CN1454912A - Optical angle discolouring powder material, and preparing method and use thereof - Google Patents
Optical angle discolouring powder material, and preparing method and use thereof Download PDFInfo
- Publication number
- CN1454912A CN1454912A CN 03114913 CN03114913A CN1454912A CN 1454912 A CN1454912 A CN 1454912A CN 03114913 CN03114913 CN 03114913 CN 03114913 A CN03114913 A CN 03114913A CN 1454912 A CN1454912 A CN 1454912A
- Authority
- CN
- China
- Prior art keywords
- acid
- group
- compound
- mol
- addressed
- 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.)
- Pending
Links
Landscapes
- Paints Or Removers (AREA)
Abstract
The present invention discloses an optical angle chromotropic powder material, its preparation method and application. Said invention uses small molecule material with chiral structure as polymerization monomer and intrdouces it into polymerization reaction to make it become a part of whole high-molecular chain unit so as to form a kind of spiral structure similar to DNA. Said spiral super-grade structure can make the material have selectivity for reflection of incident light, so that under the condition of different observation angle the wavelengths of reflected light waves are different, their colours are different to produce optical angle chromotropic effect. By changing formula of raw material said product can produce different colour change, and can be made into chromotropic paint, pigment, printing ink and film, etc.
Description
Technical field
The present invention relates to a kind of powdered material, preparation method and the application in different field thereof with light angle color changing effect.
Technical background
Along with socioeconomic growing, people are more and more higher to the individual demand of commodity.Therefore the application techniques of commodity seems particularly important.Be subjected to the influence of environmental regulation to the factors such as restriction of volatile organic matter (VOC) and hazardous air pollutants (HAPs) simultaneously, coating manufacturer is devoted to develop nontoxic " greenization " product.Recently a kind of angular photochromic material of decorating with false proof effect (reflection colour of material changes with the variation of viewing angle) that has concurrently has been subjected to extensive attention.
The angular color change effect of material can obtain by the laminate structure at intermittence that forms material, and alternative metal and the coextrusion thin layer that obtains of ceramic plate are just had this effect (Dobrowolski, J.A.; Ho, F.C.and Waldorf, A., Applied Optics, 1989,28, P14).Normally the special construction that is had by material itself is produced the difference reflection of light wave.Small molecules liquid crystal material with chiral structure often shows the angular color change effect, as (patent GB 1387389) disclosed material, but because heat resistance, the ageing-resistant performance of small molecule material are poor, has therefore limited its application in every respect.
Introduce in the macromolecular chain by the small molecules that will have chiral structure, thereby form macromolecular material, make it to have the angular color change effect by the ratio of control optically-active component in macromolecular chain with optically-active component.Have now found that, form macromolecular material by introducing chirality small molecules and have the angular color change effect with special construction.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of angular color change powder coating and its production and application.
Technical conceive of the present invention is such:
The present invention will have the small molecule material of chiral structure and introduce in the polyreaction as polymerization single polymerization monomer, make it to become the part in the whole macromolecule chain section.Because the micromolecular existence of these chiralitys in the macromolecular chain makes macromolecular chain be distorted, thereby just forms the spirane structure of a kind of DNA of being similar to.Because this spirane structure is present in the macromolecular chain with higher molecular weight, can be referred to as to have spiral super-grade structure.This spiral super-grade structure makes material have selectivity to reflection of incident light, and the optical wavelength difference that reflects under different viewing angles, color are also just different, the angular color change effect also just occurred.This angular color change effect depends primarily on the pitch of spiral in the spiral super-grade structure, and pitch is short more, and the wavelength of reflecting light is also just short.
Angular color change powder coating of the present invention is the unregulated polymer that includes following group:
Wherein:
Z is other atoms except that carbon atom, hydrogen atom, comprises in haloid element, oxygen family element, nitrogen group element, carbon group element, boron group element and the transition metal etc. one or more;
R is carbon atom, hydrogen atom substituting group;
OH/NR is a capping group;
() expression can contain, but not necessarily contains;
This material can characterize with differential scanning calorimetry (DSC) and Fourier infrared spectrum methods such as (FTIR), carries out ultimate analysis for the chemical mode that can adopt that contains metallic element.Other characterizing method can carry out auxiliary or further sign as nucleus magnetic resonance, mass spectrum etc.
