CN104263229B - The film build method of a kind of preparation method of antistatic UV coating and this antistatic UV coating - Google Patents
The film build method of a kind of preparation method of antistatic UV coating and this antistatic UV coating Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
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Abstract
The present invention relates to a kind of preparation method of antistatic UV coating and the film build method of this antistatic UV coating, wherein, the preparation method of described antistatic UV coating first joins ether solvent in the large molecular solution of polythiophene, after disperseing by high-speed stirred, mix again also high-speed stirred with UV performed polymer, reactive diluent, light trigger and, to being uniformly dispersed, finally add solvent; To be that antistatic UV is coating material solidified be coated on plastic sheeting the film build method of described antistatic UV coating, and adopt low-temperature vacuum drying or the air-dry drying method of drum cooler, obtains the film that thickness is 2～5 μ m; Then be first 100-200mJ/cm at photocuring energy2Under condition, solidifying 2s-1min, is then 600-1000mJ/cm at photocuring energy2Under condition, solidify 2s-1min. The good stability of the antistatic UV coating of the present invention, this antistatic film causing also has the advantages such as good and high, the anti-scratch ability of hardness of antistatic property is strong.
Description
Technical field
The present invention relates to organic high molecular compound field, relate to and only use carbon-carbon double bond macromolecular compound, be specifically related toUV cured resin.
Background technology
In recent years, along with developing rapidly of precise electronic and precision equipment industry, for some responsive electronic original parts, coreSheet, the production environment of the products such as precision instrumentation is very strict with the requirement of packaging material. For common plastics sheet material, due toThe high impedance insulation characterisitic of plastics, under friction or sensed conditions, easily produces static. Static the in the situation that of a large amount of accumulation,Easily there is electrion, thus infringement precision equipment. Meanwhile, due to the suction-operated of static, thereby cause dust at plasticsBase material is assembled, and causes cleanliness factor to decline, and then disturbs the production of product, also can affect product quality simultaneously.
In order to reduce and reduce the harm that static brings, conventionally adopt the method that reduces coating material sheet resistance to increaseAdd the electric conductivity of material surface, thereby obtain anlistatig effect. Usual way has following three kinds: (1) has conducting functionResin be film forming matter, coating does not generally add other conductive fillers; (2) add conductive filler, by conductive filler each otherContact and generation electric conductivity; (3) add antistatic surfactant, rely in the continuous release coat of antistatic surfactantStatic, reaches the object of antistatic. Although said method plays anlistatig effect to a certain extent,, due to conductionThe synthetic difficulty of resin, and cost costliness; Add the method for conductive filler and be subject to factors as the impact of cost etc., be coated with simultaneouslyMaterial property can be also unstable; So they are not gratifying solutions all the time. Add antistatic surfactantHave simple process, the feature that cost is low, is generally considered to the effective ways in anti-static material production. But owing to playingThe molecular weight of the surfactant of anti-static function, surface migration is serious, thereby cause antistatic effect persistence andDurability is all lower, and has the problem that uses other materials that contact of polluting.
In paper Syntheticmetals139 (2003) 1-10, there is pair mechanism of action of polymeric antistatic agent: heightMolecule antistatic additive, under the impact of special solvent and resin system, after compared with low-shearing force stretching action, forms in matrixStratiform dispersed structure, thus effectively reduce the resistance of composition coating, and there is the effect of permanent anti-static.CN200610078304 mentions poly-thiophene phenol and derivative thereof because its conjugacy structure, and its electronics can or be jumped over point along strandSubchain moves and has essential electric conductivity.
Ultraviolet-curing paint, is called for short UV coating, is as the curing energy, by the light in coating using high-octane ultraviolet lightInitator produces oligomer and the reactive diluent molecule in free radical or cation and then initiation coating in ultraviolet lighting conditionCross-linking polymerization form film. Than traditional heat curing coating, UV coating has that curing rate is fast, VOC discharge capacityLow, be suitable for the features such as high-speed automated processing; And compared with heat curing coating, UV coating is by crosslinked the gathering between each componentClose, by liquid rapid curing film forming, and there is tridimensional network, the coating performance excellence of production, hardness, pliability, wear-resistingResistance to scraping, chemical proofing, high gloss, durability etc. are improved. Especially, be ultraviolet due to solidification process utilizationThe energy of light, carries out the in the situation that reaction can be at normal temperature or lower than normal temperature, does not need high-temperature heating process, so very suitableShare in the processing on the thermo-responsive plastic basis material surfaces such as PET, PP, PMMA, PC.
But because poly-thiophene phenol is the larger high polymer of a class relative molecular weight, therefore it and UV resin is compatibleProperty poor, cause its prepared paint stability poor, produce the problem such as foreign matter point and a mist, shadow in solidification process in coatingRing the performance such as outward appearance and light transmittance of product; Meanwhile, because photocureable coating is than traditional solvent reducible coatings and water paint phaseRatio, has finer and close tridimensional network, and large molecule antistatic additive is not easy to move to the surface of coating, affects the anti-of productAntistatic property, has therefore limited the application of poly-thiophene phenol in photocureable coating.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of preparation method of antistatic UV coating, and prepared by the method is anti-quietElectricity UV coating has advantages of good stability.
Another technical problem that the present invention solves is to provide a kind of film build method of antistatic UV coating. The method preparationFilm there is the advantages such as good and high, the anti-scratch ability of hardness of antistatic property is strong.
The scheme of the above-mentioned technical problem of the present invention is:
A preparation method for antistatic photocureable coating, the method is made up of following steps:
(1) by even the ether solvent dispersed with stirring of 4 times of antistatic macromolecule material and antistatic macromolecule material weight,Obtain mixed liquor A;
(2) by the polyfunctionality monomer of 0.5～1.5 times of antistatic macromolecule material weight, antistatic macromolecule material weightMeasure the polyfunctionality prepolymer of 1～3 times, the polyether-modified dimethyl silicone polymer of polyfunctionality prepolymer weight 0.5%～1%Mix with the light trigger of polyfunctionality monomer weight 1%～3%, obtain mixed liquid B;
(3) mixed liquid B is joined in mixed liquor A, dispersed with stirring obtains mixed liquor C;
(4) in mixed liquor C, add the solvent of 4～6 times of antistatic macromolecule material weight, be uniformly mixed, to obtain final productDescribed antistatic photocureable coating;
In above-mentioned steps,
Described antistatic macromolecule material is a kind of of poly-thiophene phenol and poly-(3,4-ethylene dioxythiophene) or the twoMixture, wherein, the molecular weight of described polythiophene is 30000～100000; Described poly-(3,4-ethylene dioxythiophene) molecular weightBe 20000～40000.
Described ether solvent is glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethylOne in ether, Propylene Glycol Dimethyl Ether and propane diols diethyl ether or two or more;
Described polyfunctionality monomer is tetramethylol methane tetraacrylate, ethoxyquin tetramethylol methane tetraacrylate, the third oxygenChange tetramethylol methane tetraacrylate, 2,3-hydroxymethyl-propane tetraacrylate, dipentaerythritol five acrylate, dipentaerythritolOne in six acrylate and caprolactone modification double pentaerythritol methacrylate or two or more;
Described polyfunctionality prepolymer is carboxyl acid modified polyurethane acrylic resin, and its molecular weight is 800～6000, acidValue is 1～10mgKOH/g, and the weight percentage of carboxyl is 6%～10%;
Described light trigger be 1-hydroxyl-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-I-phenyl-I-acetone andOne in TMDPO or two or more;
Described solvent is one or more in water, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, acetone and butanone.
In antistatic macromolecule material of the present invention when the mixture of polythiophene and poly-(3,4-ethylene dioxythiophene),The weight ratio of the two is better 1:1～1:2.
Above-mentioned carboxyl acid modified polyurethane acrylic resin can be that Dutch DSM (DSM) Co., Ltd producesNeoRadU-42, NeoRadU-30W, AgiSyn230A2, AgiSyn242 or AgiSyn530 can be also Changxing, Taiwan chemistryDR-U110, DR-U185 or 6170 that company produces can also be the limited production of U.S.'s Sartomer (Sartomer)CN9006NS or CN9010NS.
First the preparation method of antistatic photocureable coating of the present invention joins polythiophene by ether solvent to divide greatlyIn sub-solution, disperse by high-speed stirred, reduce after polythiophene macromolecular potential energy, then with UV performed polymer, reactive diluent, lightInitator mixing high-speed stirred are to being uniformly dispersed, thereby guarantee composition in its entirety potential energy reduces, and finally adds ethanol, water etc. moltenAgent, is down to whole system potential energy minimum, with the low-energy kinetic stability composition obtaining, and guarantee system stableProperty.
Antistatic UV prepared by method of the present invention is coating material solidified can be for the preparation of anti-static plastic film, and this is anti-The preparation method of static plastic sheeting is the conventional plastic sheeting preparation method in this area, specifically comprises coating, dry and UV solidChange step. Wherein, described coating can adopt the conventional coating process in this area, for example showering or roller coating; Described is dryDryly can adopt the conventional drying means in this area, for example low-temperature vacuum drying and cooling forced air drying.
The inventor recommends the preparation method of anti-static plastic film to be made up of following steps:
(1) by coating material solidified being coated on plastic sheeting of antistatic UV prepared said method, and adopt cryogenic vacuumBe dried or the air-dry drying method of drum cooler, obtain the film that thickness is 2～5 μ m; Wherein, described plastic sheeting is poly-methyl-propOne in olefin(e) acid methyl esters film, polycarbonate membrane and polyethylene terephthalate thin film; Described low-temperature vacuum dryingCondition is that vacuum is 0.2～1Pa, and temperature is 0～10 DEG C, and be 2-10 minute drying time; Described cooling forced air drying barPart is that air blast wind speed is 2～5m/s, temperature 10-30 degree, drying time 2-10 minute;
(2) first film step 2 being obtained is 100-200mJ/cm at photocuring energy2Under condition, solidify 2s-Then 1min is 600-1000mJ/cm at photocuring energy2Under condition, solidify 2s-1min; Wherein, solidify during light source used isPressure mercury lamp, centre wavelength is 365nm.
In the preparation method of above-mentioned anti-static plastic film, described plastic sheeting is better polycarbonate membrane; InstituteThe condition of cure of stating better, is first 100-200mJ/cm at photocuring energy2Condition lower hardening time of 2s-6s, then existsPhotocuring energy is 600-1000mJ/cm2Under condition, hardening time 2-6s.
The preparation method of above-mentioned anti-static plastic film has taked UV-curing metallization processes stage by stage, first will scribble anti-The plastic sheeting of static photopolymerizable composition is placed in low-yield (100-200mJ/cm2) ultraviolet light under solidify, to form oneHave the microgel structure of gel-solution state, this structure is conducive to polythiophene macromolecular chain fully unfolds therein, keeps awayExempt to cause because of large molecular aggregates the problem of bad dispersibility together, thereby ensure polythiophene uniform and stable dividing in systemLoose; Meanwhile, first adopt low-energy ultraviolet light polymerization also avoided because of one-step solidification need light energy too high, curing rate mistakeHurry up, the poly-large molecule of thiophene phenol occurs being separated and causes precipitation with UV resin and monomer in solidification process, layering or gelState, makes the outward appearance of the antistatic sheet material after film forming have uneven or occur the phenomenons such as irregular brilliant point; First adopt lowThe ultraviolet light polymerization of energy can make macromolecular poly-thiophene phenol material first be dispersed in microgel polymer network, and then adoptsWith high-energy (600-1000mJ/cm2) ultraviolet light polymerization, can be by making anlistatig light by higher optical power densityPolymeric compositions fully reacts, and has promoted scratch resistance and the hardness of anti-static plastic.
Compared with prior art, the present invention has following beneficial effect:
1. polythiophene and derivative thereof have been solved poor with ultraviolet-curing paint compatibility, easily precipitation, the asking of poor stabilityTopic, thus polythiophene and derivative thereof can be applied in antistatic photocureable coating.
2. when having realized coating surface impedance with coating internal driving, reduce, antistatic property is better than professional standard.Stop the pollution problem that the micromolecular surface migration of easy migration causes, promoted the durability of antistatic performance, ensured simultaneouslyThe visible light transmissivity of coating and definition.
3. consider surface-active and the dimensional instability of plastic material, on formula Design, take into account. Having of Hardness and toughnessMachine combination, has been used polyfunctionality prepolymer and polyfunctionality prepolymer composite, makes made UV coating adhere to excellence with base material.In coating curing process, plastic basis material does not occur bending and deformation. In the time standing thermal shock, film does not ftracture.
4. consider the lower hardness of plastic material, the feature of not scratch resistance of surface, in the combination of formula and curing process,Effectively raise case hardness and the scratch resistance performance of plastic basis material.
Detailed description of the invention
Embodiment 1
1. the coating material solidified preparation of antistatic UV
(1) poly-(3,4-ethylene dioxythiophene) that the polythiophene that is 35000 by 25g molecular weight, 25g molecular weight are 25000Put into reactor 1 with the propylene glycol monomethyl ether of 200g, the rotating speed dispersed with stirring half with high-speed stirred dispersion machine with 200rpm/minHour mix and to obtain mixed liquor A;
(2) the carboxyl acid modified polyurethane acrylic resin that the model of 50gDSM-AGI company being produced is NeoRadU-42(molecular weight is 800, and acid number is 1mgKOH/g, and carboxyl-content is 6%), pentaerythrite six acrylate of 50g, 0.25g's is poly-Ether modified dimethyl polysiloxane (BYK3530) and 1g2-hydroxy-2-methyl-I-phenyl-I-acetone are put into reactor 2 togetherIn, within 1 hour, obtain mixed liquid B to mixing with the rotating speed dispersed with stirring of 200rpm/min with high-speed stirred dispersion machine;
(3) mixture B is mixed with mixture A, obtain mixture C;
(4) join in mixture C after solvent 150g ethanol and 50g water are mixed in proportion, disperse by high-speed stirredMachine, with the rotating speed dispersed with stirring of 200rpm/min 1 hour, to obtain final product.
2. the coating material solidified performance of antistatic UV
The performance that antistatic UV is coating material solidified, the results are shown in following table 1.
The performance that the antistatic UV of table 1. is coating material solidified
| Index | Detection method | Stability |
| The outward appearance of mixture | Visual | Homogeneous phase, clear |
| 90 days ambient stables | D1849 | Homogeneous phase, clear |
| The stability of 30 days 60 degree | D1849 | Homogeneous phase, clear |
| The test of cold-hot cyclical stability | D1849 | Circulate and still keep homogeneous phase, clear 20 times |
3. the preparation of anti-static plastic film
(1) by preparation the coating material solidified showering of antistatic UV on transparent Merlon (PC) basement membrane, showering thickness is4u；
(2) film that adopts cooling alternated blasting to obtain step 1 is dried, and its condition is air blast wind speed 4m/s, temperature30 DEG C, 2 minutes drying times;
(3) first film step 2 being obtained is 200mJ/cm at photocuring energy2Condition lower hardening time of 30s; ThenBe 600mJ/cm at photocuring energy2Under condition, hardening time 15s; Wherein, solidifying light source used is medium pressure mercury lamp, middle cardiac waveLong is 365nm.
4. the performance of anti-static plastic film
The performance of anti-static plastic film is as shown in table 2.
The performance of table 2. anti-static plastic film
| Performance | ASTM | Result |
| Flatness | Range estimation | OK 4 --> |
| Brilliant point | Range estimation | Nothing |
| Light transmittance/ | D1003 | 88.9 |
| Mist degree | D1003 | 0.08 |
| Pencil hardness | D3363 | 1H |
| Scratch resistance | D5264 | 20 times back and forth without scratch |
| Adhesive force | D3359 | 5B |
| Resistance value | D257 | 10^5 |
| Resistance value (after 60 days) | D257 | 10^7 |
| Heat distortion temperature/DEG C | D648 | 130 |
| Coefficient of thermal expansion | D696 | 5×10-5 |
| Thermal cycle | D6944 | Unchanged |
Embodiment 2
1. the coating material solidified preparation of antistatic UV
(1) poly-(3, the 4-enedioxy thiophene that the polythiophene that is 55000 by 16.7g molecular weight, 33.3g molecular weight are 28000Fen) and the ethylene glycol ethyl ether of 200g put into reactor 1, the rotating speed dispersed with stirring with high-speed stirred dispersion machine with 200rpm/minMix half an hour and obtain mixture A;
(2) the carboxyl acid modified polyurethane acrylic resin that the model of 70gDSM-AGI company being produced is NeoRadU-42The polyethers of (molecular weight is 800, and acid number is 1mgKOH/g, and carboxyl-content is 6%), 30g pentaerythrite six acrylate, 0.35gModified dimethyl polysiloxane (BYK3530) and 0.6g2-hydroxy-2-methyl-I-phenyl-I-acetone are put into reactor 2 togetherIn, within 1 hour, obtain mixed liquid B to mixing with the rotating speed dispersed with stirring of 200rpm/min with high-speed stirred dispersion machine;
(3) mixture B is mixed with mixture A, obtain mixture C;
(4) will solvent 150g ethanol and 100g water join in mixture C after mixing, with high-speed stirred dispersion machine withThe rotating speed dispersed with stirring of 200rpm/min 1 hour, to obtain final product.
2. the coating material solidified performance of antistatic UV
The performance that antistatic UV is coating material solidified, the results are shown in following table 3.
The performance that the antistatic UV of table 3. is coating material solidified
| Index | Detection method | Stability |
| The outward appearance of mixture | Visual | Homogeneous phase, clear |
| 90 days ambient stables | D1849 | Homogeneous phase, clear |
| The stability of 30 days 60 degree | D1849 | Homogeneous phase, clear |
| The test of cold-hot cyclical stability | D1849 | Circulate and still keep homogeneous phase, clear 20 times |
3. the preparation of anti-static plastic film
(1) the coating material solidified showering of antistatic UV of being prepared by embodiment 2 on transparent Merlon basement membrane, showering thicknessBe 3 μ m;
(2) film that adopts cryogenic vacuum to obtain step 1 is dried, and its condition is: vacuum 1pa, and 10 DEG C of temperature,2 minutes drying times;
(3) first film step 2 being obtained is 200mJ/cm at photocuring energy2Condition lower hardening time of 30s; ThenBe 600mJ/cm at photocuring energy2Under condition, hardening time 5s; Wherein, solidifying light source used is medium pressure mercury lamp, centre wavelengthFor 365nm.
4. the performance of anti-static plastic film
The performance of anti-static plastic film is as shown in table 4.
The performance of table 4. anti-static plastic film
| Performance | ASTM | Result |
| Flatness | Range estimation | OK |
| Brilliant point | Range estimation | Nothing |
| Light transmittance/ | D1003 | 89.1 |
| Mist degree | D1003 | 0.03 |
| Pencil hardness | D3363 | 2H |
| Scratch resistance | D5264 | 30 times back and forth without scratch |
| Adhesive force | D3359 | 5B |
| Resistance value | D257 | 10^6 |
| Resistance value (after 60 days) | D257 | 10^8 |
| Heat distortion temperature/DEG C | D648 | 130 |
| Coefficient of thermal expansion | D696 | 5×10-5 |
| Thermal cycle | D6944 | Unchanged |
Embodiment 3
1. the coating material solidified preparation of antistatic UV
(1) by the polythiophene of 50g and derivative thereof, (polythiophene that 12.5 molecular weight are 64000 and 37.5g molecular weight are35000 poly-(3,4-ethylene dioxythiophene)) and and the propane diols diethyl ether of 200g put into reactor 1, divide by high-speed stirredLoose machine mixes and to obtain mixture A with the rotating speed dispersed with stirring of 200rpm/min half an hour;
(2) the carboxyl acid modified polyurethane acrylic resin that the model that 70gDSM-AGI company produces is NeoRadU-30W(molecular weight is 4400, and acid number is 8mgKOH/g, and carboxyl-content is 6%), the polyethers of 30g pentaerythrite six acrylate, 0.35gModified dimethyl polysiloxane (BYK3530) and 0.6g2-hydroxy-2-methyl-I-phenyl-I-acetone are put into reactor 2 togetherIn, within 1 hour, obtain mixed liquid B to mixing with the rotating speed dispersed with stirring of 200rpm/min with high-speed stirred dispersion machine;
(3) mixture B is mixed with mixture A, obtain mixture C;
(4) will solvent 100g ethanol and 100g water join in mixture C after mixing, with high-speed stirred dispersion machine withThe rotating speed dispersed with stirring of 200rpm/min 1 hour, to obtain final product.
2. the coating material solidified performance of antistatic UV
The performance that antistatic UV is coating material solidified, the results are shown in following table 5.
The performance that the antistatic UV of table 5. is coating material solidified
| Index | Detection method | Stability |
| The outward appearance of mixture | Visual | Homogeneous phase, clear |
| 90 days ambient stables | D1849 | Homogeneous phase, clear |
| The stability of 30 days 60 degree | D1849 | Homogeneous phase, clear |
| The test of cold-hot cyclical stability | D1849 | Circulate and still keep homogeneous phase, clear 20 times |
3. the preparation of anti-static plastic film
(1) the coating material solidified showering of antistatic UV of being prepared by embodiment 3 is at transparent PETG(PET), on basement membrane, showering thickness is 2 μ m;
(2) film that adopts cryogenic vacuum to obtain step 1 is dried, and its condition is: vacuum 1pa, and 10 DEG C of temperature,5 minutes drying times;
(3) first film step 2 being obtained is 200mJ/cm at photocuring energy2Condition lower hardening time of 60s; ThenBe 800mJ/cm at photocuring energy2Under condition, hardening time 5s; Wherein, solidifying light source used is medium pressure mercury lamp, centre wavelengthFor 365nm.
4. the performance of anti-static plastic film
The performance of anti-static plastic film is as shown in table 6.
The performance of table 6. anti-static plastic film
| Performance | ASTM | Result |
| Flatness | Range estimation | OK |
| Brilliant point | Range estimation | Nothing |
| Light transmittance/ | D1003 | 89.2 |
| Mist degree | D1003 | 0.03 |
| Pencil hardness | D3363 | 2H |
| Scratch resistance | D5264 | 20 times back and forth without scratch |
| Adhesive force | D3359 | 5B |
| Resistance value | D257 | 10^5 |
| Resistance value (after 60 days) | D257 | 10^7 |
| Heat distortion temperature/DEG C | D648 | 130 |
| Coefficient of thermal expansion | D696 | 5×10-5 |
| Thermal cycle | D6944 | Unchanged |
Embodiment 4
1. the coating material solidified preparation of antistatic UV
The polythiophene that is (1) 30000 by 25g molecular weight, 25g molecular weight are 20000 poly-(3,4-ethylene dioxythiophene),50g Propylene Glycol Dimethyl Ether, 50g glycol monoethyl ether, 50g ethylene glycol monoethyl ether and 50g glycol dimethyl ether are put into reactor 1In, mix half an hour and to obtain mixed liquor A with the rotating speed dispersed with stirring of 200rpm/min with high-speed stirred dispersion machine;
(2) the carboxyl acid modified polyurethane acrylic resin that the model of 50gDSM-AGI company being produced is AgiSyn242(molecular weight is 1100, and acid number is 2mgKOH/g, and carboxyl-content is 8%), pentaerythrite six acrylate of 10g, 10g ethoxyquinTetramethylol methane tetraacrylate and 5g third is oxidized the polyether-modified dimethyl silicone polymer of tetramethylol methane tetraacrylate, 0.5g(BYK3530), 2-hydroxy-2-methyl-I-phenyl-I-acetone of 0.1g and 0.15g 2,4,6-trimethylbenzoyl hexicholBase phosphine oxide is put into reactor 2 together, uses high-speed stirred dispersion machine within 1 hour, extremely to mix with the rotating speed dispersed with stirring of 200rpm/minClose and evenly obtain mixed liquid B;
(3) mixture B is mixed with mixture A, obtain mixture C;
(4) 50g ethanol, 50g n-butanol, 50g normal propyl alcohol and 50g water are mixed and joined in mixture C afterwards, by high speedStirring dispersion machine, with the rotating speed dispersed with stirring of 200rpm/min 1 hour, to obtain final product.
2. the coating material solidified performance of antistatic UV
The performance that antistatic UV is coating material solidified, the results are shown in following table 7.
The coating material solidified performance of the antistatic UV of table 7.
| Index | Detection method | Stability |
| The outward appearance of mixture | Visual | Homogeneous phase, clear |
| 90 days ambient stables | D1849 | Homogeneous phase, clear |
| The stability of 30 days 60 degree | D1849 | Homogeneous phase, clear |
| The test of cold-hot cyclical stability | D1849 | Circulate and still keep homogeneous phase, clear 20 times |
3. the preparation of anti-static plastic film
(1) the coating material solidified showering of antistatic UV of being prepared by embodiment 4 is at transparent polymethyl methacrylate (PMMA)On basement membrane, showering thickness is 3 μ m;
(2) film that adopts cryogenic vacuum to obtain step 1 is dried, and its condition is: vacuum 1pa, and 0 DEG C of temperature,10 minutes drying times;
(3) first film step 2 being obtained is 100mJ/cm at photocuring energy2Condition lower hardening time of 1min; SoAfter be 1000mJ/cm at photocuring energy2Under condition, hardening time 2s; Wherein, solidifying light source used is medium pressure mercury lamp, centerWavelength is 365nm.
4. the performance of anti-static plastic film
The performance of anti-static plastic film is as shown in table 8.
The performance of table 8. anti-static plastic film
| Performance | ASTM | Result |
| Flatness | Range estimation | OK |
| Brilliant point | Range estimation | Nothing |
| Light transmittance/ | D1003 | 89.1 |
| Mist degree | D1003 | 0.05 |
| Pencil hardness | D3363 | 5H |
| Scratch resistance | D5264 | 20 times back and forth without scratch |
| Adhesive force | D3359 | 5B |
| Resistance value | D257 | 10^5 |
| Resistance value (after 60 days) | D257 | 10^7 |
| Heat distortion temperature/DEG C | D648 | 130 |
| Coefficient of thermal expansion | D696 | 5×10-5 |
| Thermal cycle | D6944 | Unchanged |
Embodiment 5
1. the coating material solidified preparation of antistatic UV
(1) poly-(3, the 4-enedioxy that the polythiophene that is 100000 by 16.7g molecular weight, 33.3g molecular weight are 40000Thiophene), ethylene glycol ethyl ether, 50g Propylene Glycol Dimethyl Ether and the 50g propane diols diethyl ether of 100g put into reactor 1, uses high-speed stirringMixing dispersion machine mixes and to obtain mixture A with the rotating speed dispersed with stirring of 200rpm/min half an hour;
(2) the carboxyl acid modified polyurethane acrylic resin of 150g (" the acrylate modified water that this resin is delivered by Li Zhihua etc.Synthetic and the performance characterization of based polyurethane " the described method preparation of a literary composition, its molecular weight is 5000, acid number is 1mgKOH/g, carboxylicBase content is 6%), 20g2,3-hydroxymethyl-propane tetraacrylate, 10g dipentaerythritol five acrylate, bis-seasons penta 4 of 20gThe polyether-modified dimethyl silicone polymer of alcohol six acrylate, 25g caprolactone modification double pentaerythritol methacrylate, 1.5g(BYK3530) and 0.45g2-hydroxy-2-methyl-I-phenyl-I-acetone put into together reactor 2, use high-speed stirred dispersion machineRotating speed dispersed with stirring with 200rpm/min obtains mixed liquid B to mixing in 1 hour;
(3) mixture B is mixed with mixture A, obtain mixture C;
(4) will 100g n-butanol, 100g acetone and 100g water joins in mixture C after mixing, divide by high-speed stirredLoose machine, with the rotating speed dispersed with stirring of 200rpm/min 1 hour, to obtain final product.
2. the coating material solidified performance of antistatic UV
The performance that antistatic UV is coating material solidified, the results are shown in following table 9
The performance that the antistatic UV of table 9. is coating material solidified
| Index | Detection method | Stability |
| The outward appearance of mixture | Visual | Homogeneous phase, clear |
| 90 days ambient stables | D1849 | Homogeneous phase, clear |
| The stability of 30 days 60 degree | D1849 | Homogeneous phase, clear |
| The test of cold-hot cyclical stability | D1849 | Circulate and still keep homogeneous phase, clear 20 times |
3. the preparation of anti-static plastic film
(1) the coating material solidified showering of antistatic UV of being prepared by embodiment 5 is on transparency polycarbonate film basement membrane, and showering is thickDegree is 3 μ m;
(2) film that adopts cooling alternated blasting to obtain step 1 is dried, and its condition is air blast wind speed 2m/s, temperature10 DEG C, 10 minutes drying times;
(3) first film step 2 being obtained is 200mJ/cm at photocuring energy2Condition lower hardening time of 2s; ThenBe 600mJ/cm at photocuring energy2Under condition, hardening time 1min; Wherein, solidifying light source used is medium pressure mercury lamp, middle cardiac waveLong is 365nm.
4. the performance of anti-static plastic film
The performance of anti-static plastic film is as shown in table 10.
The performance of table 10. anti-static plastic film
| Performance | ASTM | Result |
| Flatness | Range estimation | OK |
| Brilliant point | Range estimation | Nothing |
| Light transmittance/ | D1003 | 88.9 |
| Mist degree | D1003 | 0.07 |
| Pencil hardness | D3363 | 1H |
| Scratch resistance | D5264 | 20 times back and forth without scratch |
| Adhesive force | D3359 | 5B |
| Resistance value | D257 | 10^5 9 --> |
| Resistance value (after 60 days) | D257 | 10^7 |
| Heat distortion temperature/DEG C | D648 | 130 |
| Coefficient of thermal expansion | D696 | 5×10-5 |
| Thermal cycle | D6944 | Unchanged |
Embodiment 6
1. the coating material solidified preparation of antistatic UV
(1) poly-(3, the 4-enedioxy thiophene that the polythiophene that is 70000 by 12.5g molecular weight, 37.5g molecular weight are 30000Fen), 100g glycol monoethyl ether, 50g ethylene glycol monoethyl ether and 50g propane diols diethyl ether put into reactor 1, uses high-speed stirredDispersion machine mixes and to obtain mixture A with the rotating speed dispersed with stirring of 200rpm/min half an hour;
(2) (this resin is the DR-U110 of Changxing chemistry report to the carboxyl acid modified polyurethane acrylic resin of 100g, its moleculeAmount is 3400, and acid number is 6mgKOH/g, and carboxyl-content is 8%), 20g pentaerythrite six acrylate, 10g2,3-methylol thirdThe polyether-modified dimethyl silicone polymer (BYK3530) of alkane tetraacrylate, 20g dipentaerythritol five acrylate, 0.7g,0.5g2-hydroxy-2-methyl-I-phenyl-I-acetone is put into reactor 2 together with 0.5g1-hydroxyl-cyclohexyl-phenyl ketone,Within 1 hour, obtain mixed liquid B to mixing with the rotating speed dispersed with stirring of 200rpm/min with high-speed stirred dispersion machine;
(3) mixture B is mixed with mixture A, obtain mixture C;
(4) 100g ethanol, 50g acetone and 100g water are mixed and joined in mixture C afterwards, use high-speed stirred dispersion machineWith the rotating speed dispersed with stirring of 200rpm/min 1 hour, to obtain final product.
2. the coating material solidified performance of antistatic UV
The performance that antistatic UV is coating material solidified, the results are shown in following table 11.
The performance that the antistatic UV of table 11. is coating material solidified
| Index | Detection method | Stability |
| The outward appearance of mixture | Visual | Homogeneous phase, clear |
| 90 days ambient stables | D1849 | Homogeneous phase, clear |
| The stability of 30 days 60 degree | D1849 | Homogeneous phase, clear |
| The test of cold-hot cyclical stability | D1849 | Circulate and still keep homogeneous phase, clear 20 times |
3. the preparation of anti-static plastic film
(1) the coating material solidified showering of antistatic UV of being prepared by embodiment 6 is at transparent PET (PET)On basement membrane, showering thickness is 2 μ m;
(2) film that adopts cooling alternated blasting to obtain step 1 is dried, and its condition is air blast wind speed 3m/s, temperature20 DEG C, 50 minutes drying times;
(3) first film step 2 being obtained is 150mJ/cm at photocuring energy2Condition lower hardening time of 4s; ThenBe 800mJ/cm at photocuring energy2Under condition, hardening time 10s; Wherein, solidifying light source used is medium pressure mercury lamp, middle cardiac waveLong is 365nm.
4. the performance of anti-static plastic film
The performance of anti-static plastic film is as shown in table 12.
The performance of table 12. anti-static plastic film
| Performance | ASTM | Result 10 --> |
| Flatness | Range estimation | OK |
| Brilliant point | Range estimation | Nothing |
| Light transmittance/ | D1003 | 88.9 |
| Mist degree | D1003 | 0.06 |
| Pencil hardness | D3363 | 2H |
| Scratch resistance | D5264 | 20 times back and forth without scratch |
| Adhesive force | D3359 | 5B |
| Resistance value | D257 | 10^5 |
| Resistance value (after 60 days) | D257 | 10^7 |
| Heat distortion temperature/DEG C | D648 | 130 |
| Coefficient of thermal expansion | D696 | 5×10-5 |
| Thermal cycle | D6944 | Unchanged |
Embodiment 7
1. the coating material solidified preparation of antistatic UV
(1) poly-(3, the 4-enedioxy thiophene that the polythiophene that is 60000 by 16.7g molecular weight, 33.3g molecular weight are 26000Fen), ethylene glycol diethyl ether, 50g Propylene Glycol Dimethyl Ether and the 50g propane diols diethyl ether of 100g put into reactor 1, uses high-speed stirringMixing dispersion machine mixes and to obtain mixture A with the rotating speed dispersed with stirring of 200rpm/min half an hour;
(2) (this resin is pressed Synthesisand to the carboxyl acid modified polyurethane acrylic resin of 120gThe characterizationoftwo-componentwaterborneacrylic-polyure thane mono-described side of literary compositionLegal system is standby, and its molecular weight is 2400, and acid number is 3mgKOH/g, and carboxyl-content is 7.4%), 70g tetramethylol methane tetraacrylate,The polyether-modified dimethyl silicone polymer (BYK3530) of 1.0g and 0.35g2-hydroxy-2-methyl-I-phenyl-I-acetone are put togetherEnter in reactor 2, within 1 hour, mixed to mixing with the rotating speed dispersed with stirring of 200rpm/min with high-speed stirred dispersion machineLiquid B;
(3) mixture B is mixed with mixture A, obtain mixture C;
(4), by solvent 100g n-butanol, 100g acetone and 100g water join in mixture C after mixing, and use high-speed stirringMix dispersion machine with the rotating speed dispersed with stirring of 200rpm/min 1 hour, to obtain final product.
2. the coating material solidified performance of antistatic UV
The performance that antistatic UV is coating material solidified, the results are shown in following table 13
The performance of the antistatic UV coating of table 13.
| Index | Detection method | Stability |
| The outward appearance of mixture | Visual | Homogeneous phase, clear |
| 90 days ambient stables | D1849 | Homogeneous phase, clear |
| The stability of 30 days 60 degree | D1849 | Homogeneous phase, clear |
| The test of cold-hot cyclical stability | D1849 | Circulate and still keep homogeneous phase, clear 20 times |
3. the preparation of anti-static plastic film
(1) the coating material solidified showering of antistatic UV of being prepared by embodiment 7 on transparent Merlon basement membrane, showering thicknessBe 5 μ m;
(2) film that adopts cooling alternated blasting to obtain step 1 is dried, and its condition is air blast wind speed 5m/s, temperature30 DEG C, 2 minutes drying times;
(3) first film step 2 being obtained is 160mJ/cm at photocuring energy2Condition lower hardening time of 4s; ThenBe 750mJ/cm at photocuring energy2Under condition, hardening time 4s; Wherein, solidifying light source used is medium pressure mercury lamp, centre wavelengthFor 365nm.
4. the performance of anti-static plastic film
The performance of anti-static plastic film is as shown in table 14.
The performance of table 14. anti-static plastic film
| Performance | ASTM | Result |
| Flatness | Range estimation | OK |
| Brilliant point | Range estimation | Nothing |
| Light transmittance/ | D1003 | 89 |
| Mist degree | D1003 | 0.05 |
| Pencil hardness | D3363 | 2H |
| Scratch resistance | D5264 | 20 times back and forth without scratch |
| Adhesive force | D3359 | 5B |
| Resistance value | D257 | 10^5 |
| Resistance value (after 60 days) | D257 | 10^7 |
| Heat distortion temperature/DEG C | D648 | 130 |
| Coefficient of thermal expansion | D696 | 5×10-5 |
| Thermal cycle | D6944 | Unchanged |
Embodiment 8
1. the coating material solidified preparation of antistatic UV
The polythiophene that is (1) 45000 by 25g molecular weight, 25g molecular weight are 32000 poly-(3,4-ethylene dioxythiophene),50g Propylene Glycol Dimethyl Ether, 50g glycol monoethyl ether, 50g ethylene glycol monoethyl ether and 50g glycol dimethyl ether are put into reactor 1In, mix half an hour and to obtain mixed liquor A with the rotating speed dispersed with stirring of 200rpm/min with high-speed stirred dispersion machine;
(2) by carboxyl acid modified 50g polyurethane acrylic resin, (this resin is 6170 of Changxing chemistry, and its molecular weight is1200, acid number is 6.2mgKOH/g, and carboxyl-content is 6.8%), pentaerythrite six acrylate of 50g, 0.4g polyether-modifiedDimethyl silicone polymer (BYK3530) and 0.15g2,4,6-trimethylbenzoyl diphenyl phosphine oxide is put into reactor 2 togetherIn, within 1 hour, obtain mixed liquid B to mixing with the rotating speed dispersed with stirring of 200rpm/min with high-speed stirred dispersion machine;
(3) mixture B is mixed with mixture A, obtain mixture C;
(4) join in mixture C after solvent 100g acetone and 100g water are mixed in proportion, disperse by high-speed stirredMachine, with the rotating speed dispersed with stirring of 200rpm/min 1 hour, to obtain final product.
2. the coating material solidified performance of antistatic UV
The performance that antistatic UV is coating material solidified, the results are shown in following table 15
The performance of the antistatic UV coating of table 15.
| Index | Detection method | Stability |
| The outward appearance of mixture | Visual | Homogeneous phase, clear 12 --> |
| 90 days ambient stables | D1849 | Homogeneous phase, clear |
| The stability of 30 days 60 degree | D1849 | Homogeneous phase, clear |
| The test of cold-hot cyclical stability | D1849 | Circulate and still keep homogeneous phase, clear 20 times |
3. the preparation of anti-static plastic film
(1) the coating material solidified showering of antistatic UV of being prepared by embodiment 8 is on transparent PET basement membrane, and showering thickness is 4 μm；
(2) film that adopts cryogenic vacuum to obtain step 1 is dried, and its condition is: vacuum 1pa, and 10 DEG C of temperature,2 minutes drying times;
(3) first film step 2 being obtained is 150mJ/cm at photocuring energy2Condition lower hardening time of 20s; ThenBe 800mJ/cm at photocuring energy2Under condition, hardening time 4s; Wherein, solidifying light source used is medium pressure mercury lamp, centre wavelengthFor 365nm.
4. the performance of anti-static plastic film
The performance of anti-static plastic film is shown in table 16.
The performance of table 16. anti-static plastic film
| Performance | ASTM | Result |
| Flatness | Range estimation | OK |
| Brilliant point | Range estimation | Nothing |
| Light transmittance/ | D1003 | 89.1 |
| Mist degree | D1003 | 0.04 |
| Pencil hardness | D3363 | 3H |
| Scratch resistance | D5264 | 20 times back and forth without scratch |
| Adhesive force | D3359 | 5B |
| Resistance value | D257 | 10^5 |
| Resistance value (after 60 days) | D257 | 10^7 |
| Heat distortion temperature/DEG C | D648 | 130 |
| Coefficient of thermal expansion | D696 | 5×10-5 |
| Thermal cycle | D6944 | Unchanged |
Embodiment 9
1. the coating material solidified preparation of antistatic UV
(1) poly-(3,4-ethylene dioxythiophene) that the polythiophene that is 48000 by 25g molecular weight, 25g molecular weight are 34000Put into reactor 1 with 200g glycol monoethyl ether, the rotating speed dispersed with stirring half with high-speed stirred dispersion machine with 200rpm/minHour mix and to obtain mixed liquor A;
(2) carboxyl acid modified polyurethane acrylic resin (its point that the model of 50gSartomer being produced is CN9006NSSon amount is 2000, and acid number is 6.1mgKOH/g, and carboxyl-content is 6.0%), pentaerythrite six acrylate of 50g, 0.4g poly-Ether modified dimethyl polysiloxane (BYK3530) and 0.15g2,4,6-trimethylbenzoyl diphenyl phosphine oxide is put into togetherIn reactor 2, within 1 hour, obtain mixed liquor to mixing with the rotating speed dispersed with stirring of 200rpm/min with high-speed stirred dispersion machineB；
(3) mixture B is mixed with mixture A, obtain mixture C;
(4) join in mixture C after solvent 100g butanone and 100g water are mixed in proportion, disperse by high-speed stirredMachine, with the rotating speed dispersed with stirring of 200rpm/min 1 hour, to obtain final product.
2. the coating material solidified performance of antistatic UV
The performance that antistatic UV is coating material solidified, the results are shown in following table 17
The performance of the antistatic UV coating of table 17.
| Index | Detection method | Stability |
| The outward appearance of mixture | Visual | Homogeneous phase, clear |
| 90 days ambient stables | D1849 | Homogeneous phase, clear |
| The stability of 30 days 60 degree | D1849 | Homogeneous phase, clear |
| The test of cold-hot cyclical stability | D1849 | Circulate and still keep homogeneous phase, clear 20 times |
3. the preparation of anti-static plastic film
(1) the coating material solidified showering of antistatic UV of being prepared by embodiment 9 is on transparent PC basement membrane, and showering thickness is 5 μ m;
(2) adopt cryogenic vacuum to be dried above-mentioned film, its condition is: vacuum 1pa, 5 DEG C of temperature, drying time5 minutes;
(3) first film step 2 being obtained is 120mJ/cm at photocuring energy2Condition lower hardening time of 6s; ThenBe 800mJ/cm at photocuring energy2Under condition, hardening time 10s; Wherein, solidifying light source used is medium pressure mercury lamp, middle cardiac waveLong is 365nm.
4. the performance of anti-static plastic film
The performance of anti-static plastic film is shown in table 18.
The performance of table 18. anti-static plastic film
| Performance | ASTM | Result |
| Flatness | Range estimation | OK |
| Brilliant point | Range estimation | Nothing |
| Light transmittance/ | D1003 | 89.2 |
| Mist degree | D1003 | 0.02 |
| Pencil hardness | D3363 | 2H |
| Scratch resistance | D5264 | 20 times back and forth without scratch |
| Adhesive force | D3359 | 5B |
| Resistance value | D257 | 10^5 |
| Resistance value (after 60 days) | D257 | 10^7 |
| Heat distortion temperature/DEG C | D648 | 130 |
| Coefficient of thermal expansion | D696 | 5×10-5 |
| Thermal cycle | D6944 | Unchanged |
Embodiment 10 (comparative example 1)
1. the coating material solidified preparation of antistatic UV
Poly-(3,4-ethylene dioxythiophene), 50g that the polythiophene that is 35000 by 25g molecular weight, 25g molecular weight are 25000(its molecular weight is 800 to the carboxyl acid modified polyurethane acrylic resin that the model that DSM-AGI company produces is NeoRadU-42, acidValue is for 1mgKOH/g, and carboxyl-content is 6%), pentaerythrite six acrylate of 50g, the polyether-modified poly dimethyl silicon of 0.25gOxygen alkane (BYK3530), 1g2-hydroxy-2-methyl-I-phenyl-I-acetone and mixed solvent are (containing the propylene glycol monomethyl ether of 200g, 150gEthanol and 50g water) together with put into reactor, little with the rotating speed dispersed with stirring 2.5 of 200rpm/min with high-speed stirred dispersion machineUp to mixing, obtain photopolymerizable composition.
2. the coating material solidified performance of antistatic UV
The performance that antistatic UV is coating material solidified, the results are shown in following table 19
The performance that the antistatic UV of table 19. is coating material solidified
| Index | Detection method | Stability |
| The outward appearance of mixture | Visual | Milky gel |
| 90 days ambient stables | D1849 | , there is precipitation in layering |
| The stability of 30 days 60 degree | D1849 | , there is precipitation in layering |
| The test of cold-hot cyclical stability | D1849 | Circulate and measure existing precipitation 2 times |
From the coating material solidified preparation method of above-mentioned antistatic UV, raw material wherein and proportioning thereof and embodiment 1 are same, thatResult in table 19 is visible compared with result in table 1, only have first by macromolecular poly-thiophene phenol and poly-(3,4-enedioxy thiopheneFen) add again the UV resin and the monomer that mix with the dispersion of propylene glycol monomethyl ether, finally use solvent dilution, progressively reduce combinationThe potential energy of thing just can obtain all even stable polymer dispersion liquids, otherwise the polymer dispersion liquid obtaining is inhomogeneous and unstableFixed.
Embodiment 10 (comparative example 2)
1. the preparation of anti-static plastic film
(1) the coating material solidified showering of antistatic UV of being prepared by embodiment 2 on transparent Merlon basement membrane, showering thicknessBe 3 μ m;
(2) film that adopts cryogenic vacuum to obtain step 1 is dried, and its condition is: vacuum 1pa, and 10 DEG C of temperature,2 minutes drying times;
(3) film step 2 being obtained is directly 600mJ/cm at photocuring energy2Under condition, be cured, while solidifyingBetween be 35s; Wherein, solidifying light source used is medium pressure mercury lamp, and centre wavelength is 365nm.
2. the performance of anti-static plastic film
The performance of anti-static plastic film is shown in table 20.
The performance of table 20. anti-static plastic film
| Performance | ASTM | Result |
| Flatness | Range estimation | Uneven |
| Brilliant point | Range estimation | Have |
| Light transmittance/ | D1003 | 89 |
| Mist degree | D1003 | 2.41 |
| Pencil hardness | D3363 | 2H |
| Scratch resistance | D5264 | 30 times back and forth without scratch 15 --> |
| Adhesive force | D3359 | 5B |
| Resistance value | D257 | 10^10 |
| Resistance value (after 60 days) | D257 | 10^13 |
| Heat distortion temperature/DEG C | D648 | 130 |
| Coefficient of thermal expansion | D696 | 5×10-5 |
| Thermal cycle | D6944 | Unchanged |
By more visible to the result in upper table 20 and table 4, the anlistatig PC obtaining by the mode of high-energy one-step solidificationThe rough situation of the apparent appearance of film, and surface also has little crystal grain. At aspect of performance, high-energy one-step solidification obtainsThe mist degree of anti-static plastic film obviously larger. In anlistatig performance, it is antistatic that high-energy one-step solidification obtainsThe anti-static plastic film that the resistance value of plastic sheeting and the resistance value after 60 days all obtain than film build method described in the application is highGo out several orders of magnitude.
Claims (5)
1. a preparation method for antistatic photocureable coating, the method is made up of following steps:
(1) by even the ether solvent dispersed with stirring of 4 times of antistatic macromolecule material and antistatic macromolecule material weight, obtainMixed liquor A;
(2) by the polyfunctionality monomer of 0.5～1.5 times of antistatic macromolecule material weight, antistatic macromolecule material weight 1～The polyfunctionality prepolymer of 3 times, the polyether-modified dimethyl silicone polymer of polyfunctionality prepolymer weight 0.5%～1% and manyThe light trigger of functionality monomer weight 1%～3% mixes, and obtains mixed liquid B;
(3) mixed liquid B is joined in mixed liquor A, dispersed with stirring obtains mixed liquor C;
(4) in mixed liquor C, add the solvent of 4～6 times of antistatic macromolecule material weight, be uniformly mixed, described in obtainingAntistatic photocureable coating;
In above-mentioned steps,
Described antistatic macromolecule material is a kind of of polythiophene and poly-(3,4-ethylene dioxythiophene) or the mixing of the twoThing, wherein, the molecular weight of described polythiophene is 30000～100000; Described poly-(3,4-ethylene dioxythiophene) molecular weight is20000～40000；
Described ether solvent is glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, thirdOne in glycol dimethyl ether and propane diols diethyl ether or two or more;
Described polyfunctionality monomer is tetramethylol methane tetraacrylate, ethoxyquin tetramethylol methane tetraacrylate, the third oxidation seasonPenta tetrol tetraacrylate, 2,3-hydroxymethyl-propane tetraacrylate, dipentaerythritol five acrylate, dipentaerythritol 6 thirdOne in olefin(e) acid ester and caprolactone modification double pentaerythritol methacrylate or two or more;
Described polyfunctionality prepolymer is carboxyl acid modified polyurethane acrylic resin, this carboxyl acid modified polyurethane acrylic resinMolecular weight be 800～6000, acid number is 1～10mgKOH/g, the weight percentage of carboxyl is 6%～10%;
Described light trigger is 1-hydroxyl-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone and 2,4,One in 6-trimethylbenzoyl diphenyl phosphine oxide or two or more;
Described solvent is one or more in water, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, acetone and butanone;
When described antistatic macromolecule material is the mixture of polythiophene and poly-(3,4-ethylene dioxythiophene), the weight of the twoThan being 1:1～1:2.
2. the preparation method of a kind of antistatic photocureable coating according to claim 1, is characterized in that, described carboxylic acidModified polyurethane acrylic resin be the NeoRadU-42, the NeoRadU-30W that produce of Dutch DSM Co., Ltd,One in AgiSyn230A2, AgiSyn242 and AgiSyn530, or the DR-U110 of Changxing, Taiwan chemical company production,One in DR-U185 and 6170, or one in the CN9006NS of Sartomer Co., Ltd of U.S. production and CN9010NSKind.
3. a preparation method for anti-static plastic film, the method is made up of following steps:
(1) prepared claim 1 or 2 antistatic photocureable coating is coated on plastic sheeting, and adopts cryogenic vacuumBe dried or the air-dry drying method of drum cooler, obtain the film that thickness is 2～5 μ m; Wherein, described plastic sheeting is poly-methyl-propOne in olefin(e) acid methyl esters film, polycarbonate film and polyethylene terephthalate thin film; Described low-temperature vacuum dryingCondition is that vacuum is 0.2～1Pa, and temperature is 0～10 DEG C, and be 2-10 minute drying time; Described cooling forced air drying barPart is that air blast wind speed is 2～5m/s, temperature 10-30 DEG C, drying time 2-10 minute;
(2) first film step (1) being obtained is 100-200mJ/cm at photocuring energy2Under condition, solidify 2s-1min, soAfter be 600-1000mJ/cm at photocuring energy2Under condition, solidify 2s-1min; Wherein, solidifying light source used is medium pressure mercury lamp,Centre wavelength is 365nm.
4. the preparation method of a kind of anti-static plastic film according to claim 3, is characterized in that, described in step (2)Condition of cure be to be first 100-200mJ/cm at photocuring energy2Condition lower hardening time of 2s-6s, then at photocuringEnergy is 600-1000mJ/cm2Under condition, hardening time 2-6s.
5. according to the preparation method of a kind of anti-static plastic film described in claim 3 or 4, it is characterized in that, described mouldsMaterial film is polycarbonate film.
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| CN105524543B (en) * | 2015-08-12 | 2018-07-06 | 国网山东省电力公司临沂供电公司 | A kind of arc welding transformer for saving electromagnetic wire |
| CN105820746A (en) * | 2016-05-05 | 2016-08-03 | 宁波智锐新材料有限公司 | Preparation method and application of neutral polythiophene antistatic paint |
| CN106085083B (en) * | 2016-06-23 | 2018-07-13 | 苏州吉人高新材料股份有限公司 | A kind of aqueous composite paint and preparation method thereof of environmental protection |
| CN106867299A (en) * | 2017-02-13 | 2017-06-20 | 深圳市贝菲科技有限公司 | The preparation method and its film build method of a kind of antistatic photocureable coating |
| CN107418422A (en) * | 2017-05-27 | 2017-12-01 | 苏州辅朗光学材料有限公司 | A kind of antistatic UV coating, antistatic MS sheet materials |
| CN111073498B (en) * | 2020-01-02 | 2021-07-23 | 湖南宏泰新材料有限公司 | UV (ultraviolet) curing self-repairing antistatic coating |
| JP2022068706A (en) * | 2020-10-22 | 2022-05-10 | 富士フイルムビジネスイノベーション株式会社 | Liquid composition, metallic luster film and article |
| CN113928034A (en) * | 2021-10-13 | 2022-01-14 | 石家庄沃佳玛智能科技有限公司 | Method for manufacturing scratch-resistant thermal transfer printing ribbon |
| CN115521702B (en) * | 2022-09-23 | 2023-10-17 | 湖南纳昇电子科技有限公司 | PEDOT (polyether urethane) PSS (polyphenylene sulfide) electronic coating capable of enhancing reflection and high in hardness as well as preparation method and application thereof |
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| CN101423675A (en) * | 2008-11-25 | 2009-05-06 | 四川大学 | Ultraviolet curing coating for preventing static on plastic surface and method for preparing the same |
| CN103788859A (en) * | 2014-01-08 | 2014-05-14 | 华东理工大学 | Antistatic coating for ultraviolet curing and preparation method thereof |
| CN103833952A (en) * | 2014-02-20 | 2014-06-04 | 山西省应用化学研究所 | Preparation method of carboxyl modification polyurethane acrylic acid ester |
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| CN101423675A (en) * | 2008-11-25 | 2009-05-06 | 四川大学 | Ultraviolet curing coating for preventing static on plastic surface and method for preparing the same |
| CN103788859A (en) * | 2014-01-08 | 2014-05-14 | 华东理工大学 | Antistatic coating for ultraviolet curing and preparation method thereof |
| CN103833952A (en) * | 2014-02-20 | 2014-06-04 | 山西省应用化学研究所 | Preparation method of carboxyl modification polyurethane acrylic acid ester |
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