag, Au, Sn, Sb, W, and Ce; more specifically, fine particles of an inorganic oxide or a composite inorganic oxide containing at least one element selected from the group consisting of Si, Al, Ag, Ti, Fe, Zr, Sb, and W may be more preferably used. The inorganic oxide fine particles preferably have a primary particle diameter of about 1 to 300nm as observed by a Transmission Electron Microscope (TEM). The fine particles having such a particle diameter are generally used in a state where they are dispersed in water as a dispersion medium or in a part of an organic solvent (particularly, an alcoholic solvent) described later; colloidal dispersions are commonly used to prevent fine particles from coagulating. For example, in the present invention, from the viewpoint that the inorganic oxide fine particles are homogeneously dispersed in the color-changing film, it is preferable to add the inorganic oxide fine particles to the color-changing film in the form of a sol in which they are dispersed in a water-soluble organic solvent such as methanol, ethanol, isopropanol, or the like, or water.
As described above, as the water-soluble organic solvent used for the dispersion medium for the inorganic oxide fine particles, alcohol solvents such as methanol, ethanol, isopropanol, and the like; however, methyl ethyl ketone, methyl isobutyl ketone, dimethylacetamide, and the like can also be used.
That is, in the present invention, it is preferable to mix the inorganic oxide fine particles with other components in the form of a sol in which the inorganic oxide fine particles are dispersed in water or the above-mentioned water-soluble organic solvent, specifically, in the form of a silica sol, an inorganic oxide fine particle sol, or a composite inorganic oxide fine particle sol. The order of mixing the inorganic oxide fine particles with the other components is not particularly limited.
The silica sol may be commercially available; for example, sols containing water as the dispersing medium are available from NISSAN CHEMICAL INDUSTRIES, LTD under the registered trade names "Snowtex", "Snowtex OS", "Snowtex O", or "Snowtex O-40". Sols containing a water-soluble organic solvent as a dispersion medium are commercially available from NISSAN CHEMICAL INDUSTRIES under the trade names "methanol silica sol", "MA-ST-MS" (dispersion medium: methanol), "IPA-ST" (dispersion medium: isopropanol), etc.
The sol of the composite inorganic oxide fine particles may also be commercially available; for example, "HX series", "HIT series" or "HT series" manufactured by NISSAN CHEMICAL INDUSTRIES, LTD and "opthale" (registered trademark) manufactured by JGC Catalyst and Chemicals LTD.
The second aspect of the present invention provides a method for preparing the color-changing article, comprising the following steps:
providing a substrate and a color-changing film;
wherein the base material and the base resin are the same;
and (3) bonding the base material and the color-changing film in a melting mode.
In a third aspect, the present invention provides a method for preparing the color-changing article, comprising the steps of:
providing a substrate and a color-changing film;
wherein, the base material and the base resin are different;
and at least partially covering the upper surface of the base material with an adhesive to ensure that the base material is attached with the color-changing film.
A fourth aspect of the present invention provides use of the color changing film in eyeglasses, a display device or a communication device.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are commercially available, unless otherwise specified, and the parts used for the following materials are parts by weight.
Raw materials：
Base material and base resin：
A1: polycarbonate, film thickness 0.8 mm;
a2: cellulose triacetate, the film thickness is 0.9 mm;
a3: amorphous copolyester with a film thickness of 1 mm;
the preparation method of the amorphous copolyester comprises the following steps:
into a 500mL round-bottomed flask were charged 77.7g of dimethyl terephthalate (0.40mol), 31.3g of neopentyl glycol (0.30mol), 43.3g of 2,2,4, 4-tetramethylcyclobutanediol (0.30mol), 0.02g of butyltin tris-2-ethylhexanoate, 0.05g of lithium hydroxide monohydrate, 0.03g of aluminum isopropoxide, and 0.03g of triphenyl phosphate, and then the mixture was heated at 290 ℃ to react for 4 hours.
A4: polyurethane polymer, under the trade name "SUPERFLEX 420"; the film thickness is 1 mm;
the "SUPERFLEX 420" (registered trademark, manufactured by Dai-ichi Kogyou Seiyaku Co. Ltd., average particle diameter: 120nm, elongation: 280%, Tg: -20 ℃ C., 100% modulus: 15N/mm2Solid content (polyurethane resin) concentration: about 32 mass%, water: about 65% by mass, contains a skeleton derived from polycarbonate, is a polycarbonate urethane, and is crosslinkable).