Differential scanning calorimetry mainly provides second-order transition temperature, fusing point and/or clearing point, the decomposition temperature equitemperature scope of material, different ingredients synthetic material, concrete first endothermic temperature and/or the second endothermic temperature difference, scope first endothermic temperature roughly is between 70～350 ℃, second endothermic temperature is between 90～450 ℃, the material that has may have only first endothermic temperature or second endothermic temperature, and the two has the material that has.
Fourier transform infrared spectroscopy (FTIR) mainly provides the essential characteristic peak of material, and table 1 is the essential characteristic peak of the prepared material of different ratios of raw materials.Table 1 is that the substituted benzene type of the prepared material of different ratios of raw materials is at 2000～1600cm
-1Frequency multiplication, absorption curve and C-H beam frequency;
The essential characteristic peak sequence number of table 1 preparation material prepares the essential characteristic peak range of spectra local/cm of material
-11 capping group O-H, N-H stretching vibration 4000～30002 C-H stretching vibrations 3300～27003 O=C-stretching vibrations, 1900～1650
The frequency multiplication of C-H flexural vibration and 1500～10006 C-O stretching vibrations of sum of fundamental frequencies 4 aromatic rings 1675～15005 C-H in-plane bending vibrations, C-C skeletal vibration 1300～1000 in the aromatic hydrocarbons
This material has the characteristics of reflection efficiency height, chromaticity superior performance.Prescription by the change raw material can produce that blue stain is red, red stain is yellow, red stain is green, blue stain is green, the product of Jin Bianlan or the like different colours conversion.This material also has good water-fast, acid and alkali-resistance, wear-resisting, temp. variation resistant, weather resistance simultaneously.By after-processing technology, material further can be processed into powder allochroic paint, optically variable pigments, photochromatic printing ink, the light-variation film of direct spraying.
The angular photochromic material that the present invention produced has wide application field.
(1) field of coating: base materials such as this material and metal, glass, pottery, plastics, rubber, stone material, timber, paper have good adhesive, and film forming is even, color is beautiful.Can be widely used in the vehicle body of high-grade car and aircraft and the coating on surfaces such as parts, steamer, motorcycle, household electrical appliances, five metals device, light fixture, building materials and articles for daily use (mobile phone, walkman, wrist-watch).
(2) false proof field: this material has the advantages that color changes with the change of viewing angle, and it easily observes, can not duplicate the anti-false fidelity that characteristic can be used for famous-brand and high-quality commodity, currency, certificate, Valued Securities.
(3) temperature indicating element: this material has special thermocolour performance simultaneously.When reaching certain high temperature, material becomes transparent, loses the angular color change function simultaneously.Can be used for as goods temperature indicatings such as pipeline, motors.
The present invention adopts the method for melt condensation commonly used, is solvent with the acid anhydrides, high vacuum (0～10mbar), carry out under the condition of high temperature (100～550 ℃).
Concrete preparation method comprises the steps:
(1) several different monomers with bifunctional and chipal compounds are reacted according to certain ratio, hydroxyl that is had on monomer that is added and the chipal compounds or ratio amino and carboxyl maintenance 1: 0.5～1.5, under the protection of inactive gas, add solvent, be warming up to backflow, form micromolecular performed polymer;
Its add-on is 1～0.5: 1.5 (mol ratios), and temperature of reaction is 100～300 ℃, and the reaction times is 1.5～7.5 hours;
The solvent of being addressed comprises the acid (acid anhydride) that acetate (acid anhydride), propionic acid (acid anhydride), formic acid (acid anhydride) or phenylformic acid (acid anhydride) etc. can steam under normal temperature or reduced pressure;
Two or the multi-functional monomer of being addressed comprises the compound with hydroxyl and/or carboxyl and/or amido and/or acid amides, preferably one or more in benzene two/triphenol, dibasic alcohol, polyvalent alcohol, dihydroxy naphthlene, poly-hydroxy naphthalene, diprotic acid, polyprotonic acid, P-hydroxybenzoic acid, the hydroxynaphthoic acid;
The chipal compounds of being addressed is the chipal compounds with bifunctional, preferably 1,4,3, and 6-two dehydration-D-sorbs (sugar) alcohol, D-dextrocamphoric acid, 2, one or more in 3-dihydroxyl butane or the 3-methyl hexanodioic acid etc.;
In optimized technical scheme of the present invention, in order to improve the processing suitability of material, also can in macromolecular chain, introduce the compound of some simple function groups, as phenol, lipid acid, formaldehyde etc., with the degree of branching of raising macromolecular chain, and then strengthen being cross-linked with each other of macromolecular chain.
Angular photochromic material described in the invention can be produced the material with different color changeable effects by different prescriptions, and it is as follows mainly to fill a prescription:
0.1 one or more of～99%mol pair hydroxyl (or amino) compound is as aromatic diol (ammonia), heterocycle dibasic alcohol (ammonia), aliphatic dihydric alcohol (ammonia) etc.
0.1 one or more of～70%mol pair carboxylic compound is as aromatic binary carboxylic acid, heterocycle di-carboxylic acid, fat dicarboxylic acid etc.
0.1 the bifunctional compound of～60%mol generally is the compound that contains carboxyl and hydroxyl (or amino) simultaneously.
0.1 one or more chipal compounds of～50%mol.
0.1 one or more simple function group compounds of～10%mol.
In addition, in order to improve the performance of material, also can add a spot of catalyzer, toughner, softening agent in prescription, addition is 1～5 ‰ of total prescription.
Described catalyzer is mainly acids or can serves as the catalyzer of salt, polyester catalyzer commonly used such as Phenylsulfonic acid, sulfuric acid, carboxylic acid sodium, carboxylic acid barium preferably.
Described toughner is general plastics toughner, the preferably elastomerics of the polyolefine of stearic acid, lower molecular weight, dynamic vulcanization.
Described softening agent is general Plasticizer for plastics, is mainly the higher ester class of fusing point, preferably stearic acid, dioctyl phthalate (DOP) (DNOP), diethyl phthalate (DEP), dibutyl phthalate (DBP).
(2) be warming up to 270～550 ℃, temperature difference, the color of product are also different, begin underpressure distillation then, and vacuum tightness reaches 5～20mbar as far as possible, certain hour, and color will appear in system.Stopped reaction, the color of product can be fixed up along with the cooling of system.In addition, because the color of this macromolecular material and the influence that color changeable effect is subjected to temperature of reaction, therefore the different types of cooling will produce distinct colors and color changeable effect, adopt slowly cooling and two kinds of method of cooling of quenching usually.
Products therefrom is the solid that has color, has metalluster.
Material described in the invention can make it to reach light angle color changing effect by following post-treatment method, and is applied in the various fields.According to the different purposes of material, material can be made light respectively and be become coating, photochromatic printing ink, light-variation film.And realize the commercialization of material with technologies such as spraying, dip-coating, thermography and blowings.
1, light becomes the preparation of coating
1,1 spraying method
Spraying method mainly passes through pulverizing, spraying and three steps of aftertreatment of material.
At first be that material is pulverized.Crushing process can adopt for two steps carried out, and was bigger particulate state with its precrushing earlier, and particle diameter is about 1～5mm.And then carry out careful grinding, and make it to reach the powder of micron level, be generally 5～50 μ m.Material after the grinding will sieve.The formed powder of materials of different colors can carry out blend according to different ratios to be handled, to reach different effects.
Be spraying process then.Powder directly is sprayed at substrate surface.Spraying process can adopt methods such as electrostatic spraying, flame plating, corona spraying; Coat-thickness is at 10～60 microns.
Be last handling process at last.Base material after the spraying is heat-treated, and temperature is between 250～300, and treating processes can be carried out in air blast or infrared drying tunnel.Formed transparent film at substrate surface like this with light angle color changing effect.
1,2 thermography methods
The thermography method comprises pulverizing, printing and three steps of aftertreatment of material.Wherein pulverizing is identical with spraying method with last handling process.
Printing process is material powder to be mixed by a certain percentage solvent such as toluene, propyl carbinol, dimethylbenzene, tetrahydrofuran (THF) etc. with solvent earlier.After dispersing at a high speed, emulsion is injected printing press, after heating, directly print with substrate surface.Obtain angular photochromic film after the drying.Printing process adopts the hot melt stencil usually, hot melt offset printing, hot melt gravure etc.
Except spraying and thermography, handle the film that obtains having angular color change equally again after also material powder can being deposited on substrate surface by fluidized-bed.In above method, material is filmed at the deposit thickness of substrate surface and the different variable colors that will form different wavelength range of heat treated temperature.
2, the preparation of light-variation film
2,1 plasticising blow moulding
This method will add a certain proportion of softening agent in reaction, make the material plasticizing, before reaction end back system is uncolled, material is injected in the blow machine, just can form the film that has light angle color changing effect through blow molding.Also can earlier reaction product be passed through extruding pelletization, and then enter in the blow moulding machine, be blow molded into film through after the heating and melting.
2,2 blending methods
Be material granule to be carried out blend according to certain ratio and plastic material handle, again the material after the blend carried out the blowing film forming and handle, to produce uniform film.The intermingling material that is usually used in has PVC, PP, PU, PE etc.This transparent film with light angle color changing effect can be compound with paper, plastics, metal etc., also can use separately.It is false proof to be suitable for packing, certificate etc.
3, the preparation of photochromatic printing ink
Photochromatic printing ink be will prepare earlier the variable color powder or the film that crushes, after high speed dispersion, form photochromatic printing ink with resin and each analog assistant.
4, the preparation of optically variable pigments
With variable color powder and the various tinting material blend for preparing, the preparation optically variable pigments.Addition is 0～55% of a total amount of material.Tinting material is organic dye and pigment dyestuff.Zhu is Yaoed Wei perylene, perylene ketone, anthracene embedding (buttress) anthraquinone, anthraquinone, dioxazine, phthalein green grass or young crops, isoindoline, quinacridone, diketopyrrolo-pyrrole serial pigment or dyestuff.
Description of drawings
Fig. 1 is that the substituted benzene type of the prepared material of different ratios of raw materials is at 2000～1600cm
-1Frequency multiplication, absorption curve and C-H beam frequency.
Embodiment
Embodiment 1
The 13g P-hydroxybenzoic acid, the 4g terephthalic acid, the 1g Resorcinol, the 2.5g Isosorbide adds in the reactor, adds the 40ml diacetyl oxide, mechanical stirring, nitrogen protection is heated to backflow, keeps 30min; Temperature of reaction is increased to 300C gradually, keeps 30min.After not having liquid to steam, the beginning underpressure distillation, vacuum tightness constantly is increased to 10mbar, keeps 30min.System viscosity begins to strengthen, and darkens, and strengthens and stirs, and behind maintenance high vacuum, the high temperature 30min, reactant becomes blueness, and slowly cooling recovers normal pressure, and the blueness of material slowly is fixed up, and takes out.The gained material is in Fourier transformation infrared spectrometer (FTIR) test down, and the essential characteristic peak is as shown in table 2.The gained material is in down test of differential scanning calorimetry (DSC), and the second-order transition temperature Tg shown in the essential characteristic curve, the first endothermic temperature T1, the second endothermic temperature T2, decomposition temperature T3 are as shown in table 3.
The response sample film forming is smeared in heating on glass baseplate, and 90 degree are observed and presented blueness, and 30 degree take on a red color, and material is transparent.
Embodiment 2
21.4g 4-hydroxyl-4-formic acid biphenyl, the 10.8g Ursol D, the 13.8g P-hydroxybenzoic acid, the 33.2g terephthalic acid, in 14.6g Isosorbide and the 40ml diacetyl oxide adding system, mechanical stirring, nitrogen protection is heated to backflow, keeps 30min; Temperature of reaction is increased to 300 ℃ gradually, keeps 30min.After not having liquid to steam, the beginning underpressure distillation, vacuum tightness constantly is increased to 10mbar, keeps 30min.System viscosity begins to strengthen, and darkens, and strengthens and stirs, and behind maintenance high vacuum, the high temperature 30min, reactant becomes golden yellow, and slowly cooling recovers normal pressure, and the golden yellow of material slowly is fixed up, and takes out.The gained material is in Fourier transformation infrared spectrometer (FTIR) test down, and the essential characteristic peak is as shown in table 2.The gained material is in down test of differential scanning calorimetry (DSC), and the second-order transition temperature Tg shown in the essential characteristic curve, the first endothermic temperature T1, the second endothermic temperature T2, decomposition temperature T3 are as shown in table 3.
The response sample film forming is smeared in heating on glass baseplate, and 90 degree are observed and presented golden yellow, and 30 degree are golden red, and material is transparent.
Embodiment 3
13.8g P-hydroxybenzoic acid, the 11g Resorcinol, the 33.2g m-phthalic acid, 13.7g4-amino-phenylformic acid, in 14.6g Isosorbide and the 50ml diacetyl oxide adding system, mechanical stirring, nitrogen protection is heated to backflow, keeps 30min; Temperature of reaction is increased to 280 ℃ gradually, keeps 30min.After not having liquid to steam, the beginning underpressure distillation, vacuum tightness constantly is increased to 5mbar, keeps 30min.System viscosity begins to strengthen, and darkens, and strengthens and stirs, and behind maintenance high vacuum, the high temperature 30min, reactant becomes golden yellow, and slowly cooling recovers normal pressure, and the golden yellow of material slowly is fixed up, and takes out.The gained material is in Fourier transformation infrared spectrometer (FTIR) test down, and the essential characteristic peak is as shown in table 2.The gained material is in down test of differential scanning calorimetry (DSC), and the second-order transition temperature Tg shown in the essential characteristic curve, the first endothermic temperature T1, the second endothermic temperature T2, decomposition temperature T3 are as shown in table 3.
The response sample film forming is smeared in heating on glass baseplate, and 90 degree are observed and presented golden red, and 30 degree are yellow-green colour, and material is transparent.
Embodiment 4
13.8g P-hydroxybenzoic acid, the 22g Resorcinol, 18.8g2-hydroxyl-6-naphthoic acid, the 16.6g terephthalic acid, 20g D-dextrocamphoric acid, in the 30ml diacetyl oxide adding system, mechanical stirring, nitrogen protection is heated to backflow, keeps 30min; Begin to steam water and acetate, temperature of reaction is increased to 270 ℃ gradually, keeps 60min.After not having liquid to steam, the beginning underpressure distillation, vacuum tightness constantly is increased to 5mbar, keeps 60min.System viscosity begins to strengthen, and darkens, and strengthens and stirs, and behind maintenance high vacuum, the high temperature 30min, reactant becomes golden yellow, and slowly cooling recovers normal pressure, and the blue-greenish colour of material slowly is fixed up, and takes out.The gained material is in Fourier transformation infrared spectrometer (FTIR) test down, and the essential characteristic peak is as shown in table 2.The gained material is in down test of differential scanning calorimetry (DSC), and the second-order transition temperature Tg shown in the essential characteristic curve, the first endothermic temperature T1, the second endothermic temperature T2, decomposition temperature T3 are as shown in table 3.
The response sample film forming is smeared in heating on glass baseplate, and 90 degree are observed and presented blue-greenish colour, and 30 degree are bluish voilet, and material is transparent.
The infrared spectra unit at the principal character peak of table 2 embodiment 1～4 gained material: cm
-1
| Embodiment | ????C＝O | ????C-O | ?????C-H | O-H fills the air the peak | Phenyl ring | 1,4 two replaces | Substituted benzene type C-H out-of-plane vibration frequency | |||
| On the aromatic ring | On the aliphatic hydrocarbon | 1,2 two replaces | 1,2,3 three replace | 1,3,5 three replace | ||||||
| ????1 ????2 ????3 ????4 | ????1680 ????1740 ????1800 ????1850 | ????1180 ????1126 ????1270 ????1240 | ??1811???2970 ??1690???2980 ??1900???2965 ??1770???2985 | ????3500 ????3450 ????3300 ????3500 | ??1500～ ??1675 ??1500～ ??1675 ??1500～ ??1675 ??1500～ ??1675 | ??840～ ??810 ??840～ ??810 ??840～ ??810 ??840～ ??810 | ??770～ ??735 ??770～ ??735 ??770～ ??735 ??770～ ??735 | ??780～705 ??780～705 ??780～705 ??780～705 | ??865～675 ??865～675 ??865～675 ??865～675 | |
Characteristic temperature unit on the DSC curve of table 3 embodiment 1～4 gained material: ℃
| Embodiment Tg T1 T2 T3 |
| ????1????????90????99????180???400 ????2????????100???107???195???395 ????3????????110???200???320???410 ????4????????125???192???270???380 |
Embodiment 5
The material of producing in the example 1 is added in the pulverizer, carry out coarse reduction, be ground into about the about 2mm of particle diameter.The product after the coarse reduction is joined again and carry out careful pulverizing in the ultrafine crusher, the particle diameter after the screening is approximately about 20 microns.
Material powder after pulverizing is added (electrostatic potential 20～60kv) in the electrostatic sprayer, after heating, be sprayed on glass surface, form the uniform films of about 20 micron thickness, the glass that will coat film again takes out after putting into 250 ℃ IR bake heating 30min, just forms the fine and close transparent film of one deck at glass surface.Be blue when right-angle view, 30 degree angles take on a red color when observing.
Embodiment 6
The material of producing in the example 1 is added in the pulverizer, carry out coarse reduction, be ground into about the about 2mm of particle diameter.The product after the coarse reduction is joined again and carry out careful pulverizing in the ultrafine crusher, the particle diameter after the screening is approximately about 20 microns.
Material powder after pulverizing is added in the flame sprayer, after heating, under 280 ℃ hot environment, be painted on the surface of aluminum plate of anticipating, form the uniform films of about 30 micron thickness, the aluminium sheet that spraying is good is put into the cold water quenching, just forms the fine and close transparent film of one deck in surface of aluminum plate.Be blue when right-angle view, 30 degree angles take on a red color when observing.
Embodiment 7
The material of producing in the example 2 is added in the pulverizer, carry out coarse reduction, be ground into about the about 2mm of particle diameter.The product after the coarse reduction is joined again and carry out careful pulverizing in the ultrafine crusher, the particle diameter after the screening is approximately about 20 microns.
Powder and dimethylbenzene after pulverizing is miscible, after the high speed dispersion, adopt stencil to be printed in glass surface, take out after again glass being put into 245 ℃ IR bake heating 30min, just form the transparent film of one deck densification at glass surface.Be golden yellow when right-angle view, 30 degree angles are golden red when observing.
Embodiment 8
The material of producing in the example 3 is added in the pulverizer, carry out coarse reduction, be ground into about the about 2mm of particle diameter.The product after the coarse reduction is joined again and carry out careful pulverizing in the ultrafine crusher, the particle diameter after the screening is approximately about 60 microns.
Powder is directly added in the hot melt screen process press, adopt the hot melt silk screen print method to be printed in glass surface, take out after again glass being put into 275 ℃ IR bake heating 30min, just form the fine and close transparent film of one deck at glass surface.Be golden red when right-angle view, 30 degree angles are yellow-green colour when observing.
Embodiment 9
In example 4, in reaction, add small amount of plasticizer DBP, after reaction finishes, before the reactant cooling, reactant is injected forcing machine, carry out extruding pelletization, form homogeneous granules.Again cooled particle is added in the blow moulding machine, heat the blowing film forming, just produce the uniform thin film of about 5 micron thickness.Film is transparent, and film is overlying on the blank sheet of paper, and right-angle view is a blue-greenish colour, and 30 degree are viewed as the basket purple.Film is overlying on the black background, and effect is more obvious.
Embodiment 10
In example 1, after reaction finishes, before the reactant cooling, reactant is injected forcing machine, directly carry out extruding pelletization, form homogeneous granules.Again cooled particle and PVC particle are carried out blend and extrude, the blend ratio is 5: 1, and the material after the blend is carried out the blowing film forming, generates the uniform thin film of about 4 micron thickness.Film is transparent, and film is overlying on the blank sheet of paper, and right-angle view is blue, and 30 degree are viewed as redness.Film is overlying on the black background, and effect is more obvious.
Claims (15)
1. angular color change powdered material is characterized in that for including the unregulated polymer of following group:
-OH
Wherein:
Z is other atoms except that carbon atom, hydrogen atom, comprises in haloid element, oxygen family element, nitrogen group element, carbon group element, boron group element and the transition metal etc. one or more;
R is carbon atom, hydrogen atom substituting group;
Ring-type contains the organism of assorted element, monocycle or many rings;
Phenyl ring;
Naphthalene nucleus
OH/NR is a capping group
() expression can contain, but not necessarily contains;
Above material can be characterized by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR), and its concrete data are as follows:
Differential scanning calorimetry (DSC) is characterized by: material has one or two endothermic temperature, and first endothermic temperature is between 70～350 ℃, and second endothermic temperature is between 90～450 ℃;
Fourier transform infrared spectroscopy (FTIR) provides the essential characteristic peak of material, and table 1 is the essential characteristic peak of material:
The essential characteristic peak range of spectra local/cm of the essential characteristic peak sequence number material of table 1 material
-11 capping group O-H, N-H stretching vibration 4000～30002 C-H stretching vibrations 3300～27003 O=C-stretching vibrations, 1900～1650
The frequency multiplication of C-H flexural vibration and 1500～10006 C-O stretching vibrations of sum of fundamental frequencies 4 aromatic rings 1675～15005 C-H in-plane bending vibrations, C-C skeletal vibration 1300～1000 in the aromatic hydrocarbons
2. according to the preparation method of the described angular color change powdered material of claim 1, it is characterized in that, comprise the steps:
(1) several different monomers with bifunctional and chipal compounds are reacted under the reflux temperature in solvent, the reaction times is 1.5～7.5 hours, forms micromolecular performed polymer; Hydroxyl that is had on monomer that is added and the chipal compounds or molar ratio amino and carboxyl maintenance 1: 0.5～1.5;
(2) be warming up to 220～350 ℃, underpressure distillation, cooling promptly obtains the angular color change powdered material.
Two or the multi-functional monomer of being addressed comprises the compound with hydroxyl and/or carboxyl and/or amido and/or acid amides;
The chipal compounds of being addressed is the chipal compounds with bifunctional.
3. method according to claim 2 is characterized in that, adds the compound of simple function group.
4. method according to claim 3 is characterized in that the compound of said simple function group comprises phenol, lipid acid or formaldehyde.
5. method according to claim 2, it is characterized in that the two or multi-functional monomer of being addressed is one or more in benzene two/triphenol, dibasic alcohol, polyvalent alcohol, dihydroxy naphthlene, poly-hydroxy naphthalene, diprotic acid, polyprotonic acid, P-hydroxybenzoic acid or the hydroxynaphthoic acid; The chipal compounds of being addressed is 1,4:3,6-two dehydration-D-sorbs (sugar) alcohol, D-dextrocamphoric acid, 2, one or more in 3-dihydroxyl butane or the 3-methyl hexanodioic acid etc.; The solvent of being addressed comprises acetate (acid anhydride), propionic acid (acid anhydride), formic acid (acid anhydride) or phenylformic acid (acid anhydride).
6. method according to claim 2 is characterized in that, the prescription of each component is as follows:
0.1 one or more of～99%mol pair hydroxyl (or amino) compound is as aromatic diol (ammonia), heterocycle dibasic alcohol (ammonia) or aliphatic dihydric alcohol (ammonia);
0.1 one or more of～70%mol pair carboxylic compound is as aromatic binary carboxylic acid, heterocycle di-carboxylic acid or fat dicarboxylic acid;
0.1 contain the bifunctional compound of carboxyl and hydroxyl (or amino) in the time of～60%mol;
0.1 one or more chipal compounds of～50%mol;
0.1 one or more simple function group compounds of～10%mol.
7. method according to claim 6 is characterized in that adding a spot of catalyzer, toughner, softening agent, and addition is 1～5 ‰ of total prescription.
8. method according to claim 7 is characterized in that described catalyzer is mainly acids or can serves as the catalyzer of salt.
9. method according to claim 7 is characterized in that catalyzer Phenylsulfonic acid, sulfuric acid, carboxylic acid sodium or carboxylic acid barium; Described toughner is the polyolefine of stearic acid, lower molecular weight or the elastomerics of dynamic vulcanization; Described softening agent is stearic acid, dioctyl phthalate (DOP) (DNOP), diethyl phthalate (DEP), dibutyl phthalate (DBP).
10. the application of material according to claim 1 is characterized in that, is used to prepare light and becomes material.
11. the application of material according to claim 1 is characterized in that, is used to prepare light-variation film.
12. the application of material according to claim 1 is characterized in that, is used to prepare photochromatic printing ink.
13. the application of material according to claim 1 is characterized in that, is used to prepare optically variable pigments.
14. method according to claim 13 is characterized in that adding small amount of coloring, addition is 0～55% of a total amount of material.
15. method according to claim 14, it is characterized in that described tinting material is organic dye and pigment dyestuff, Bao Kuo perylene, perylene ketone, anthracene embedding (buttress) anthraquinone, anthraquinone, dioxazine, phthalein green grass or young crops, isoindoline, quinacridone, diketopyrrolo-pyrrole serial pigment or dyestuff.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03114913 CN1454912A (en) | 2003-01-15 | 2003-01-15 | Optical angle discolouring powder material, and preparing method and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03114913 CN1454912A (en) | 2003-01-15 | 2003-01-15 | Optical angle discolouring powder material, and preparing method and use thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1454912A true CN1454912A (en) | 2003-11-12 |
Family
ID=29260040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03114913 Pending CN1454912A (en) | 2003-01-15 | 2003-01-15 | Optical angle discolouring powder material, and preparing method and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1454912A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100586740C (en) * | 2008-07-24 | 2010-02-03 | 上海复旦天臣新技术有限公司 | False proof thin film and preparation thereof |
| CN101885242B (en) * | 2009-05-11 | 2013-01-02 | 无锡市岚峰制膜有限公司 | Method for manufacturing intelligent protective film |
-
2003
- 2003-01-15 CN CN 03114913 patent/CN1454912A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100586740C (en) * | 2008-07-24 | 2010-02-03 | 上海复旦天臣新技术有限公司 | False proof thin film and preparation thereof |
| CN101885242B (en) * | 2009-05-11 | 2013-01-02 | 无锡市岚峰制膜有限公司 | Method for manufacturing intelligent protective film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Fabrication of UV-curable solvent-free epoxy modified silicone resin coating with high transparency and low volume shrinkage | |
| CN102020871B (en) | Pigment synergist | |
| CN1153685C (en) | Process for the preparation of decorated substrate | |
| EP0787731A2 (en) | Polymerizable diketopyrrolopyrroles and polymers thereof | |
| CN101353546A (en) | Coating material compositions | |
| Batson et al. | Towards a perylene-containing nanohoop | |
| CN1053680C (en) | Thermosetting compounds, cured product thereof and method of preparing the thermosetting compound | |
| EP3134457B1 (en) | Titanium-based catalyst for vitrimer resins of expoxy/anhyride type | |
| CN1080291C (en) | Preparation of mixed crystals and solid of 1,4-diketopyrrolopyrroles | |
| CN1252078A (en) | Chinrally nematic polyesters | |
| US20210179858A1 (en) | Polymers, processes, compositions & uses | |
| CN1990620A (en) | Branched structure compound containing UV crosslinking reactive group and application thereof | |
| CN1882666A (en) | Coating compositions, their preparation, and coated articles made therefrom | |
| CN100344709C (en) | Composition for cutting off heat-ray, film formed therefrom and method for forming the composition and the film | |
| JPH0695401A (en) | Manufacture of laminated-photoconductive-image forming member | |
| CN1454912A (en) | Optical angle discolouring powder material, and preparing method and use thereof | |
| CN1217008A (en) | Powder coatings with color effect depending on viewing angle | |
| TW200405039A (en) | Use of polymerisable diketopyrrolopyrroles in colour filters | |
| CN107778974B (en) | Connecting material for OMD (organic chemical vapor deposition) ink, OMD ink and preparation method of OMD ink | |
| CN103158386A (en) | Thermal transfer film and method of manufacturing OLED display | |
| Zhou et al. | Synthesis of UV-curable polyesters with lateral double bonds by ring-opening polymerization and their properties | |
| CN1535303A (en) | Coloured paint for screen printing of inner side of insert-moulding pieces | |
| CN1945396A (en) | Liquid crystal display panel | |
| CN1643074A (en) | Anthraquinone dyes | |
| KR20190017749A (en) | An aromatic polyketone having two different structural units |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |