CN106433609A - Allochromatic product as well as preparation method and application thereof - Google Patents

Allochromatic product as well as preparation method and application thereof Download PDF

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Publication number
CN106433609A
CN106433609A CN201610807924.1A CN201610807924A CN106433609A CN 106433609 A CN106433609 A CN 106433609A CN 201610807924 A CN201610807924 A CN 201610807924A CN 106433609 A CN106433609 A CN 106433609A
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Prior art keywords
color
base material
changing membrane
photochromic
adhesive
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Granted
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CN201610807924.1A
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CN106433609B (en
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黄肃明
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Wenzhou Fuqi Shi Photoelectric Material Co Ltd
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Wenzhou Fuqi Shi Photoelectric Material Co Ltd
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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
    • 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

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  • 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 an allochromatic product, which at least comprises a base material and an allochromatic film, wherein the base material is connected with the allochromatic film through fusion or through an adhesive; the allochromatic film at least comprises a substrate resin and a photochromic compound. The allochromatic product provided by the invention has better weather fastness and longer service life.

Description

Photochromic article, its preparation method and its application
Technical field
The present invention relates to optical element technology field, more particularly it relates to a kind of photochromic article, its preparation method And its application.
Background technology
Off-color material is a kind of new optical function material, under daylight or other light sources irradiate can rapidly by colourless or Light color becomes the shades of colour such as red, green, blue, purple, and can return to original state with after the irradiation of another light source or lucifuge, and Can reversible change repeatedly.The research of off-color material is constantly expanded in recent years and is goed deep into, the purposes of photochromic material More and more extensive.In recent years, photochromic material gradually walks out the high-technology fields such as the optical information storage of tradition application, starts Show up prominently in civil area, illustrate magical effect of off-color material.
Photochromic article causes extensive concern both domestic and external in recent years, and causes every field to have the reason interested in it Following some：One is that the irradiation that it has in varying strength and wavelength light issues raw photochromic photosensitive property, industrially In addition to making general decoration and packaging material, it is additionally operable to protect the infringement to human eye, the person for the high light radiations such as nuclear explosion test； Two is the change performance due to can be there is Reversible Cycle by varying strength and wavelength light irradiation, can be made into various optical gates, picture recording is situated between Information storage elements in matter, computer, especially laser provide various necessary luminous intensities after occurring, and have more promoted it in letter Application in breath data system；Three is that it also produces sensitive color change to different degrees of heat, can be used as temperature instruction, controls chemistry Polymerisation；Four is the specific discoloration that it has, and is mainly used as false proof and false distinguishing material in recent years.
Additionally, off-color material is in autography photographic film and holography material, anti-counterfeit recognition technology, military hidden camouflage The application in the fields such as material is also increasing, and market prospects are considerable.
Existing photochromic article is usually that the surface directly allochroic paint being coated in base material obtains, this color-changing membrane at present Highly unstable and easily destroyed, hence it is highly desirable to pass through technological improvement, with obtain a kind of can Long-Time Service resistance to old Change the photochromic article of excellent performance.
Content of the invention
In order to solve the above problems, the first aspect of the invention provides a kind of photochromic article, at least includes,
Base material；With
Color-changing membrane；
Described base material and color-changing membrane are connected by melting or are connected by adhesive；
Described color-changing membrane at least includes base resin and photochromic compound.
In a preferred embodiment, described base material, base resin can be identical or different, and select independently of one another The copolymer of self-polycarbonate, amorphous copolyester, polyamide, polyethylene terephthalate, ENB and ethene, vinegar Sour cellulose butyrate, Triafol T, polyurethane polymer, amino resins are birdsed of the same feather flock together compound and acrylic polymer In at least one.
In a preferred embodiment, described polyurethane polymer includes polycarbonate polyurethane.
In a preferred embodiment, described adhesive is selected from (methyl) esters of acrylic acid adhesive, epoxy resin At least one in class adhesive, polyurethane tackifier and polyimide adhesive.
In a preferred embodiment, described adhesive is esters of acrylic acid adhesive, and described acrylate Class adhesive, its preparing raw material includes：
The acrylate copolymer of 100 weight portions；
The ester plasticiser of 0.01～20 weight portion；
The alkali metal salt of 0.001～7 weight portion；
Amino silane modified beta-schardinger dextrin-graphene oxide-the polybenzimidazole compound of 0.01～10 weight portion and
The epoxy-capped polyetheramine of 0.01～10 weight portion.
In a preferred embodiment, described color-changing membrane at least includes
Base resin 100 weight portion；With
Photochromic compound 0.1-30 weight portion.
In a preferred embodiment, described photochromic compound is selected from：Aphthopyrans, chromene, indoles Any one in aphthopyrans, phenanthro- pyrans, spiro-pyrans.
A second aspect of the present invention provides the preparation method of described photochromic article, comprises the following steps：
Base material and color-changing membrane are provided；
Wherein, base material, base resin are identical；
Base material is fitted by way of melting with color-changing membrane.
A third aspect of the present invention provides the preparation method of described photochromic article, comprises the following steps：
Base material and color-changing membrane are provided；
Wherein, base material, base resin differ；
Adhesive is at least partially covered over the upper surface of described base material, so that base material is fitted with color-changing membrane.
A fourth aspect of the present invention provides application in glasses, display device or communication equipment for the color-changing membrane.
It is more readily understood the above-mentioned of the application and other features, aspect and advantage with reference to described further below.
Brief description
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing Have technology description in required use accompanying drawing be briefly described it should be apparent that, drawings in the following description be only this Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, acceptable Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1：Photochromic article schematic diagram obtained by embodiment 1,
Wherein, 1 represent color-changing membrane, 2 represent base material；
Fig. 2：Photochromic article schematic diagram obtained by embodiment 10,
Wherein, 3 represent color-changing membrane, 4 represent adhesive；5 represent base material.
Specific embodiment
The embodiment of the participation in the election detailed description being preferable to carry out method of the invention below and inclusion can be more easily understood this public affairs Open content.A large amount of terms can be referred in description below and claims, these terms are defined as following meanings.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise.
" optional " or " any one " refers to that the item describing thereafter or event may or may not occur, and should Description includes the situation that the situation of event generation and event do not occur.
One scope of expression includes all integers in the range of this and its fraction.One scope of expression also includes this scope End points, do not consider that this scope indicates whether a numerical value of some described numerical value " interior " or " between " or " ".In the disclosure Hold and be intended to particularly including four corner with the scope described in claim and not just one or more end points.For example, 0 to Scope illustrated by 10 is intended to disclose all integers between 0 and 10, and such as 1,2,3,4 etc., all fractions between 0 and 10, Such as 1.5,2.3,4.57,6.1113 etc., and end points 0 and 10.
As used herein, term " variable color " and similar terms such as " photochromic compound " represent at least may be used See that light has absorption spectrum, it is in response at least absorption of photochemical radiation and changes.Additionally, as used herein, art Language " photochromic material " represents any such material, and it is suitable to show that photochromic properties (that is, are suitable to have at least may be used See the absorption spectrum of light, it is in response at least absorption of photochemical radiation and changes), and it includes at least one light-induced variable Color compound.