Color-changing film
B1: the layer thickness of the color-changing film is 0.15 mm;
the color-changing film comprises:
100 parts by weight of a base resin; and
0.1 part by weight of a photochromic compound;
the photochromic compound is a spiro (chromane) naphthopyran.
B2: the layer thickness of the color-changing film is 0.2 mm;
the color-changing film comprises:
100 parts by weight of a base resin; and
30 parts of photochromic compound;
the photochromic compound is benzopyran.
B3: the layer thickness of the color-changing film is 0.2 mm;
the color-changing film comprises:
100 parts by weight of a base resin; and
10 parts of photochromic compound;
the photochromic compound is an indole naphthopyran.
B4: the layer thickness of the color-changing film is 0.1 mm;
the color-changing film comprises:
base resin 100 parts by weight
10 parts by weight of photochromic compound;
5 parts by weight of gamma-glycidoxypropylmethyldiethoxysilane;
the photochromic compound is phenanthropyran.
B5: the layer thickness of the color-changing film is 0.1 mm;
the color-changing film comprises:
base resin 100 parts by weight
10 parts by weight of photochromic compound;
5 parts by weight of gamma-glycidoxypropylmethyldiethoxysilane;
and 5 parts by weight of nano silica.
The photochromic compound is a spiro (chromane) naphthopyran.
B6: the layer thickness of the color-changing film is 0.1 mm;
the color-changing film comprises:
base resin 100 parts by weight
10 parts by weight of photochromic compound;
5 parts by weight of gamma-glycidoxypropylmethyldiethoxysilane;
and 5 parts by weight of nano silicon dioxide; and
10 parts by weight of composite inorganic oxide fine particles;
the photochromic compound is a spiro (chromane) naphthopyran.
The composite inorganic oxide fine particles include 5 parts by weight of nano silica, 4 parts by weight of tin oxide, 3 parts by weight of antimony pentoxide, and 3 parts by weight of iron sesquioxide.
Adhesive agent
C1: a Thalassia Hantaeda Technomelt Q8783 layer thickness of 100 microns;
c2: acrylate adhesive with a layer thickness of 120 microns;
the preparation method of the acrylate adhesive comprises the following steps:
uniformly mixing 100 parts by weight of polybutyl acrylate, 5 parts by weight of tetraethyleneglycol di-2-ethyl hexanoate, 4 parts by weight of lithium perchlorate and 5 parts by weight of epoxy terminated polyether amine to obtain the acrylate adhesive;
the epoxy-terminated polyether amine is prepared by the following method:
dissolving 100 g of epoxy resin E51 and 0.23 mol of benzylamine in 2000 g of propylene glycol methyl ether, reacting for 4 hours at 100 ℃ under the protection of nitrogen, cooling to room temperature, repeatedly washing the product with deionized water, and drying for 5 hours at 50 ℃ in a vacuum oven to obtain the epoxy terminated polyetheramine.
C3: acrylic ester adhesive with a layer thickness of 130 microns;
the preparation method of the acrylate adhesive comprises the following steps:
uniformly mixing 100 parts by weight of polybutyl acrylate, 5 parts by weight of tetraethyleneglycol di-2-ethyl hexanoate, 4 parts by weight of lithium perchlorate and 5 parts by weight of aminosilane-modified beta-cyclodextrin-graphene oxide-polybenzimidazole compound to obtain the acrylate adhesive;
the amino silane modified beta-cyclodextrin-graphene oxide-polybenzimidazole compound is prepared by the following method:
1) dissolving 0.16 mol of 3,3 ', 4,4' -tetraaminodiphenylsulfone in 1000 g of polyphosphoric acid containing 85 wt% of phosphorus pentoxide, then adding 0.1mol of 1,3, 5-m-trimellitic acid into the reaction solution, reacting at 200 ℃ for 20 hours, cooling to room temperature, precipitating into water, neutralizing with ammonia water, filtering, and drying in vacuum at 100 ℃ to obtain amino-terminated hyperbranched polybenzimidazole;
2) fully dissolving 10 g of beta-cyclodextrin in an acetic acid solution, adding 10 g of the amino-terminated hyperbranched polybenzimidazole obtained in the step 1), 3g of graphene oxide, 3g of an aminosilane coupling agent KH-550, 2g of glutaraldehyde and 2g of 1, 3-dibromopropane, and performing ultrasonic dispersion to adjust the pH value of the solution to be 8.0-9.0; stirring for 1.5-2.5 h at 55-65 ℃ to obtain a precipitate, cleaning to be neutral, and drying to obtain the aminosilane-modified beta-cyclodextrin-graphene oxide-polybenzimidazole compound.
C4: acrylate adhesive with a layer thickness of 150 microns;
the preparation method of the acrylate adhesive comprises the following steps:
uniformly mixing 100 parts by weight of polybutyl acrylate, 5 parts by weight of tetraethylene glycol di-2-ethyl hexanoate, 4 parts by weight of lithium perchlorate, 5 parts by weight of aminosilane modified beta-cyclodextrin-graphene oxide-polybenzimidazole compound and 5 parts by weight of epoxy terminated polyether amine to obtain the acrylate adhesive;
