CN103694866B - A kind of photocuring insullac and preparation and application thereof - Google Patents
A kind of photocuring insullac and preparation and application thereof Download PDFInfo
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- CN103694866B CN103694866B CN201310696676.4A CN201310696676A CN103694866B CN 103694866 B CN103694866 B CN 103694866B CN 201310696676 A CN201310696676 A CN 201310696676A CN 103694866 B CN103694866 B CN 103694866B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D175/04—Polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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- Wood Science & Technology (AREA)
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- Paints Or Removers (AREA)
- Organic Insulating Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of photocuring insullac, including photoreactive resin, photolytic activity diluent, light trigger, cross-linking agent, defoamer, levelling agent, coupling agent。Described photocuring insullac can solidify under the ultraviolet light irradiation of certain power density, forms the insulation paint film with certain electrical insulation properties and mechanical performance。Without VOC in formula for a product prepared by this invention, will not to environment in using, environmental-protecting performance highlights。The invention also discloses the preparation method of above-mentioned photocuring insullac and using method。
Description
Technical field
The invention belongs to insulating material field。Particularly belong to insullac used by enamel covered wire, enamel insulated aluminium wire and composite type varnished wire；Varnished insulation insullac；Bonding insullac；Covering insullac；The manufacture field of the aspect insullac such as stalloy (silicon steel sheet) insulation insullac used。
Background technology
Paint is the general name of the colloid solution that film forming matter dispersion is formed in a solvent。Insullac is then a special kinds of paint apoplexy due to endogenous wind。Insullac is based on macromolecular material, can be solidified into dielectric film or the important insulant of insulation entirety under certain conditions。Insullac belongs to the one in five big class insulant (i.e. insullac, dipping fiber, laminate, mica products and compression molding material), being a kind of typical dielectric substance, its basic feature is by sensing rather than to transmit the role and influence of electricity in the way of conducting。Its performance characteristics is presented as: excellent insulating property；Adhesive force is good, mechanical strength is higher；Shrinkage stress is little；Thermostability can meet the different requirements of transformator；Outdoor or special environment can be met its particular/special requirement, radioprotective, anticorrosion, anti-ultraviolet etc.；Manufacturability is good, good operability, nontoxic or low toxicity, drying time are short。Thus obtain a wide range of applications, insullac of good performance is to ensure that one of essential condition of electrical equipment normal operation, occupies critical role in electric insulation field。
But traditional insullac is solvent based product, its solid content only has about 33% even lower, VOC(volatile organic matter, mainly a series of organic solvent in this series products) content is up to nearly 70%, substantial amounts of VOC evaporate in air when product uses, and environment is caused serious injury。Polluting for reducing, VOC is reclaimed after-combustion and processes by most producers, but still has strong penetrating odor, and partial organic substances burning can produce a certain amount of carcinogenic, teratogen, and resident's health near operator and plant area is had certain impact；Being undertaken burning by valuable Organic substance is also a kind of huge wasting of resources, and especially fossil resources is gradually exhausted, and organic solvent price rises steadily, and reduces VOC content and has the meaning of environment benefits and economic gains two aspect。
It is a kind of novel environmental protection paint that ultraviolet light polymerization (is often simply called UV to solidify) paint。By preparing and the special resin of this process matching and diluent make special paint vehicle, this kind of paint under the irradiation of ultraviolet light, can be formed dry paint film by the curing of coating of the paint with mobility within the several seconds to the time of tens of seconds。Owing to hardening time is extremely short and resin and diluent system are respectively provided with light reaction, VOC content when paint vehicle uses can be reduced to the degree close to zero。Thus ultraviolet-cured paint is the novel paint of a kind of environmental-friendly and efficient rate。If changing resin and the diluent system thereof of existing insullac, so as to meet the requirement of UV curing technology, then the VOC content being substantially reduced during insullac uses, it is thus achieved that the New insulated paint of environmental protection。
Summary of the invention
Too high for existing insullac VOC content, environmental-protecting performance is poor, use in air pollution is serious, the defect such as operator's working condition is severe, it is an object of the invention to prepare a kind of resin (functional group simultaneously required containing aspects such as can meeting insulation paint film mechanical performance, chemical property, hot property in resin) containing ultraviolet light active group and the diluent system matched thereof and be configured to paint vehicle, this paint vehicle can under the effect of the ultraviolet light of certain power and finite concentration light trigger fast setting, form dry paint film。The release of this paint vehicle in use almost VOC free, environmental-protecting performance is splendid, can fundamentally solve a series of environmental issues of conventional insulator paint。
The above-mentioned purpose of the present invention is achieved by the following technical solution: a kind of photocuring insullac, including the raw material of following weight portion:
Photoreactive resin 100 weight portion；
Photolytic activity diluent 20 ~ 60 weight portion；
Light trigger 0.5 ~ 10 weight portion；
Cross-linking agent 0.1 ~ 1.5 weight portion；
Defoamer 0.1 ~ 1 weight portion；
Levelling agent 0.1 ~ 1 weight portion；
Coupling agent 0.1 ~ 1 weight portion。
In the present invention, described photoreactive resin refers to one or more in photolytic activity polyester resin, photolytic activity polyurethane resin or both modified products。Wherein, described photolytic activity polyester resin or its modified resin refer in molecular structure containing the photoreactive resin of certain proportion ester bond (-COO-), and it is by containing double bond raw material, hydroxyl (or amino) raw material, obtain through polyreaction containing carboxy starting material or containing several in anhydride starting material。Photolytic activity polyurethane resin or its modified resin refer to the photoreactive resin of the carbamate containing certain proportion (-NHCOO-) group in molecular structure, and it is by obtaining with the raw material reaction containing isocyano containing double bond raw material, (mainly hydroxyl or amino starting materials) containing active hydrogen raw material。
Specifically, described photolytic activity polyester resin or its modified resin be by by a certain proportion of several containing double bond raw material, hydroxyl (or amino) raw material, containing carboxy starting material or carry out polyreaction at a certain temperature containing anhydride starting material, by measuring the degree that acid number detection reaction carries out。Stop heating, cooling when question response tends to complete, add photolytic activity diluent and polymerization inhibitor, stir, discharging and prepare。
Specifically, described photolytic activity polyurethane resin or its modified resin be by by a certain proportion of several containing double bond raw material, be polymerized under uniform temperature in case with depositing at a certain amount of catalyst containing isocyano raw material containing active hydrogen raw material (mainly hydroxyl or amino starting materials), utilize the detection of di-n-butylamine titrimetry to react the degree carried out。Stop heating, cooling when question response tends to complete, add photolytic activity diluent and polymerization inhibitor, stir, discharging and prepare。
In technique scheme, the described raw material containing double bond refers in those structures containing the unsaturated materials of double bond, it is possible to be alkene or containing the unsaturated acids of double bond, alcohol, ammonia, ester, anhydride etc.。Specifically, the heretofore described raw material containing double bond includes but not limited to: Hydroxypropyl acrylate, 2-(Acryloyloxy)ethanol, hy-droxybutyl, cis maleic anhydride, trans maleic anhydride, 1-propenol-3 (also known as propenyl), dicyclopentadiene etc.。
In technique scheme, described hydroxyl (or amino) raw material refers to the material in those structures containing hydroxyl (or amino), it is possible to be alcohol, including monohydric alcohol, polyhydric alcohol；Phenol, including monohydric phenol, polyhydric phenols；Or amine, aminoacid etc.。Specifically, heretofore described hydroxyl (or amino) raw material includes but not limited to: carbamide, tripolycyanamide, hexamethylene diamine, cyclohexanediamine, ethylene glycol, propylene glycol, glycerol, bisphenol-A, polyethylene glycol 200, PEG400, Macrogol 600, neopentyl glycol, 1-propenol-3 (also known as propenyl), various commercially available polyether Glycols or polyether polyol, various commercial polyesters dihydroxylic alcohols or PEPA etc.。
In technique scheme, described containing carboxy starting material or the material referring to the acid anhydride structure formed containing carboxyl or carboxyl dehydration in those structures containing anhydride starting material。Can be saturated acid or unsaturated acids, it is possible to be monoacid can also be polyprotic acid。Specifically, described phthalic anhydride, p-phthalic acid, M-phthalic acid, phthalic acid, cis maleic anhydride, trans maleic anhydride, adipic acid etc. are included but not limited to containing carboxy starting material or containing anhydride starting material。
In technique scheme, the described raw material containing isocyano includes but not limited to: toluene di-isocyanate(TDI), isophorone diisocyanate, methyl diphenylene diisocyanate, hexamethylene diisocyanate etc.。
In the present invention, described photolytic activity diluent refers to double bond containing small molecular ester, includes but not limited to butyl acrylate, ethyl acrylate, carbamate mono acrylic ester, hexanediyl ester, butanediol diacrylate, neopentylglycol diacrylate, double pentaerythritol methacrylate, trimethylolpropane trimethacrylate, styrene, methyl methacrylate etc.。Its consumption can be 20,25,30,35,40,45,50 or 55 weight portions。
In the present invention, described polymerization inhibitor refers to that molecule with chain radical reaction, can form the low activity free radical that non-free radical material maybe can not cause, so that the material of polymerization。Can be phenolic inhibitor, quinones polymerization inhibitor, arene nitro compound polymerization inhibitor, inorganic compound polymerization inhibitor。Specifically, described polymerization inhibitor include but not limited to hydroquinone, 1,4-benzoquinone, phenothiazine, beta-phenyl naphthylamines, p-tert-butyl catechol, methylene blue, 1,1-diphenyl-2-hardship hydrazine, 2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical, methylnaphthohydroquinone, MEHQ, 2-tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinones etc.。
In prepared by photolytic activity polyester resin or its modified resin, control in raw material the amount of substance of hydroxyl and carboxyl ratio for 1.3:1 ~ 0.9:1；Can be specifically 0.95:1,1.0:1,1.05:1,1.1:1,1.15:1,1.2:1 or 1.25:1；Or the amount of substance of hydroxyl and anhydride can be specifically 0.95:0.5,1.0:0.5,1.05:0.5,1.1:0.5,1.15:0.5,1.2:0.5 or 1.25:0.5 than for 1.3:0.5 ~ 0.9:0.5 in control raw material；Or the amount of substance of hydroxyl and (summations of carboxyl and 2 times of anhydride) is than for 1.3:1 ~ 0.9:1, can be specifically 0.95:1,1.0:1,1.05:1,1.1:1,1.15:1,1.2:1 or 1.25:1。The temperature of reaction is 140 ~ 230 DEG C。
In prepared by photolytic activity polyester resin or its modified resin, measuring particularly as follows: add the sample 0.5g through accurate weighing in conical flask of acid number, add proper amount of acetone and dissolve, add 2 ethanolic phenolphthalein solution。It is titrated to the KOH standard solution of 0.1mol/l in pink and red 20s and does not take off。The acid number of sample calculates by following formula 1。
(1)。
In formula 1:
AN is the acid number of sample, unit mg/g。
N is the concentration of KOH standard solution, unit mol/l。
The volume of the KOH solution consumed when l is titration, units/ml。
W is the quality of affiliated sample, unit g。
S is the solid content of sample。
In prepared by photolytic activity polyurethane resin or its modified resin, control the ratio containing active hydrogen raw material (hydroxyl or amino starting materials) and the amount of substance containing active hydrogen in isocyano raw material and isocyano for 1.02:1 ~ 1.15:1, can be specifically 1.05:1,1.08:1,1.1:1,1.12:1 etc.。Reaction temperature is 50 ~ 120 DEG C。Described catalyst can be the organic tins such as dibutyl tin laurate。Its ratio is the 0.2% ~ 1% of total quality of material mark。It is preferably 0.5%。
In the preparation of photolytic activity polyurethane resin or its modified resin, the reaction of di-n-butylamine titration measuring carries out degree method particularly includes: adds the di-n-butylamine toluene standard solution that 4ml concentration is 0.1mol/L in conical flask, weighs, peeling。Taking about the 0.5g sample of accurate weighing in this conical flask, stirring shakes up, after reaction 15min, add 2 bromophenol blue indicators, add the isopropanol of about 15ml, with the HCl standard solution titration of 0.01mol/L, color is turned yellow green by indigo plant, separately does blank assay。The content of isocyano calculates by following formula 2。
(2)。
In formula 2:
WNCOFor the content of isocyano, unit mmol/g in system。
V1For the amount of the standard hydrochloric acid that blank sample consumes, units/ml。
V2For the amount of the standard hydrochloric acid that testing sample consumes, units/ml。
C is the molar concentration of standard hydrochloric acid, unit mol/L。
M is the quality of sample, unit g。
In the present invention, in above-mentioned two resinoids, the mass ratio of photolytic activity diluent and synthetic resin is 1:5 ~ 3:5。The mass ratio of polymerization inhibitor and resin is 1:1000 ~ 1:100。
The photocuring insullac of the present invention is prepared via a method which: the above-mentioned photoreactive resin made is proportionally added into light trigger, cross-linking agent, defoamer, levelling agent, coupling agent, stir, it is ground by three-roll grinder, discharging, obtains insullac。Wherein, photoreactive resin can be in photolytic activity polyester resin or photolytic activity polyurethane resin or its modified resin any one or multiple。
In the present invention, described light trigger is preferably cracking type initiator, includes but not limited to 1173,184,907,369,1490,1700 etc.。Light trigger is preferably 0.5 in insullac, 0.8,1.0,1.2,2,4,6,8,9 weight portions。
In the present invention, cross-linking agent refers at intermolecular bridging action of line style so that multiple linear molecule is mutually bonded the material being cross-linked into network structure, is chiefly to facilitate or regulates polymer molecule interchain covalent bond or ionic bond is formed。Such as: be often the material containing multiple functional groups in molecule, such as organic dibasic acid, polyhydric alcohol etc.；Or molecule is contained within the compound of multiple unsaturated double-bond, such as divinylbenzene and diisocyanate, N,N methylene bis acrylamide (MBA) etc.。Specifically, the cross-linking agent of the present invention includes but not limited to: divinylbenzene, N,N methylene bis acrylamide (MBA), butyl titanate, tetraethyl titanate, dibutyl tin laurate。Its consumption can be 0.5 in photocuring insullac, 0.8,1.0,1.2 weight portions。
In the present invention, described defoamer can be commercially available for the paint organosiloxane of froth breaking, polyethers, silicon and ether grafting, containing defoamer such as amine, imines and amide-types, specifically, the defoamer of the present invention includes but not limited to: polydimethylsiloxane, tributyl phosphate, organic silicon defoamer etc.。Its consumption can be 0.3 in photocuring insullac, 0.5,0.8 weight portion。
In the present invention, described levelling agent can be commercially available for the various levelling agents of photocureable coating system, including organic silicon type, for instance silicone oil, polydimethylsiloxane, polyether polyester modified organic silicon oxygen alkane, alkyl-modified organosiloxane, terminal groups modification organosilicon；Can also be acrylic ester type, for instance acrylic resin, Lauxite and melamine resin etc.。Its consumption can be 0.3 in photocuring insullac, 0.5,0.8 weight portion。
In the present invention, described coupling agent can be commercially available for the various coupling agents of photocureable coating system, including organochromium complexes, silanes, titanate ester and aluminated compound etc.。Its consumption can be 0.3 in photocuring insullac, 0.5,0.8 weight portion。
It is a further object of the present invention to provide the using method of a kind of above-mentioned photocuring insullac, comprise the steps:
(1) parts of insullac to be coated are annealed, at its top finishing paint film, and carry out levelling；
(2) utilize ultraviolet light that paint film is carried out hardening with radiation。
In the present invention, parts described in said method can be enamel-covered wire bare wire to be produced, includes but not limited to copper cash, aluminum steel, alloy wire；Outward appearance is circle or the flat of various sizes。Can also be other parts needing to carry out insulation processing。
In the above-mentioned methods, flow time described in step 1 is 3 ~ 600s；Ultraviolet light described in step 2 is provided by the uviol lamp of certain power, and its power can be 0.2 ~ 25kW；The distance of paint film distance uviol lamp is preferably 5 ~ 80cm, and the time of hardening with radiation is preferably 5 ~ 600s。
In the said method of the present invention, sometimes for performances such as the softening improving the pliability of paint film, paint film and the adhesive force of base material, paint film further puncture, at some, properties of product are had the field of particular/special requirement, the step of heat cross-linking can also be set after ultraviolet light polymerization, including the parts after ultraviolet light polymerization being sent into heating in the stove with thermograde, complete the heat cross-linking of paint film。
In above-mentioned thermal crosslinking step, thermograde is the gradient of the even variation from low temperature to high temperature。Low-temperature end is 120 ~ 300 DEG C, and temperature end is 250 ~ 550 DEG C。The length of thermograde is 2 ~ 10m, to ensure there is certain heat time heating time wherein by the parts of enamel-cover。Heat time heating time is 0.2 ~ 45min。
For different insulative grade and the different requirements to insullac film thickness, the parameters such as viscosity according to dissimilar ultraviolet light activity insullac and ambient temperature when producing, the step repeating above-mentioned photocuring, heat cross-linking capable of circulation, finally gives satisfactory, to have certain thickness insulation paint film parts。
The said method of the present invention can be widely applied in the production technology of enamel-covered wire。Due in prior art the production technology of enamel-covered wire generally by bare wire (i.e. conductor material, conventional has copper, aluminum and alloy etc.) after annealed softening, form then through " japanning, the baking " that repeatedly circulate, can be used for the insullac preparing enamel-covered wire based on solvent-thinned paint。Therefore, in the manufacture process of enamel-covered wire, the component of about 80% evaporate in air when product uses, and environment is caused serious injury。And adopt said method to produce enamel-covered wire, the then VOC content being substantially reduced in insullac use procedure。
The beneficial effects of the present invention is:
1) described photocuring insullac can solidify under the ultraviolet light irradiation of certain power density, forms the insulation paint film with certain electrical insulation properties and mechanical performance。Without VOC in formula for a product prepared by this invention, will not to environment in using, environmental-protecting performance highlights。
2) using method of the photocuring insullac of the present invention, can complete the solidification of paint film in Production of Enamel Wires in time several seconds to tens of seconds, the VOC discharged in enamel-covered wire manufacture process can be made close to zero。Simultaneously, for meeting some field particular/special requirement to properties of product, the method has carried out heat cross-linking after the ultraviolet light polymerization stage, the performance such as further increase the adhesive force of the pliability of paint film, paint film and base material, the softening of paint film punctures, product and tradition a few indifference of enameled wire performance, it is possible to meet the needs of winding wire。Particular, it is important that the method does not discharge VOC in the manufacture process of enamel-covered wire, fundamentally solve a series of environmental issues when tradition enamel-covered wire manufactures。And products obtained therefrom performance does not decline compared with properties of product prepared by conventional insulator paint。Being make enamel insulated round copper wire on the circular copper cash of 1mm as ultraviolet curing type insullac provided by the invention is coated to nominal diameter by supporting technology provided by the invention, its indices is superior to national standard。It it is the enamel-covered wire product of about 0.04mm (diameter of enamel-covered wire is 1.08mm) to insullac film thickness, its room temperature breakdown voltage is up to more than 10kV, winding diameter is that 1mm does not ftracture, in film integrity, pinhole number is zero, softening punctures 10min at 240 DEG C and does not puncture, do not ftracture under 3 times of diameters of thermal shock, jerk have no progeny coat of paint and copper cash without departing from。
Accompanying drawing explanation
Fig. 1 is the preparation technology flow chart of the photocuring insullac of the present invention。
Detailed description of the invention
Embodiment 1
Stainless steel cauldron at 1000L (is furnished with dephlegmator, the fractional distillation ability of 3 theoretical trays of tool；By heat-conducting oil heating, and the temperature of 140 ~ 230 DEG C can be provided to material in reactor) in be sequentially added into cis-butenedioic anhydride 93kg, phthalic anhydride 240kg, adipic acid 92kg, propylene glycol 144kg, bisphenol-A 144kg, glycerol 87kg。Close reactor, pass into the noble gas such as nitrogen or argon。Start stirring motor。Open heat conduction oil circulating pump, material in reactor is heated, regulate material temperature at about 160 DEG C, control fractionating column outlet temperature and must not exceed 100 DEG C。Temperature of charge starts timing when reaching 160 DEG C, every 60min measures an acid number, and acid number changes every 15min into once lower than the mensuration acid number time after 160mg/g。After acid number is lower than 130mg/g, system is carried out decompression distillation, acid number rapid decrease。After acid number is lower than 50mg/g, stops heating, stops distillation, product is pumped in cooling reactor, Temperature fall or utilize hypothermic saline to cool down by coil pipe。
When temperature of charge is lower than 100 DEG C, add 200kg styrene and 200kg methyl methacrylate, 1kg hydroquinone, continue stirring, cool to room temperature。Adding 0.7kg tetraethyl titanate, 0.5kg organic silicon defoamer, 0.5kg levelling agent, 0.5kg coupling agent, 30kg light trigger 1173, pumping material grinds 15min, discharging in three-roll grinder, loads lighttight osculum metal bucket or Plastic Drum。Product preserves in less than 10 DEG C low temperature, shading。
Embodiment 2
Stainless steel cauldron at 2000L (is furnished with dephlegmator, the fractional distillation ability of 3 theoretical trays of tool；By heat-conducting oil heating, and the temperature of 50 ~ 120 DEG C can be provided to material in reactor) in be sequentially added into 700kg ethyl acetate, 550kg toluene di-isocyanate(TDI), 85kg hydroxypropyl acrylate, 800kg PEG400, ethylene glycol 118kg, glycerol 30kg。Close reactor, pass into the noble gas such as nitrogen or argon。Start stirring motor。Open heat conduction oil circulating pump, material in reactor is heated, regulate material temperature at about 65 DEG C, control fractionating column outlet temperature and must not exceed 50 DEG C。Temperature of charge starts timing when reaching 65 DEG C, control temperature and react 3h。Then add 5kg dibutyl tin laurate in a kettle., be warmed up to 95 DEG C and continue reaction。After reaction mass temperature reaches 95 DEG C, start timing, survey the content of isocyanates in a system per half an hour, after isocyanate content is lower than 20mg/g, system is carried out decompression distillation, steams ethyl acetate。When dephlegmator head temperature substantially rises, stop heating, stop distillation, product is pumped in cooling reactor, Temperature fall or utilize hypothermic saline to cool down by coil pipe。
When temperature of charge is lower than 100 DEG C, add 150kg butyl acrylate and 250kg methyl methacrylate, 1.2kg hydroquinone, continue stirring, cool to room temperature。Adding 1.0kg butyl titanate, 0.6kg organic silicon defoamer, 0.6kg levelling agent, 0.6kg coupling agent, 35kg light trigger 1173, pumping material grinds 15min, discharging in three-roll grinder, loads lighttight osculum metal bucket or Plastic Drum。Product preserves in less than 10 DEG C low temperature, shading。
Embodiment 3
Circular copper cash outer surface after annealed, that nominal diameter is 1.0mm is coated with and is decorated with the ultraviolet light active polyester class insullac paint film that thickness is about 8 μm, levelling 10s。With the uviol lamp that four power is 500w respectively from the four direction center of four lamps (copper cash after japanning be positioned at) distance paint film 20cm, to the copper cash irradiation 30s after japanning, complete the solidification of insullac。Putting in heating furnace by the enamel-covered wire after solidifying, the temperature of heating furnace one end is 200 DEG C, and the other end is 350 DEG C, and length is 4m。Enamel-covered wire uniform motion 5min wherein completes the heat cross-linking of paint film。Take out, cool down, obtain the enamel-covered wire that film thickness is about 8 μm。Repeat this photocuring, thermal crosslinking step 8 times, obtain the polyester enamelled wire product that film thickness is about 60 μm。
Embodiment 4
Circular copper cash outer surface after annealed, that nominal diameter is 2.0mm is coated with and is decorated with the ultraviolet light active polyurethane class insullac paint film that thickness is about 10 μm, levelling 10s。With the uviol lamp that four power is 1000w respectively from the four direction center of four lamps (copper cash after japanning be positioned at) distance paint film 10cm, to the copper cash irradiation 10s after japanning, complete the solidification of insullac。Putting in heating furnace by the enamel-covered wire after solidifying, the temperature of heating furnace one end is 180 DEG C, and the other end is 420 DEG C, and length is 6m。Enamel-covered wire uniform motion 4min wherein completes the heat cross-linking of paint film。Take out, cool down, obtain the enamel-covered wire that film thickness is about 10 μm。Repeat this photocuring, thermal crosslinking step 10 times, obtain the polyurethane enamelled wire product that film thickness is about 100 μm。
Claims (12)
1. a photocuring insullac, including the raw material of following weight portion:
Photoreactive resin 100 weight portion；
Photolytic activity diluent 20-60 weight portion；
Light trigger 0.5-10 weight portion；
Cross-linking agent 0.1-1.5 weight portion；
Defoamer 0.1-1 weight portion；
Levelling agent 0.1-1 weight portion；
Coupling agent 0.1-1 weight portion；
One or more in photolytic activity polyester resin, photolytic activity polyurethane resin or both modified products of wherein said photoreactive resin；Described photolytic activity polyester resin or its modified product be by by a certain proportion of several containing double bond raw material, hydroxyl or amino starting materials, obtain containing carboxy starting material or react at a certain temperature containing anhydride starting material；Described photolytic activity polyurethane resin or its modified product are to be obtained by containing double bond raw material, hydroxyl or amino starting materials, the raw material reaction containing isocyano；In described photolytic activity polyester resin or the preparation of its modified resin, control in raw material the amount of substance of hydroxyl and carboxyl ratio for 1.3:1 ~ 0.9:1；In described photolytic activity polyurethane resin or the preparation of its modified resin, control hydroxyl or amino starting materials and the amount of substance containing active hydrogen in isocyano raw material and isocyano ratio for 1.02:1 ~ 1.15:1。
2. photocuring insullac as claimed in claim 1, wherein said containing double bond raw material selected from Hydroxypropyl acrylate, 2-(Acryloyloxy)ethanol, hy-droxybutyl, cis maleic anhydride, trans maleic anhydride, 1-propenol-3 or dicyclopentadiene。
3. photocuring insullac as claimed in claim 1, wherein said hydroxyl or amino starting materials are selected from carbamide, tripolycyanamide, hexamethylene diamine, cyclohexanediamine, ethylene glycol, propylene glycol, glycerol, bisphenol-A, polyethylene glycol 200, PEG400, Macrogol 600, neopentyl glycol, 1-propenol-3, polyether polyol, PEPA。
4. photocuring insullac as claimed in claim 1, wherein said hydroxyl raw material is polyether Glycols or polyester diol。
5. photocuring insullac as claimed in claim 1, wherein said containing carboxy starting material or containing anhydride starting material selected from phthalic anhydride, p-phthalic acid, M-phthalic acid, phthalic acid, cis maleic anhydride, trans maleic anhydride, adipic acid。
6. photocuring insullac as claimed in claim 1, wherein said containing isocyano raw material selected from toluene di-isocyanate(TDI), isophorone diisocyanate, methyl diphenylene diisocyanate or hexamethylene diisocyanate。
7. photocuring insullac as claimed in claim 1, one or more in butyl acrylate, ethyl acrylate, carbamate mono acrylic ester, hexanediyl ester, butanediol diacrylate, neopentylglycol diacrylate, double pentaerythritol methacrylate, trimethylolpropane trimethacrylate, styrene, methyl methacrylate of described photolytic activity diluent；One or more in divinylbenzene, N,N methylene bis acrylamide (MBA), butyl titanate, tetraethyl titanate, dibutyl tin laurate of described cross-linking agent；
One or more in tributyl phosphate, organic silicon defoamer of described defoamer；Described levelling agent is selected from silicone oil, polydimethylsiloxane, polyether polyester modified organic silicon oxygen alkane, alkyl-modified organosiloxane, terminal groups modification organosilicon, acrylic resin, Lauxite and one or more in melamine resin；
One or more in organochromium complexes, silanes, titanate ester and aluminated compound of described coupling agent；
Described light trigger is selected from one or more of 1173,184,907,369,1490,1700。
8. photocuring insullac as claimed in claim 7, wherein said defoamer is selected from polydimethylsiloxane。
9. a using method for the photocuring insullac as described in any one of claim 1-8, comprises the steps:
(1) parts of insullac to be coated are annealed, at its top finishing photocuring insulation paint film, and carry out levelling；
(2) utilize ultraviolet light that paint film is carried out hardening with radiation。
10. using method as claimed in claim 9, wherein flow time described in step 1 is 3 ~ 600s；Described in step 2, ultraviolet light is provided by uviol lamp, and its power is 0.2 ~ 25kW；The distance of paint film distance uviol lamp is preferably 5 ~ 80cm, and the time of hardening with radiation is preferably 5 ~ 600s。
11. using method as claimed in claim 9, thermal crosslinking step can being set after step 2 again, including the parts after ultraviolet light polymerization being sent into heating in the stove with thermograde, completing the heat cross-linking of paint film。
12. such as the using method that claim 11 is stated, described thermograde is low-temperature end 120 ~ 300 DEG C, temperature end 250 ~ 550 DEG C；The length of thermograde is 2 ~ 10m, and heat time heating time is 0.2 ~ 45min。
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310696676.4A CN103694866B (en) | 2013-12-18 | 2013-12-18 | A kind of photocuring insullac and preparation and application thereof |
| PCT/CN2014/093444 WO2015090150A1 (en) | 2013-12-18 | 2014-12-10 | Photo-curable insulating varnish, preparation method therefor and application method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201310696676.4A CN103694866B (en) | 2013-12-18 | 2013-12-18 | A kind of photocuring insullac and preparation and application thereof |
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| CN103694866A CN103694866A (en) | 2014-04-02 |
| CN103694866B true CN103694866B (en) | 2016-06-22 |
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| CN201310696676.4A Expired - Fee Related CN103694866B (en) | 2013-12-18 | 2013-12-18 | A kind of photocuring insullac and preparation and application thereof |
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| WO (1) | WO2015090150A1 (en) |
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| CN103694866B (en) * | 2013-12-18 | 2016-06-22 | 四川优特光电科技有限公司 | A kind of photocuring insullac and preparation and application thereof |
| US9790640B2 (en) * | 2014-02-24 | 2017-10-17 | Gary S Selwyn | Composition and process for applying hydrophobic coating to fibrous substrates |
| CN104152034B (en) * | 2014-08-28 | 2016-11-23 | 重庆界威模具股份有限公司 | A kind of pottery ultraviolet curing acrylic ester composite paint |
| CN104177880B (en) * | 2014-09-09 | 2016-09-21 | 苏州圣谱拉新材料科技有限公司 | A kind of pottery lead-free paint |
| CN104356933A (en) * | 2014-11-04 | 2015-02-18 | 四川优特光电科技有限公司 | Heat-resistant ultraviolet-curing insulation paint and preparation method thereof |
| CN104387958A (en) * | 2014-12-03 | 2015-03-04 | 四川优特光电科技有限公司 | Ultraviolet-curing insulating paint with high heat resistance grade and preparation method of ultraviolet-curing insulating paint with high heat resistance grade |
| CN109104865A (en) * | 2016-03-04 | 2018-12-28 | 陶氏环球技术有限责任公司 | curable urethane acrylate composition |
| CN106118320A (en) * | 2016-07-28 | 2016-11-16 | 上海维凯光电新材料有限公司 | A kind of ultraviolet light polymerization Insulation primer compositions and application thereof |
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| CN108059905A (en) * | 2017-12-22 | 2018-05-22 | 四川东材科技集团股份有限公司 | A kind of ultraviolet-cured paint enamel and preparation method thereof |
| CN108795107A (en) * | 2018-03-24 | 2018-11-13 | 成都迪泰化工有限公司 | The method of modifying and its product and UV photocureable coating of a kind of graphene |
| CN111704851B (en) * | 2018-11-07 | 2021-11-30 | 苏州太湖电工新材料股份有限公司 | Preparation method of ATF oil-resistant flame-retardant insulating paint for electric automobile |
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| KR102340545B1 (en) * | 2019-10-02 | 2021-12-20 | 주식회사 케이씨씨 | Composition for clear coat |
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| CN111019471B (en) * | 2019-12-24 | 2021-07-09 | 无锡统力电工有限公司 | Preparation method of water-soluble ultraviolet curing wire enamel and coating curing method |
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| CN114133869A (en) * | 2021-12-17 | 2022-03-04 | 重庆绿涂腾科技有限公司 | Graphene-modified ultraviolet-curing insulating paint and preparation method thereof |
| CN114907538B (en) * | 2022-06-27 | 2023-07-14 | 韦尔通科技股份有限公司 | Ultraviolet light curing resin, ultraviolet light curing adhesive and preparation method thereof |
| CN117511383B (en) * | 2023-11-01 | 2024-04-12 | 东莞市瑞盟涂料有限公司 | Environment-friendly ultraviolet curing insulating paint and preparation process thereof |
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| CN103694866A (en) | 2014-04-02 |
| WO2015090150A1 (en) | 2015-06-25 |
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