As used herein, term " photochromic compound " include thermal reversion photochromic compound and non-thermal can Inverse photochromic compound.As used herein, term " photochromic compound/material of thermal reversion " represents such Compound/material, it can be converted into the second state example from first state such as " pellucidity " when responding photochemical radiation As " colored state ", and it is restored back to first state when responding heat energy.As used herein, the term " light of non-thermoreversible Cause electrochromic compound/material " represent such compound/material, it can be from first state example when responding photochemical radiation As " pellucidity " changes into the second state such as " colored state " and essentially identical with the absorption of the state of coloring in response The photochemical radiation of wavelength when be restored back to first state (for example, stop be exposed to such photochemical radiation).
As used herein, term " piece " represents a kind of preforming film, and it has generally uniform thickness and can Control oneself.
As used herein, term " polymer " " represent homopolymers (for example being prepared), copolymerization by single monomeric substance Thing (for example by least two monomeric substance preparations) and graft polymers.
As used herein, term " (methyl) acrylate " and similar terms such as " (methyl) acrylate " represent Methacrylate and/or acrylate.As used herein, term " (methyl) acrylic acid " represent methacrylic acid and/ Or acrylic acid.
As used herein, term " copolyesters " is understood to mean that more with two by one or more bifunctional carboxylic acid Plant the synthetic polymer of difunctional hydroxyl compound's polycondensation preparation.Typically, bifunctional carboxylic acid is dicarboxylic acids, and bifunctional hydroxy Compound is dihydroxylic alcohols, for example, for example glycols (glycol) and glycols (diol).
As used herein, term " residue " represents by being related to the polycondensation reaction of corresponding monomer and is incorporated in polymer Any organic structure.As used herein, term " repetitive " represents that the dicarboxylic acids having via carbonyl epoxide bonding is residual Base and the organic structure of diol residue.Therefore, dicarboxylic acid residue can derived from dicarboxylic acid monomer or its combine acyl halide, Ester, salt, acid anhydrides or its mixture.Therefore, as used herein, term dicarboxylic acids is intended to include can be used for the polycondensation side with glycol Method to produce the dicarboxylic acids of high molecular weight copolyester and any derivative of dicarboxylic acids, the acyl halide that combines including it, ester, half Ester, salt, half salt, acid anhydrides, mixed acid anhydride, or its mixture.
In the present invention, described " photochromic article " can make film, piece, block and coating etc..
In order to solve the above problems, the first aspect of the invention provides a kind of photochromic article, at least includes,
Base material；With
Color-changing membrane；
Described base material and color-changing membrane are connected by melting or are connected by adhesive；
Described color-changing membrane at least includes base resin and photochromic compound.
Base material and base resin
In the present invention, the plastics for forming the base material of the application are not particularly limited, and can close for commercially available or experiment Become.
Described base material, base resin can be identical or different, and are each independently selected from Merlon, amorphous copolymerization The copolymer of ester, polyamide, polyethylene terephthalate, ENB and ethene, acetylbutyrylcellulose, three acetic acid are fine At least one that dimension element, polyurethane polymer, amino resins are birdsed of the same feather flock together in compound and acrylic polymer.
Amorphous copolyester of the present invention, represents that this polyester comprises the disordered regions of polymer substantially.Amorphous copolymerization Ester usually not fusing point.
The amorphous copolyester of the present invention shows at least 90 DEG C of glass transition temperature (here is abbreviated as " Tg "), such as by Known technology, for example, for example differential scanning calorimetry (" DSC "), using the TA DSC purchased from TA Instruments 2920 with the scan rate measurement of 20 DEG C/min.
It is desirable that the Tg of amorphous copolyester shows at least 92 DEG C, or at least 94 DEG C, or at least 96 DEG C, or at least 98 DEG C, Or at least 100 DEG C, or at least 102 DEG C, or at least 104 DEG C, or at least 106 DEG C, or at least 108 DEG C, or at least 110 DEG C, or extremely Few 112 DEG C, or at least 144 DEG C, or at least 116 DEG C, or at least 118 DEG C, or at least 120, and at most 185 DEG C, or be at most less than 170 DEG C, or at most 160 DEG C, or it is less than 150 DEG C, or it is less than 140 DEG C, or it is less than 138 DEG C, or it is less than 136 DEG C, or it is less than 134 DEG C, or it is less than 132 DEG C, or it is less than 130 DEG C, or it is less than 128 DEG C, or it is less than 126 DEG C, or it is less than 124 DEG C, or it is less than 122 DEG C, or Less than 120 DEG C, or it is less than 118 DEG C, or the Tg less than 116 DEG C.
The example of scope is included at 90 to 185 DEG C；90 to 180 DEG C；90 to 170 DEG C；90 to 160 DEG C；90 to 155 DEG C；90 To 150 DEG C；90 to 145 DEG C；90 to 140 DEG C；90 to 138 DEG C；90 to 135 DEG C；90 to 130 DEG C；90 to 125 DEG C；90 to 120 ℃；90 to 115 DEG C；90 to 110 DEG C；90 to 105 DEG C；90 to 100 DEG C；90 to 95 DEG C；92 to 185 DEG C；92 to 180 DEG C；92 to 170℃；92 to 160 DEG C；92 to 155 DEG C；92 to 150 DEG C；92 to 145 DEG C；92 to 140 DEG C；92 to 138 DEG C；92 to 136 DEG C； 92 to 134 DEG C；92 to 132 DEG C；92 to 130 DEG C；92 to 128 DEG C；92 to 126 DEG C；92 to 124 DEG C；100 to 185 DEG C；100 to 160℃；100 to 150 DEG C；100 to 145 DEG C；100 to 140 DEG C；100 to 138 DEG C；100 to 136 DEG C；100 to 134 DEG C；100 to 132℃；100 to 130 DEG C；100 to 128 DEG C；100 to 126 DEG C；105 to 185 DEG C；105 to 160 DEG C；105 to 150 DEG C；105 to 145℃；105 to 140 DEG C；105 to 136 DEG C；105 to 132 DEG C；105 to 128 DEG C；110 to 185 DEG C；110 to 160 DEG C；110 to 150℃；110 to 145 DEG C；110 to 140 DEG C；110 to 136 DEG C；110 to 132 DEG C；With the Tg in the range of 110 to 128 DEG C.
Preferably, the amorphous copolyester polymer of the present invention contains terephthalic acids alkylene ester in polymer chain and repeats Unit.
Amorphous copolyester can be by making the C of NPG and TACD and terephthalic acid (TPA)1-C4Dialkyl reaction produces ester list Body and/or oligomer, then make its polycondensation produce copolyesters to prepare.Can make during the method more than one containing one Or the compound of multiple hydroxy-acid group or one or more derivatives reaction.The entrance being changed into a part for copolyester product should The all compounds containing one or more hydroxy-acid groups in method or one or more derivative constitute " acid constituents ".Contain One or more compound of one or more hydroxy-acid groups or " residue " of one or more derivative is had to represent allization One or more of copolyester product is remained in after the copolyester polymer chain of compound condensation and polycondensation formation different length The part of compound.
More than one compound containing one or more hydroxyls or derivatives thereof can be changed into one or more copolyesters The part of polymer product.In the access method of the part being changed into one or more copolyester product containing one or more hydroxyls All compounds of base or derivatives thereof constitute hydroxy component.It is changed into one or more hydroxyl-functional of the part of copolyester product The residue of compound or derivatives thereof represents, in this compound and one or more chemical combination containing one or more hydroxy-acid groups Thing or one or more derivative condensation go forward side by side one one-step polycondensation formed different length copolyester polymer chain after, remain in The part of one or more of copolyester product compound.
The mol% of the OH residues in one or more product and carboxylic acid residues can be by proton NMR or gas chromatography Measure.
Preferably, this amorphous copolyester polymer comprises：
(a) acid constituents, it comprises at least 80mol%, or at least 85mol%, or at least 90mol%, or at least 92mol%, or at least terephthalic acid (TPA) of 96mol%, or the C of ideally terephthalic acid (TPA)1-C4The residue of dialkyl, or At least 85mol% in any case, or at least 90mol%, or at least 92mol%, or at least inclusion of 96mol% is bonded to virtue The terephthalate unit of-C (O) the O- group of race's ring；With
(b) hydroxy component, it comprises at least 85mol%, or at least 90mol%, or at least 92mol%, or at least The residue of TACD and NPG of 96mol%；
Based on the acid constituents residue of 100mol% in copolyester polymer and the hydroxy component residues of 100mol%.
The reaction of the acid constituents and hydroxy component of preparing copolyester polymer is not limited to described mole percent, because Can be with the hydroxy component of excessive addition during manufacture.But, the copolyester polymer being obtained by reaction is by containing described sour group Divide the amount with hydroxy component.
The derivative of terephthalic acid (TPA) includes terephthalic acid (TPA) C1-C4Dialkyl, such as dimethyl terephthalate (DMT).Reason Think ground, the described amount of acid constituents is the C of terephthalic acid (TPA)1-C4Dialkyl, or the residue of dimethyl terephthalate (DMT).
C except terephthalic acid (TPA) and terephthalic acid (TPA)1-C4Dialkyl, outside TACD and NPG, other acid constituents and hydroxyl Component can serve as modifying agent, as long as the Tg of polymer is maintained at least 90 DEG C of level.
The example of sour modifying agent includes aromatic dicarboxylic acid, and it preferably has 8 to 14 carbon atoms, aliphatic dicarboxylic acid, and it is excellent Choosing has 4 to 12 carbon atoms, or alicyclic dicarboxylic acid, and it preferably has 8 to 12 carbon atoms.Can be used as one or more acid The more particular example of the modifying agent dicarboxylic acids of component is phthalic acid, M-phthalic acid, naphthalene -2,6- dioctyl phthalate, hexamethylene -1, 4- dioctyl phthalate, cyclohexanediacetic, diphenyl -4,4'- dioctyl phthalate, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, Decanedioic acid, dimeric dibasic acid, sulfoisophthalic acid, fumaric acid, maleic acid, itaconic acid, 1,3- cyclohexane cyclohexanedimethanodibasic, diglycolic acid, 2,5- norbornane dioctyl phthalate, diphenic acid, 4,4'- oxygen dibenzoic acid, 4,4'- sulfonyl dibenzoic acid, its mixture etc..Should Understand that the corresponding acid anhydrides using these acid, ester and acyl chlorides are included in term " carboxylic acid ".Three carboxyl compounds and have higher The compound of hydroxy-acid group number equally can be with modified copolyester.
In addition to the hydroxy component comprising NPG and TACD, the hydroxy component of copolyesters of the present invention can include modifying agent.Hydroxyl Base modifying agent is any hydroxyl compound in addition to NPG and TACD.Hydroxyl modification agent includes single methanol, glycol, or conduct Change the compound with higher hydroxyl value of monomer.The example of modifying agent hydroxy compounds includes alicyclic diol, and it preferably has There are 6 to 20 carbon atoms and/or aliphatic diol, it preferably has 2 to 20 carbon atoms.The more particular example of this glycol includes Ethylene glycol, diethylene glycol (DEG)；Triethylene glycol；1,2- cyclohexanedimethanol；1,3- cyclohexanedimethanol；1,4 cyclohexane dimethanol；1,2- Propane diols；1,3- propane diols；1,4- butanediol；1,5- pentanediol；1,6-HD；3- methyl -2,4-PD；2- methyl- 1,4- pentanediol；2,2,4- trimethylpentane -1,3- glycol；2,5- ethyl hexane -1,3- glycol；2,2- diethyl -1,3- third Glycol；1,3- hexylene glycol；1,4- bis--(hydroxyl-oxethyl)-benzene；2,2- bis--(4- hydroxy-cyclohexyl)-propane；2,4- dihydroxy- 1,1,3,3- tetramethyl-cyclobutane；2,2- bis--(3- hydroxyethoxyphenyl)-propane；2,2- bis--(4- hydroxy propyloxy group benzene Base)-propane；2- butyl -2- ethyl -1,3-PD, 2- ethyl -2- isobutyl group -1,3-PD, 2,2,4,4- tetramethyls - 1,6- hexylene glycol, 1,10- decanediol, Isosorbide-5-Nitrae-benzene dimethanol, hydrogenated bisphenol A, different de- two water D-sorbites, propane diols, dipropyl is sweet Alcohol, polytetramethylene glycol, tetraethylene glycol, polyethylene glycol, and can serve as the higher functional hydroxy compounds of hyperbranched compounds, including 1,1, 1- trimethylolpropane, 1,1,1- trimethylolethane, glycerine, pentaerythrite, antierythrite, threitol, dipentaerythritol, mountain Pears sugar alcohol, its mixture etc..
One example of modifying agent includes M-phthalic acid or the naphthalenedicarboxylic acid adding as sour modifying agent, and as hydroxyl The cyclohexanedimethanol that base modifying agent adds, ethylene glycol, or diethylene glycol (DEG).
In addition to NPG and TACD, hydroxyl modifying agent with less than 40mol%, or can be less than 20mol%, or is less than 10mol%, or it is less than 8mol%, or it is less than 5mol%, or it is less than 3mol%, or it is less than 2mol%, or it is less than 1mol%, or little In 0.5mol%, or the amount less than 0.25mol% is added, and ideally completely without based in polymer Its each component of 100mol%, acid or hydroxyl.In addition to NPG and TACD, hydroxyl modifying agent is also ideally to be less than 20mol%, or it is less than 10mol%, or it is less than 5mol%, or it is less than 4mol%, or it is less than 2mol%, or it is less than 1mol%, or Amount less than 0.5mol% is present in polymer, and (it passes through definition and includes hydroxyl the molal quantity based on residues all in copolyesters Base and the residue of acid constituents).
It is desirable that removing terephthalate, beyond NGP and TACD part, present in copolyesters, the amount of all parts, all wraps Those being formed in situ during including those and melt phase polymerization owing to the modifying agent adding, are less than 12mol%, or not More than 10mol%, or it is less than 8mol%, or is less than 6mol%, or be less than or be less than 5mol%, or be less than 5mol%, or it is less than 4mol%, or it is less than 2mol%, or it is less than 1mol%, or be less than less than 0.5mol%, or not More or less than 0.25mol%, or it is less than or is less than 0.1mol%, or be 0mol%, based on residues all in copolyesters Molal quantity.
It is desirable that the copolyesters of the present invention is included less than 5mol%, or it is less than 4mol%, or is less than 3mol%, or be less than 2mol%, or the glycol residue less than 1mol%, the molal quantity based on residues all in copolyesters.It is desirable that without second Glycol, unless added it as the carrier of catalyst metal compound.Alternatively, without ethylene glycol.
The polyester of the present invention can comprise at least one chain extender.Suitable chain extender is including but not limited to multifunctional (to be wrapped Include but be not limited to difunctionality) isocyanates, multi-functional epoxy's compound, including such as epoxidised novolaks, and phenoxy group tree Fat.In certain embodiments, chain extender can add at the end of polymerization or after polymerization.If poly- Add after conjunction method, chain extender can be drawn by mixing or by adding during method for transformation (be for example molded or extrude) Enter.The amount of the chain extender using can be different, depending on the specific monomer composition using and required physical property, but logical Chang Weiyue 0.1wt% to about 10wt%, e.g., from about 0.1wt% are to about 5wt%, the gross weight based on polyester.
In one embodiment, in described amorphous copolyester, described 2,2,4,4- tetraalkyl -1,3- cyclobutanediol Residue includes the residue of the compound by following representation：
Wherein R1, R2, R3And R4Represent the alkyl with 1 to 8 carbon atom independently of one another.Alkyl can be linear, Branched, or linear and branched-alkyl combination, it is desirable that R1, R2, R3And R4At least one be methyl, preferably R1, R2, R3 And R4Each be methyl.
The corresponding 2,2,4,4- tetraalkyl -1,3- cyclobutanediol that can serve as TACD compound includes 2,2,4,4- tetramethyl Base -1,3- cyclobutanediol (" TMCD "), 2,2,4,4- tetraethyl -1,3- cyclobutanediol, 2,2,4,4- tetra--n-propyl -1,3- ring Butanediol, 2,2,4,4- tetra--normal-butyl -1,3- cyclobutanediol, 2,2,4,4- tetra--n-pentyl -1,3- cyclobutanediol, 2,2,4,4- Four-n-hexyl -1,3- cyclobutanediol, 2,2,4,4- tetra--n-heptyl -1,3- cyclobutanediol, 2,2,4,4- tetra--n-octylcyclams, 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- diη-propyl -1,3- cyclobutanediol, 2,4- Positive 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.It is desirable that TACD compound comprises 2,2,4,4- tetramethyl -1,3- ring fourth Glycol.
Based on the hydroxy component of 100mol%, the molal quantity of TACD residue can be at least 20mol%, or at least 30mol%, or at least 40mol%, or at least 50mol%, or at least 60mol%, or at least 70mol%, or at least 80mol%, and it is less than 90mol%, or it is less than 85mol%, or it is less than 80mol%, or it is less than 75mol%, or be less than 70mol%, or it is less than 65mol%, the whole molal quantitys based on the hydroxy component adding.Suitable scope includes 20-90, or 20-85, or 20-80, or 20-75, or 20-70, or 20-65, or 30-90, or 30-85, or 30-80, or 30-75, or 30- 70, or 30-65, or 30-60, or 40-90, or 40-85, or 40-80, or 40-75, or 40-70, or 40-65, or 40-60, or 50-90, or 50-85, or 50-80, or 50-75, or 50-70, or 50-65, or 50-60, or 60-90, or 60-85, or 60- 80, or 60-75, or 60-70, or 60-65, or 70-90, or 70-85, or 70-80, or 70-75, or 80-90, or 80-85, It is the mol% form based on hydroxy component molal quantity in the case of each.
Based on the molal quantity of residues all in copolyesters, present in copolyesters, the mol% of TACD residue can be at least 10mol%, or at least 15mol%, or at least 20mol%, or at least 25mol%, or at least 30mol%, or at least 35mol%, or at least 40mol%, and it is less than 45mol%, or it is less than 40mol%, or it is less than 35mol%, or be less than 30mol%.Suitable scope includes 10-45, or 15-45, or 20-45, or 25-45, or 30-45, or 35-45, or 40-45, Or 10-40, or 15-40, or 20-40, or 25-40, or 30-40, or 35-40, or 10-35, or 15-35, or 20-35, or 25- 35, or 30-35, or 10-30, or 15-30, or 20-30, or 25-30, or 10-25, or 15-25, or 20-25, or 15-20, Molal quantity based on residues all in copolyesters in the case of each.
Copolyesters also contains the residue of neopentyl glycol (or 2,2- dimethyl -1,3- propane diols) (" NPG ").It is based on The amount of the hydroxy component of 100mol%, the amount of the NPG of addition is at least 10mol%, or at least 15mol%, or at least 20mol%, or at least 30mol%, or at least 40mol%, or at least 50mol%, or at least 60mol%, or at least 70mol%, and it is less than 80mol%, or it is less than 75mol%, or it is less than 70mol%, or it is less than 65mol%, or be less than 60mol%, or it is less than 55mol%, or it is less than 50mol%, or it is less than 45mol%.Suitable scope includes 10-80, or 10- 75, or 10-70, or 10-65, or 10-60, or 10-60, or 10-55, or 10-50, or 10-45, or 20-80, or 20-75, or 20-70, or 20-65, or 20-60, or 20-65, or 20-60, or 20-55, or 20-50, or 20-45, or 30-80, or 30- 75, or 30-70, or 30-65, or 30-60, or 30-55, or 30-50, or 30 45, or 40-80, or 40-75, or 40-70, or 40-65, or 40-60,40-55, or 40-50, or 40 45, or 50-80, or 50-75, or 50-70, or 50-65, or 50-60, Or 60-80, or 60-75, or 60-70, or 60-65, or 70-80, or 70-75, or 80-90, or 80-85, in every case for Mol% form based on hydroxy component molal quantity.
Based on the molal quantity of residues all in copolyesters, present in copolyesters, the mol% of NPG residue can be at least 5mol%, or at least 7mol%, or at least 8mol%, or at least 10mol%, or at least 15mol%, or at least 20mol%, or At least 25mol%, or at least 30mol%, or at least 35mol%, or at least 40mol%, and it is less than 40mol%, or be less than 35mol%, or it is less than 30mol%.Suitable scope includes 5-40, or 7-40, or 8-40, or 10-40, or 15-40, or 20- 40, or 25-40, or 30-40, or 35-40,5 to 35, or 7 to 35, or 8 to 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 5-20, or 7-20, or 8-20, or 15-20, in every case It is the mol% form based on residue molal quantitys all in copolyesters.
In one embodiment, described amorphous copolyester has following one or more feature：
(1) light transmittance>90%, mist degree<1%；
(2) low pressure heat distortion temperature (HDT@0.455MPa) is between 94 DEG C -109 DEG C；
(3), under the conditions of 2.16kgf pressure, 280 DEG C of melt temperatures, melting means (MI) is between 15.3-29.5 for test condition；
(4) at least 90 DEG C of glass transition temperature.
In a preferred embodiment, described polyurethane polymer includes polycarbonate polyurethane.
Polycarbonate polyurethane has the skeleton from Merlon due to polyurethane resin, and therefore it comprises poly- carbonic acid Ester polyol and the product of polyisocyanates.As polycarbonate polyol, can be unrestrictedly using known poly- carbonic acid Ester polyol, and can example poly- (alkylene carbonate) such as poly- (hexa-methylene carbonic ester) etc..
Usually as the polyalcohol constituting polyurethane resin, PAG, PEPA can also be used, gather Ethoxylated polyhydric alcohol, polyester ether polylol etc..
Additionally, as polyurethane resin used in the present invention, preferably using the polyurethane resin with cross-linked structure.Logical Cross using the polyurethane resin in molecule with cross-linked structure, the coating composition being used for being formed hard conating is applied to silane coupling agent When in coating, the manufacturing time to shorten duplexer for the dissolubility resistent to coating composition for the silane coupling agent coating can be strengthened.And, by The duplexer that this obtains is excellent in terms of outward appearance and resistance to impact.
Adhesive
In the present invention, described adhesive is selected from：(methyl) esters of acrylic acid adhesive, epoxy resin tackifier, poly- ammonia At least one in ester adhesive and polyimide adhesive.
Described gluing oxidant layer is arranged between base material and color-changing membrane, so that base material is fitted with color-changing membrane.
In a preferred embodiment, adhesive used by gluing oxidant layer is esters of acrylic acid adhesive, and described Esters of acrylic acid adhesive, its preparing raw material includes：
The acrylate copolymer of 100 weight portions；
The ester plasticiser of 0.01～20 weight portion；
The alkali metal salt of 0.001～7 weight portion；
Amino silane modified beta-schardinger dextrin-graphene oxide-the polybenzimidazole compound of 0.01～10 weight portion and
The epoxy-capped polyetheramine of 0.01～10 weight portion；
Weight average molecular weight Mw of described acrylate copolymer is 100000～2000000, and decentralization Mw/Mn is 4～20；
Described ester plasticiser is selected from diethylene glycol-two 2 ethyl hexanoic acid ester, TEG two -2 ethyl hexanoic acid ester, poly- second Glycol two -2 ethyl hexanoic acid ester, triethylene glycol diethyl butyrate, polyethylene glycol diethyl butyrate, polypropylene glycol diethyl Capronate, triethylene glycol dibenzoate, polyethylene glycol dibenzoate, dibenzonate and polyethylene glycol -2- Any one or more in ethyl hexyl hydrochlorate benzoic ether；
Described alkali metal salt is selected from any one or more in lithium perchlorate, TFMS lithium and sodium perchlorate.
In one embodiment, described acrylate copolymer is to cause comonomer by molten by radical initiator Liquid polymerization obtains；Initiator is one of azo-bis-isobutyl cyanide or dibenzoyl peroxide, the gross weight that initiator adds For total monomer weight 0.03%～0.6%；Copolymerization temperature is 50 DEG C～100 DEG C；Polymerization process adopts N2Protection；Polymerisation in solution The solvent of middle employing is organic solvent, is aromatic hydrocarbon, esters, the mixture of one or more of alcohols and ketone.
In one embodiment, described amino silane modified beta-schardinger dextrin-graphene oxide-polybenzimidazole compound Prepared by following methods：
1) by 0.16 mole 3,3 ', 4,4 '-tetramino diphenyl sulphone (DPS) is first dissolved in 1000 containing 85wt% phosphorus pentoxide In gram polyphosphoric acids, then by the 1 of 0.1 mole, between 3,5-, benzenetricarboxylic acid is added in reactant liquor, after 200 DEG C of reactions 20 hours, It is down to room temperature, precipitating, in water, is then neutralized with ammoniacal liquor, filters, be vacuum dried, obtain amino-terminated hyperbranched at 100 DEG C Polybenzimidazoles；
2) 10 grams of beta-schardinger dextrins are completely dissolved in after acetum, add 10 grams of steps 1) described in amino-terminated over-expense Change polybenzimidazoles, 3 grams of graphene oxides, 3 grams of amino silicane coupling agent KH-550,2 grams of glutaraldehydes and 2 grams of 1,3- dibromos third Alkane ultrasonic disperse, adjust pH value of solution between 8.0～9.0；Stir 1.5～2.5h at 55～65 DEG C, obtain sediment, cleaning To neutral and dry, obtain amino silane modified beta-schardinger dextrin-graphene oxide-polybenzimidazole compound.
In one embodiment, described epoxy-capped polyetheramine is prepared by following methods：
The benzylamine of 100 grams of epoxy resin E51 and 0.23 mole is dissolved in 2000 grams of propylene glycol monomethyl ethers, nitrogen is protected Under shield, after 100 DEG C are reacted 4 hours, after being down to room temperature deionized water cyclic washing product, 50 DEG C of dryings in vacuum drying oven 5 hours, obtain described epoxy-capped polyetheramine.
Color-changing membrane
In a preferred embodiment, described color-changing membrane at least includes
Base resin 100 weight portion；With
Photochromic compound 0.1-30 weight portion.
In a preferred embodiment, described photochromic compound is selected from：Aphthopyrans, chromene, indoles Any one in aphthopyrans, phenanthro- pyrans, spiro-pyrans.
Term " photochromic compound ", photochromic compound is not particularly limited, and can use known compound.Example As the photochromic compound described in documents below can be used：Japan patent applicant announce (Toku-kai-Hei) 2- 28165th, Japan patent applicant announce (Toku-kai-Sho) 62-288830, International Publication WO94/22850 pamphlet, international public affairs Open WO96/14596 pamphlet, International Publication WO01/60811 pamphlet, United States Patent (USP) 4913544 and United States Patent (USP) 5623005. The amount of photochromic compound suitably can determine according to the purposes of photochromic smears or cast curing property composition.
In one embodiment, the non-limitative example of described photochromic compound is to have desired colourity face The photochromic compoundses of color.They generally have the absworption peak of at least one activation in the range of about 400-700nm. They be can be used alone or are used in combination with the photochromic compound supplementing its activation color.
In a non-limiting specific embodiment, described photochromic compound includes chromene, such as aphthopyrans, Chromene, indoles aphthopyrans and phenanthro- pyrans；Spiro-pyrans, such as spiral shell (benzo indoline) aphthopyrans, spiral shell (dihydro Yin Diindyl) chromene, spiral shell (indoline) aphthopyrans, spiral shell (indoline) quinopyrans and spiral shell (indoline) pyrans；Mercury Dithizonate, fulgide, prisoner's o, and the mixture of these photochromic compounds.These photochromic compounds Have in United States Patent (USP) US5,645,767, US6,153,126 and US6,296,785B1 the 30th hurdle the 44th row are to the 31st hurdle the 5th row Described.
In a preferred embodiment, the preparing raw material of described color-changing membrane also includes：Organic containing hydrolyzable groups Silicon compound 1-20 weight portion and inorganic oxide fine particle 10-200 weight portion.
The illustrative examples preferably containing the organo-silicon compound of hydrolyzable groups include γ-epoxypropoxy trimethoxy Base silane, γ-glycidoxypropyl dimethoxysilane, γ-glycidoxypropyl diethoxy silane, γ-ring Oxygen the third oxygen propyl-triethoxysilicane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane, tetraethoxysilane, vinyl Trimethoxy silane, VTES, vinyltriacetoxy silane, MTMS, methyl three Ethoxy silane, methyl triple phenoxyl silane, dimethyldimethoxysil,ne, trimethylmethoxysilane, phenyl trimethoxy silicon Alkane, dimethoxydiphenylsilane, Cyclohexyl Methyl Dimethoxysilane, n-propyl trimethoxy silane, normal-butyl trimethoxy Base silane, trimethoxysilane, isobutyl triethoxy silane, n-hexyl trimethoxy silane, n-hexyl three ethoxy Base silane, n-octytriethoxysilane, positive decyl trimethoxy silane, 1,6- double trimethoxy silane, 3- ureido-propyl three Ethoxysilane, double [3- (diethoxymethyl silicyl) propyl group] carbonic ester, trifluoro propyl trimethoxy silane, perfluor are pungent Ethyl triethoxysilane, γ-r-chloropropyl trimethoxyl silane, vinyl three ('beta '-methoxy-ethyoxyl) silane, pi-allyl three Methoxy silane, γ-acryloxypropyl trimethoxy silane, γ-acryloxypropyl triethoxysilane, γ-first Base acryloxypropyl trimethoxy silane, γ-methacryloxypropyl, γ-methacryl Epoxide dimethylamine epoxide methyl-monosilane, γ-mercaptopropyi trialkoxy silane, γ-aminopropyltrimethoxysilane, γ-ammonia Propyl-triethoxysilicane, N- phenyl-γ-aminopropyltrimethoxysilane, 3- triethoxysilyl-N- (1,3- diformazan Base-butylidene) propylamine, N-2- (aminoethyl) -3- aminopropyl triethoxysilane, N-2- (aminoethyl) -3- aminopropyl trimethoxy Base silane, N-2- (aminoethyl) -3- aminopropyltriethoxy dimethoxysilane, to styryl trimethoxy silane, 3- isocyanic acid Ester propyl-triethoxysilicane etc. and their part or all of hydrolysate or partial condensation products thereof.Wherein, preferably γ-glycidoxypropyltrimethoxy silane, γ-glycidoxypropyl dimethoxysilane, tetraethoxysilane, methyl Three ethoxy silane, γ-acryloxypropyl trimethoxy silane, γ-acryloxypropyl triethoxysilane, γ-methyl-prop Alkene monomethacryloxypropyl trimethoxy silane etc..
In a preferred embodiment, inorganic oxide fine particle can also be added in described color-changing membrane, inorganic oxygen Compound fine grained can improve the refractive index of color-changing membrane, and can more improve the marresistance of color-changing membrane.Inorganic oxide fine particle Can be used together with the above-mentioned organo-silicon compound containing hydrolyzable groups or be used alone.
Specifically, silica can be used as inorganic oxide fine particle.When adding inorganic oxygen to increase refractive index During compound fine grained, preferably using the group comprising selected from Si, Al, Ti, Fe, In, Zr, Ag, Au, Sn, Sb, W and Ce composition In the inorganic oxide of at least one element or composite inorganic oxide fine grained；More particularly it may be more preferable to use bag Inorganic oxide containing at least one element in the group selected from Si, Al, Ag, Ti, Fe, Zr, Sb and W composition or composite inorganic The fine grained of oxide.Make that the particle diameter of inorganic oxide fine particle is preferably observed by transmission electron microscope (TEM) about 1 The primary particle size of～300nm.Have the fine grained of this particle diameter generally using its be scattered in as in the water of decentralized medium or partly after The state stated in organic solvent (especially, alcohol race solvent) uses；Colloidal dispersion is commonly used to prevent fine grained and condenses.Example As in the present invention, being homogeneously scattered in the viewpoint color-changing membrane from inorganic oxide fine particle, preferably by inorganic oxide fine particle It is added in color-changing membrane with the solation that they are scattered in water-miscible organic solvent such as methyl alcohol, ethanol, isopropanol etc. or water.
As described above, as the water-miscible organic solvent for inorganic oxide fine particle decentralized medium, preferable alcohol Solvent such as methyl alcohol, ethanol, isopropanol etc.；But also can use MEK, methyl iso-butyl ketone (MIBK), dimethylacetylamide etc..
That is, in the present invention, be preferably dispersed in water with inorganic oxide fine particle or above-mentioned water-miscible organic solvent in Solation, specifically with silicon dioxide gel, inorganic oxide fine particle colloidal sol or composite inorganic oxide fine particle colloidal sol Form, inorganic oxide fine particle is mixed with other components.Inorganic oxide fine particle is suitable with what other components mixed Sequence is not particularly limited.
Silica sol can be obtained commercially；For example, the colloidal sol comprising water as decentralized medium is from NISSAN CHEMICAL INDUSTRIES, LTD registration mark is " Snowtex ", " Snowtex OS ", " Snowtex O " or " Snowtex O-40 " buys.The colloidal sol comprising water-miscible organic solvent as decentralized medium from NISSAN CHEMICAL INDUSTRIES, LTD trade name " methanol silica sol ", " MA-ST-MS " (decentralized medium：Methyl alcohol), " IPA-ST " (decentralized medium： Isopropanol) etc. buy.
The colloidal sol of composite inorganic oxide fine particle can also be obtained commercially；For example, example is by NISSAN " the HX series ", " HIT series " or " HT series " of CHEMICAL INDUSTRIES, LTD manufacture with by JGC Catalyst and " OPTLAKE " (registration mark) that Chemicals Ltd. manufactures.
A second aspect of the present invention provides the preparation method of described photochromic article, comprises the following steps：
Base material and color-changing membrane are provided；
Wherein, base material, base resin are identical；
Base material is fitted by way of melting with color-changing membrane.
A third aspect of the present invention provides the preparation method of described photochromic article, comprises the following steps：
Base material and color-changing membrane are provided；
Wherein, base material, base resin differ；
Adhesive is at least partially covered over the upper surface of described base material, so that base material is fitted with color-changing membrane.
A fourth aspect of the present invention provides application in glasses, display device or communication equipment for the color-changing membrane.
Below by embodiment, the present invention is specifically described.Be necessary it is pointed out here that, following examples are only used In the invention will be further described it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field Some the nonessential improvement made according to the content of the invention described above and adjustment, still fall within protection scope of the present invention.
In addition, if not having other explanations, raw materials used is all commercially available, and number used by following material is weight Part.
Raw material：
Base material and base resin：
A1：Merlon, thickness is 0.8 millimeter；
A2：Triafol T, thickness is 0.9 millimeter；
A3：Amorphous copolyester, thickness is 1 millimeter；
The preparation method of described amorphous copolyester is：
In 500mL round-bottomed flask, add dimethyl terephthalate (DMT) (0.40mol)=77.7g, neopentyl glycol (0.30mol)=31.3g, 2,2,4,4- tetramethylcyclobutanediol (0.30mol)=43.3g, three -2 ethyl hexanoic acid butyl tin 0.02g, lithium hydroxide monohydrate 0.05g, AIP 0.03g, Triphenyl phosphate 0.03g, then heat up 290 DEG C instead Answer 4 hours and obtain.
A4：Polyurethane polymer, the trade mark is " SUPERFLEX420 "；Thickness is 1 millimeter；
Described " SUPERFLEX420 " (registration mark, is manufactured by Dai-ichi Kogyou Seiyaku Co.Ltd., puts down All particle diameters：120nm, percentage elongation：280%, Tg：- 20 DEG C, 100% modulus：15N/mm2Gu, composition (polyurethane resin) concentration： About 32 mass %, water：About 65 mass %, containing the skeleton from Merlon, are polycarbonate polyurethane, cross-linking).
Color-changing membrane
B1：Color-changing membrane, thickness is 0.15 millimeter；
Described color-changing membrane includes：
Base resin 100 weight portion；With
Photochromic compound 0.1 weight portion；
Described photochromic compound is spiral shell (benzo indoline) aphthopyrans.
B2：Color-changing membrane, thickness is 0.2 millimeter；
Described color-changing membrane includes：
Base resin 100 weight portion；With
30 parts of photochromic compound；
Described photochromic compound is chromene.
B3：Color-changing membrane, thickness is 0.2 millimeter；
Described color-changing membrane includes：
Base resin 100 weight portion；With
10 parts of photochromic compound；
Described photochromic compound is indoles aphthopyrans.
B4：Color-changing membrane, thickness is 0.1 millimeter；
Described color-changing membrane includes：
Base resin 100 weight portion
Photochromic compound 10 weight portion；
γ-glycidoxypropyl diethoxy silane 5 weight portion；
Described photochromic compound is phenanthro- pyrans.
B5：Color-changing membrane, thickness is 0.1 millimeter；
Described color-changing membrane includes：
Base resin 100 weight portion
Photochromic compound 10 weight portion；
γ-glycidoxypropyl diethoxy silane 5 weight portion；
With nano silicon 5 weight portion.
Described photochromic compound is spiral shell (benzo indoline) aphthopyrans.
B6：Color-changing membrane, thickness is 0.1 millimeter；
Described color-changing membrane includes：
Base resin 100 weight portion
Photochromic compound 10 weight portion；
γ-glycidoxypropyl diethoxy silane 5 weight portion；
With nano silicon 5 weight portion；With
Composite inorganic oxide fine particle 10 weight portion；
Described photochromic compound is spiral shell (benzo indoline) aphthopyrans.
Described composite inorganic oxide fine particle includes nano silicon 5 weight portion, tin oxide 4 weight portion, five oxidations Two antimony 3 weight portion, di-iron trioxide 3 weight portion.
Adhesive
C1：The safe happy pine Technomelt Q 8783 of Henkel, thickness is 100 microns；
C2：Esters of acrylic acid adhesive, thickness is 120 microns；
The preparation method of described esters of acrylic acid adhesive is：
By the butyl polyacrylate of 100 weight portions, tetraethylene glycol two -2 ethyl hexanoic acid ester of 5 weight portions, 4 weight portions height The epoxy-capped polyetheramine of lithium chlorate and 5 weight portions mixes and obtains final product described esters of acrylic acid adhesive；
Described epoxy-capped polyetheramine is prepared by following methods：
The benzylamine of 100 grams of epoxy resin E51 and 0.23 mole is dissolved in 2000 grams of propylene glycol monomethyl ethers, nitrogen is protected Under shield, after 100 DEG C are reacted 4 hours, after being down to room temperature deionized water cyclic washing product, 50 DEG C of dryings in vacuum drying oven 5 hours, obtain described epoxy-capped polyetheramine.
C3：Esters of acrylic acid adhesive, thickness is 130 microns；
The preparation method of described esters of acrylic acid adhesive is：
By the butyl polyacrylate of 100 weight portions, tetraethylene glycol two -2 ethyl hexanoic acid ester of 5 weight portions, 4 weight portions height Amino silane modified beta-schardinger dextrin-graphene oxide-the polybenzimidazole compound of lithium chlorate and 5 weight portions mixes i.e. Obtain described esters of acrylic acid adhesive；
Described amino silane modified beta-schardinger dextrin-graphene oxide-polybenzimidazole compound is prepared into by following methods Arrive：
1) by 0.16 mole 3,3 ', 4,4 '-tetramino diphenyl sulphone (DPS) is first dissolved in 1000 containing 85wt% phosphorus pentoxide In gram polyphosphoric acids, then by the 1 of 0.1 mole, between 3,5-, benzenetricarboxylic acid is added in reactant liquor, after 200 DEG C of reactions 20 hours, It is down to room temperature, precipitating, in water, is then neutralized with ammoniacal liquor, filters, be vacuum dried, obtain amino-terminated hyperbranched at 100 DEG C Polybenzimidazoles；
2) 10 grams of beta-schardinger dextrins are completely dissolved in after acetum, add 10 grams of steps 1) described in amino-terminated over-expense Change polybenzimidazoles, 3 grams of graphene oxides, 3 grams of amino silicane coupling agent KH-550,2 grams of glutaraldehydes and 2 grams of 1,3- dibromos third Alkane ultrasonic disperse, adjust pH value of solution between 8.0～9.0；Stir 1.5～2.5h at 55～65 DEG C, obtain sediment, cleaning To neutral and dry, obtain amino silane modified beta-schardinger dextrin-graphene oxide-polybenzimidazole compound.
C4：Esters of acrylic acid adhesive, thickness is 150 microns；
The preparation method of described esters of acrylic acid adhesive is：
By the butyl polyacrylate of 100 weight portions, tetraethylene glycol two -2 ethyl hexanoic acid ester of 5 weight portions, 4 weight portions height Lithium chlorate, the amino silane modified beta-schardinger dextrin-graphene oxide-polybenzimidazole compound of 5 weight portions and 5 weight portions Epoxy-capped polyetheramine mixes and obtains final product described esters of acrylic acid adhesive；
The same B3 of preparation method of described amino silane modified beta-schardinger dextrin-graphene oxide-polybenzimidazole compound.
Described epoxy-capped polyetheramine is prepared by following methods：
The benzylamine of 100 grams of epoxy resin E51 and 0.23 mole is dissolved in 2000 grams of propylene glycol monomethyl ethers, nitrogen is protected Under shield, after 100 DEG C are reacted 4 hours, after being down to room temperature deionized water cyclic washing product, 50 DEG C of dryings in vacuum drying oven 5 hours, obtain described epoxy-capped polyetheramine.
Embodiment 1
A kind of photochromic article, includes base material (A1) and color-changing membrane (B1) from the bottom to top；
Described variable color membrane preparation method：
Described base resin is A1；
A1 is fitted by way of melting with B1.
Embodiment 2
A kind of photochromic article, includes base material (A2) and color-changing membrane (B2) from the bottom to top；
Described variable color membrane preparation method：
Described base resin is A2；
A2 is fitted by way of melting with B2.
Embodiment 3
A kind of photochromic article, includes base material (A3) and color-changing membrane (B3) from the bottom to top；
Described variable color membrane preparation method：
Described base resin is A3；
A3 is fitted by way of melting with B3.
Embodiment 4
A kind of photochromic article, includes base material (A4) and color-changing membrane (B4) from the bottom to top；
Described variable color membrane preparation method：
Described base resin is A4；
A4 is fitted by way of melting with B4.
Embodiment 5
A kind of photochromic article, includes base material (A4) and color-changing membrane (B5) from the bottom to top；
Described variable color membrane preparation method：
Described base resin is A4；
A4 is fitted by way of melting with B5.
Embodiment 6
A kind of photochromic article, includes base material (A4) and color-changing membrane (B6) from the bottom to top；
Described variable color membrane preparation method：
Described base resin is A4；
A4 is fitted by way of melting with B6.
Embodiment 7
A kind of photochromic article, includes base material (A4), adhesive (C1), color-changing membrane (B6) from the bottom to top；
Described variable color membrane preparation method：
Described base resin is A1；
C1 is at least partially covered over the upper surface of A4, so that A4 is fitted with B6.
Embodiment 8
A kind of photochromic article, includes base material (A4), adhesive (C2), color-changing membrane (B6) from the bottom to top；
Described variable color membrane preparation method：
Described base resin is A1；
C2 is at least partially covered over the upper surface of A4, so that A4 is fitted with B6.
Embodiment 9
A kind of photochromic article, includes base material (A4), adhesive (C3), color-changing membrane (B6) from the bottom to top；
Described variable color membrane preparation method：
Described base resin is A1；
C3 is at least partially covered over the upper surface of A4, so that A4 is fitted with B6.
Embodiment 10
A kind of photochromic article, includes base material (A4), adhesive (C4), color-changing membrane (B6) from the bottom to top；
Described variable color membrane preparation method：
Described base resin is A1；
C4 is at least partially covered over the upper surface of A4, so that A4 is fitted with B6.
Durability test
The chemical durability of the color-changing membrane manufacturing to be assessed by being immersed in variable color diaphragm 10 hours in boiling water.Boiling examination Adhesion level is assessed by attempting release coating with standard viscose band before and after testing.
Test result is shown in Table 1.
Embodiment Polarization efficiency before durability test Durability test rear polarizer efficiency Peelable degree after durability test
Embodiment 1 86% 82% More difficult stripping
Embodiment 2 88% 85% More difficult stripping
Embodiment 3 93% 90% More difficult stripping
Embodiment 4 93% 92% More difficult stripping
Embodiment 5 95% 94% More difficult stripping
Embodiment 6 100% 100% More difficult stripping
Embodiment 7 100% 90% More difficult stripping
Embodiment 8 100% 94% More difficult stripping
Embodiment 9 100% 97% More difficult stripping
Embodiment 10 100% 100% More difficult stripping
The photochromic article that data above can be seen that the present invention is respectively provided with more preferable weatherability and longer service life, It is thus provided that the Advantageous Effects of the present invention.
Aforesaid example is merely illustrative, for explaining some features of the feature of the disclosure.Appended claim It is intended to the scope as wide as possible requiring to be contemplated that, and embodiments as presented herein is only according to all possible embodiment The embodiment of the selection of combination explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention The example of feature selectional restriction.And the progress in science and technology will be formed due to language performance inaccurate reason and not The possible equivalent being presently considered or son are replaced, and these changes also should be interpreted by appended in the conceived case Claim covers.

Claims (10)

1. a kind of photochromic article is it is characterised in that at least include,
Base material；With
Color-changing membrane；
Described base material and color-changing membrane are connected by melting or are connected by adhesive；
Described color-changing membrane at least includes base resin and photochromic compound.
2. photochromic article as claimed in claim 1 is it is characterised in that described base material, base resin can be identical or different, and It is each independently selected from Merlon, amorphous copolyester, polyamide, polyethylene terephthalate, ENB and second The copolymer of alkene, acetylbutyrylcellulose, Triafol T, polyurethane polymer, amino resins are birdsed of the same feather flock together compound and third At least one in olefin(e) acid esters polymer.
3. photochromic article as claimed in claim 2 is it is characterised in that described polyurethane polymer includes polycarbonate type Polyurethane.
4. photochromic article as claimed in claim 1 is it is characterised in that described adhesive is gluing selected from (methyl) esters of acrylic acid At least one in agent, epoxy resin tackifier, polyurethane tackifier and polyimide adhesive.
5. photochromic article as claimed in claim 4 is it is characterised in that described adhesive is esters of acrylic acid adhesive, and institute The esters of acrylic acid adhesive stated, its preparing raw material includes：
The acrylate copolymer of 100 weight portions；
The ester plasticiser of 0.01～20 weight portion；
The alkali metal salt of 0.001～7 weight portion；
Amino silane modified beta-schardinger dextrin-graphene oxide-the polybenzimidazole compound of 0.01～10 weight portion and
The epoxy-capped polyetheramine of 0.01～10 weight portion.
6. photochromic article as claimed in claim 1 is it is characterised in that described color-changing membrane at least includes
Base resin 100 weight portion；With
Photochromic compound 0.1-30 weight portion.
7. photochromic article as claimed in claim 6 is it is characterised in that described photochromic compound is selected from：Aphthopyrans, benzene And any one in pyrans, indoles aphthopyrans, phenanthro- pyrans, spiro-pyrans.
8. the preparation method of photochromic article as claimed in claim 1 is it is characterised in that comprise the following steps：
Base material and color-changing membrane are provided；
Wherein, base material, base resin are identical；
Base material is fitted by way of melting with color-changing membrane.
9. the preparation method of photochromic article as claimed in claim 1 is it is characterised in that comprise the following steps：
Base material and color-changing membrane are provided；
Wherein, base material, base resin differ；
Adhesive is at least partially covered over the upper surface of described base material, so that base material is fitted with color-changing membrane.
10. application in glasses, display device or communication equipment for the photochromic article as described in claim 1～7.
CN201610807924.1A 2016-09-07 2016-09-07 Color-changing product, preparation method and application thereof Active CN106433609B (en)

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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
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
JP2019111808A (en) * 2017-12-25 2019-07-11 株式会社トクヤマ Laminate, optical substrate comprising the laminate, and optical article including the optical substrate
CN111116956A (en) * 2019-12-26 2020-05-08 中国乐凯集团有限公司 TAC functional film and preparation method thereof

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JP2019111808A (en) * 2017-12-25 2019-07-11 株式会社トクヤマ Laminate, optical substrate comprising the laminate, and optical article including the optical substrate
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
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CN111116956A (en) * 2019-12-26 2020-05-08 中国乐凯集团有限公司 TAC functional film 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

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