the preparation method of the aminosilane modified beta-cyclodextrin-graphene oxide-polybenzimidazole compound is the same as B3.
The epoxy-terminated polyether amine is prepared by the following method:
dissolving 100 g of epoxy resin E51 and 0.23 mol of benzylamine in 2000 g of propylene glycol methyl ether, reacting for 4 hours at 100 ℃ under the protection of nitrogen, cooling to room temperature, repeatedly washing the product with deionized water, and drying for 5 hours at 50 ℃ in a vacuum oven to obtain the epoxy terminated polyetheramine.
Example 1
A color-changing article comprises a substrate (A1) and a color-changing film (B1) from bottom to top;
the preparation method of the color-changing film：
The base resin is A1;
a1 and B1 were bonded by melting.
Example 2
A color-changing article comprises a substrate (A2) and a color-changing film (B2) from bottom to top;
the preparation method of the color-changing film：
The base resin is A2;
a2 and B2 were bonded by melting.
Example 3
A color-changing article comprises a substrate (A3) and a color-changing film (B3) from bottom to top;
the preparation method of the color-changing film：
The base resin is A3;
a3 and B3 were bonded by melting.
Example 4
A color-changing article comprises a substrate (A4) and a color-changing film (B4) from bottom to top;
the preparation method of the color-changing film：
The base resin is A4;
a4 and B4 were bonded by melting.
Example 5
A color-changing article comprises a substrate (A4) and a color-changing film (B5) from bottom to top;
the preparation method of the color-changing film：
The base resin is A4;
a4 and B5 were bonded by melting.
Example 6
A color-changing article comprises a substrate (A4) and a color-changing film (B6) from bottom to top;
the preparation method of the color-changing film：
The base resin is A4;
a4 and B6 were bonded by melting.
Example 7
A color-changing product comprises a base material (A4), an adhesive (C1) and a color-changing film (B6) from bottom to top;
the preparation method of the color-changing film：
The base resin is A1;
c1 was at least partially covered on the upper surface of A4 to attach A4 to B6.
Example 8
A color-changing product comprises a base material (A4), an adhesive (C2) and a color-changing film (B6) from bottom to top;
the preparation method of the color-changing film：
The base resin is A1;
c2 was at least partially covered on the upper surface of A4 to attach A4 to B6.
Example 9
A color-changing product comprises a base material (A4), an adhesive (C3) and a color-changing film (B6) from bottom to top;
the preparation method of the color-changing film：
The base resin is A1;
c3 was at least partially covered on the upper surface of A4 to attach A4 to B6.
Example 10
A color-changing product comprises a base material (A4), an adhesive (C4) and a color-changing film (B6) from bottom to top;
the preparation method of the color-changing film：
The base resin is A1;
c4 was at least partially covered on the upper surface of A4 to attach A4 to B6.
Durability test
The chemical durability of the manufactured discoloration film was evaluated by immersing the discoloration film in boiling water for 10 hours. The level of adhesion was assessed before and after the boil test by attempting to peel the coating off with standard adhesive tape.
The test results are shown in Table 1.
Examples Polarization efficiency before durability test Polarization efficiency after durability test Extent of peelability after durability test
Example 1 86％ 82％ Is difficult to be stripped
Example 2 88％ 85％ Is difficult to be stripped
Example 3 93％ 90％ Is difficult to be stripped
Example 4 93％ 92％ Is difficult to be stripped
Example 5 95％ 94％ Is difficult to be stripped
Example 6 100％ 100％ Is difficult to be stripped
Example 7 100％ 90％ Is difficult to be stripped
Example 8 100％ 94％ Is difficult to be stripped
Example 9 100％ 97％ Is difficult to be stripped
Example 10 100％ 100％ Is difficult to be stripped
From the above data, it can be seen that the color-changing articles of the present invention all have better weatherability and longer service life, thus providing the beneficial technical effects of the present invention.
The foregoing examples are illustrative only, and serve to explain some of the features of the present disclosure. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. And that advances in science and technology will result in possible equivalents or sub-substitutes not currently contemplated for reasons of inaccuracy in language representation, and such changes should also be construed where possible to be covered by the appended claims.

Claims (3)

1. A color-changing product is characterized by comprising a base material, an adhesive and a color-changing film from bottom to top;
the base material is polyurethane polymer, and the film thickness is 1 mm;
the thickness of the color-changing film is 0.1 mm; the color-changing film comprises: 100 parts by weight of a base resin; 10 parts by weight of photochromic compound; 5 parts by weight of gamma-glycidoxypropylmethyldiethoxysilane; and 5 parts by weight of nano silicon dioxide; 10 parts by weight of composite inorganic oxide fine particles; the photochromic compound is a spiro (chromane) naphthopyran; the composite inorganic oxide fine particles comprise 5 parts by weight of nano silicon dioxide, 4 parts by weight of tin oxide, 3 parts by weight of antimony pentoxide and 3 parts by weight of ferric oxide; the substrate resin is polycarbonate;
the adhesive is acrylate adhesive, and the thickness of the layer is 150 microns; the preparation method of the acrylate adhesive comprises the following steps: uniformly mixing 100 parts by weight of polybutyl acrylate, 5 parts by weight of tetraethylene glycol di-2-ethyl hexanoate, 4 parts by weight of lithium perchlorate, 5 parts by weight of aminosilane modified beta-cyclodextrin-graphene oxide-polybenzimidazole compound and 5 parts by weight of epoxy terminated polyether amine to obtain the acrylate adhesive;
the amino silane modified beta-cyclodextrin-graphene oxide-polybenzimidazole compound is prepared by the following method:
1) dissolving 0.16 mol of 3,3 ', 4,4' -tetraaminodiphenylsulfone in 1000 g of polyphosphoric acid containing 85 wt% of phosphorus pentoxide, then adding 0.1mol of 1,3, 5-m-trimellitic acid into the reaction solution, reacting at 200 ℃ for 20 hours, cooling to room temperature, precipitating into water, neutralizing with ammonia water, filtering, and drying in vacuum at 100 ℃ to obtain amino-terminated hyperbranched polybenzimidazole;
2) fully dissolving 10 g of beta-cyclodextrin in an acetic acid solution, adding 10 g of the amino-terminated hyperbranched polybenzimidazole obtained in the step 1), 3g of graphene oxide, 3g of an aminosilane coupling agent KH-550, 2g of glutaraldehyde and 2g of 1, 3-dibromopropane, and performing ultrasonic dispersion to adjust the pH value of the solution to be 8.0-9.0; stirring for 1.5-2.5 h at 55-65 ℃ to obtain a precipitate, cleaning to be neutral, and drying to obtain an aminosilane-modified beta-cyclodextrin-graphene oxide-polybenzimidazole compound;
the epoxy-terminated polyether amine is prepared by the following method:
dissolving 100 g of epoxy resin E51 and 0.23 mol of benzylamine in 2000 g of propylene glycol methyl ether, reacting for 4 hours at 100 ℃ under the protection of nitrogen, cooling to room temperature, repeatedly washing the product with deionized water, and drying for 5 hours at 50 ℃ in a vacuum oven to obtain the epoxy terminated polyetheramine.
2. The method of making a color-changing article of claim 1, comprising the steps of:
providing a substrate and a color-changing film;
wherein, the base material and the base resin are different;
and at least partially covering the upper surface of the base material with an adhesive to ensure that the base material is attached with the color-changing film.
3. Use of the color changing article of claim 1 in eyewear, display devices, or communication devices.
CN201610807924.1A 2016-09-07 2016-09-07 Color-changing product, preparation method and application thereof Active CN106433609B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610807924.1A CN106433609B (en) 2016-09-07 2016-09-07 Color-changing product, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610807924.1A CN106433609B (en) 2016-09-07 2016-09-07 Color-changing product, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN106433609A CN106433609A (en) 2017-02-22
CN106433609B true CN106433609B (en) 2020-12-29

Family

ID=58165286

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610807924.1A Active CN106433609B (en) 2016-09-07 2016-09-07 Color-changing product, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN106433609B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7118876B2 (en) * 2017-12-25 2022-08-16 株式会社トクヤマ Laminate, optical substrate comprising said laminate, and optical article provided with said optical substrate
CN109694459A (en) * 2018-12-29 2019-04-30 东莞市康诚鞋材有限公司 A kind of sensitization discoloration TPU shoes accessory material and preparation method thereof
CN109648956B (en) * 2018-12-29 2021-03-05 温州富奇士光电材料有限公司 Photochromic material and preparation method and application thereof
CN109942861A (en) * 2019-03-12 2019-06-28 无锡创彩光学材料有限公司 A kind of photochromic composite membrane of flexibility and preparation method thereof
CN111116956B (en) * 2019-12-26 2022-11-15 乐凯光电材料有限公司 TAC functional film and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7189456B2 (en) * 2004-03-04 2007-03-13 Transitions Optical, Inc. Photochromic optical article
KR101007100B1 (en) * 2007-11-01 2011-01-10 주식회사 엘지화학 Photochromic compositions and photochromic films
WO2010056082A2 (en) * 2008-11-14 2010-05-20 주식회사 엘지화학 Laminate
US8623483B1 (en) * 2012-10-23 2014-01-07 Eastman Chemical Company Copolyesters containing neopentyl glycol and 2,2,4,4-tetraalkyl 1,3-cyclobutanediol

Also Published As

Publication number Publication date
CN106433609A (en) 2017-02-22

Similar Documents

Publication Publication Date Title
CN106433609B (en) Color-changing product, preparation method and application thereof
KR100831457B1 (en) Adhesion enhancing coating composition, process for using and coated or laminated articles produced
JP5918138B2 (en) Primer composition for optical article and optical article
TWI415916B (en) A photohardenable adhesive, a polarizing plate using the photohardenable adhesive, a method of manufacturing the same, an optical member, and a liquid crystal display device
JP5566306B2 (en) Coating composition, method for producing the composition, and laminate having a hard coat layer
JP4292634B2 (en) Method for manufacturing antireflection laminate
CN110121418B (en) Transparent resin substrate
CN103703036B (en) Monolayer film and hydrophilic material comprising same
TW201111465A (en) Polarizing plate and laminated optical component using the same
AU2010250467A1 (en) Coating composition and optical article
CN103748488A (en) Polarizing plate
CN107000397A (en) Three-dimensionally shaped product decoration laminated film, its manufacture method and method for three-dimensional decoration
CN105452380A (en) Aqueous resin composition, laminate produced using same, and image display device
WO2010122912A1 (en) Coating composition
JP4121370B2 (en) Transparent heat-absorbing plastic molding material
CN105026961A (en) Plastic lens and production method therefor
JP5766001B2 (en) Photochromic composition
JP2012032759A (en) Selective wavelength reflection film
KR102590266B1 (en) Coated Optical Articles
TW202136470A (en) Photochromic optical article
KR102664602B1 (en) Polycarbonate Based Optical Laminate, Preparation thereof and Coverwindow Using the Same
JP2018027992A (en) Coating composition, and optical article having coat layer made of the coating composition
WO2011055667A1 (en) Coating composition and optical article
JP2022110332A (en) Antireflection substrate
KR101967147B1 (en) Composition For Hard Coating and Hard Coating film Including Cured Product Of The Same As The Coating Layer

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant