CN103224735B - Benzoxazine-modified epoxy glass printing ink and preparation method and application thereof - Google Patents
Benzoxazine-modified epoxy glass printing ink and preparation method and application thereof Download PDFInfo
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- CN103224735B CN103224735B CN201310118219.7A CN201310118219A CN103224735B CN 103224735 B CN103224735 B CN 103224735B CN 201310118219 A CN201310118219 A CN 201310118219A CN 103224735 B CN103224735 B CN 103224735B
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Abstract
The present invention discloses benzoxazine-modified epoxy glass printing ink and preparation method and application thereof. The preparation method comprises dissolving epoxy resin in the organic solvent, evenly stirring, to obtain liquid epoxy resin, based on the mass portion, blending 60 to 80 parts of liquid epoxy resin with 8 to 20 parts of benzoxazine, heating and stirring the resultant blendings at the temperature of between 60 and 80DEG C for 10 to 25 minutes to be uniformly dissolved to obtain the ink binder; evenly mixing the resultant ink binder, 0.1 to 2 parts of defoamer, 1 to 4 parts of leveling agent, 1 to 3 parts of thickener, 8 to 15 parts of inorganic pigments, 0.1 to 1 parts of dispersants and 1 to 5 parts of inorganic filler, grinding the resultant mixture until the fineness is below 16 Mum to obtain the finished printing ink. The printing ink provided by the invention, a curing agent and a coupling agent are mixed and cured, the cured mixture is directly printed onto the glass panel, which is placed in oven for cross-linking curing to obtain the ink film with good adhesion, high hardness and excellent solvent resistance.
Description
Technical field
The present invention relates to a kind of glass epoxy ink, particularly relate to a kind of benzoxazine modified epoxy glass ink for ambetti surface and preparation method thereof.
Background technology
At present, glass has become indispensable material in the modern life, people require more and more higher to the appearance packaging of category of glass goods, the personalized designs of glass appearance has become main development trend, and glass web printing ink makes the diversified important means of category of glass products appearance color exactly.
For many years, common glass decoration technique mainly contains high temperature sintering type silk screen printing process and solvent-borne type low-temperature curing silk screen printing process, and two kinds of techniques all exist certain shortcoming.High temperature sintering type technological temperature is 600-800 DEG C, consumes a large amount of energy, and cost of manufacture is high; The pigment major part using in high temperature sintering ink is all that high temperature contains lead oxides, and heavy metal content is high, serious to harm.Low-temperature curing solvent type ink is to grow up on the basis of fired-ink, and energy consumption is low, and pigment is environmentally friendly, but the sticking power of low-temperature curing ink and stock is not strong, and hardness is not high, and acid and alkali-resistance, water, alcohol are also undesirable.The keying action of glass and common polymer a little less than, so even if adopt the polymkeric substance of epoxy resin this class strong adhesion to do binder, the resistance to stripping ability of ink is still undesirable, the ink of poor adhesive force is after preliminarily dried, ink film is easily drawn and is scratched.As a kind of important wrapping material, can there are various mechanical collisions in glass, also easily contact various corrosive atmosphere materials and organism unavoidably, and therefore, the sticking power of reinforcing glass ink, physical strength and chemoresistance play a key effect to its widespread use.
Benzoxazine is a kind of novel hot setting resin, it is to be made through dehydration condensation by phenolic compound, primary amine and aldehyde compound, under the effect of heating and/or catalyzer, the ring-opening polymerization of benzoxazine forms the crosslinking structure of similar resol, and there is the performance of many uniquenesses, as lower melt viscosity, when polymerization, emit without small molecules volatile matter, in polymerization process, shrink very little, approximate " zero " contraction, polymkeric substance has good thermotolerance, mechanical property, electric property and flame retardant properties.In the time that epoxy resin exists; can form three-dimensional polymer with epoxy resin copolymerization after benzoxazine open loop, improve cross-linking density, referred in glass epoxy ink, can fortified resin and glass between hydrogen bond action, thereby improve the chemical-resistant of ink, the sticking power of strengthening ink, and reduce its production cost.
Summary of the invention
The object of the invention is to overcome the shortcoming of prior art, a kind of strong adhesion is provided, corrosion resisting property is good, and the low benzoxazine modified epoxy glass ink of production cost and preparation method thereof.
The present invention also has an object to be to provide the application method of this benzoxazine modified epoxy glass ink.
Benzoxazine is a kind of novel ring-opening polymerization monomer, it is to be made through dehydration condensation by phenolic compound, primary amine and aldehyde compound, under the effect of heating and/or catalyzer, benzoxazine ring-opening polymerization forms the linear of similar resol or reticulated structure Polybenzoxazine resin.In the time that epoxy resin exists, after benzoxazine open loop, can form three-dimensional polymer with epoxy resin copolymerization.Polybenzoxazine structure rigidity is strong, has high-modulus, high glass-transition temperature, intensity of high thermal state and good thermostability.Compare with epoxy resin, under identical cross-linking density, the performance of the aspects such as the tensile modulus of Polybenzoxazine, tensile strength, elongation at break, water absorption resistance all, on epoxy resin, has outstanding erosion resistance and thermostability concurrently.Polybenzoxazine excellent properties mainly comes from a large amount of intermolecular and intramolecular hydrogen bonds, therefore, benzoxazine is introduced in epoxy resin ink system, can fortified resin and the hydrogen bond action of glass surface hydroxyl, can significantly improve the sticking power of ink, optimize mechanical property and the chemical resistance of resin simultaneously.The manufacturing cost of benzoxazine is lower than epoxy resin, also can suitably reduce production costs with Polybenzoxazine modified epoxy glass ink.
Object of the present invention is achieved through the following technical solutions:
A preparation method for benzoxazine modified epoxy glass ink, comprises the steps:
A) epoxy resin is dissolved in organic solvent, after stirring, obtains liquid-state epoxy resin; Described organic solvent is one or more in nylon acid dimethyl ester (DBE), isophorone, ethylene glycol monobutyl ether, ethylene glycol ether acetate, pimelinketone and diacetone alcohol;
B), in mass fraction, by liquid-state epoxy resin 60-80 part and the blend of benzoxazine 8-20 part, and by its heated and stirred 10-25 minute at 60-80 DEG C, after uniform dissolution, obtain ink adhesive; Described benzoxazine is phenylol monocycle benzoxazine, dihydric phenols benzoxazine, binary amine benzoxazine, aphthols benzoxazine and containing one or more in unsaturated link(age) class benzoxazine;
C) in mass fraction, by step b) after gained ink adhesive, defoamer 0.1-2 part, flow agent 1-4 part, thickening material 1-3 part, mineral dye 8-15 part, dispersion agent 0.1-1 part and inorganic fillings 1-5 part mixing and stirring, grind until fineness reaches below 16 μ m, obtain finished product ink; Described defoamer is silicone antifoam agent; Described flow agent is EFKA flow agent; Described thickening material is aerosil thickening material; Described mineral dye is one or more in titanium dioxide, carbon black, cobalt blue, chromoxide green, red iron oxide and lead-chrome yellow; Described dispersion agent is one or more in CH series hyper-dispersant; Described inorganic fillings is superfine alumina silicate and/or talcum powder.
Preferably, described phenylol monocycle benzoxazine is phenol/aniline type benzoxazine, phenol/benzene methanamine type benzoxazine or phenol/3,5-xylidine type benzoxazine; Described dihydric phenols benzoxazine is dihydroxyphenyl propane/aniline type benzoxazine, bisphenol S/aniline type benzoxazine or Bisphenol F/benzene methanamine type benzoxazine; Described binary amine benzoxazine is phenol/diphenylmethane diamine type benzoxazine, phenol/3,5-xylidine type benzoxazine, dihydroxyphenyl propane/diphenylmethane diamine type benzoxazine or phenol/diaminodiphenylsulfone(DDS) base benzoxazine; Described aphthols benzoxazine is naphthols/aniline type benzoxazine, naphthols/benzene methanamine type benzoxazine or naphthols/3,5-xylidine type benzoxazine; Described is o-allyl phenol/ADP methylmethane type benzoxazine, o-allyl phenol/aniline type benzoxazine or o-allyl phenol/benzene methanamine type benzoxazine containing unsaturated link(age) class benzoxazine.
Described epoxy resin and organic solvent mass ratio are 2: 1-3: 1; Described grinding is until fineness reaches 16 μ m below for grinding until fineness reaches below 16 μ m through three-roll grinder.Described epoxy resin is one or more the mixture in E-03, E-04, E-06, E-12, E-14, E-20, E-31, E-35, E-42, E-44, E-51, E-55, F-41, F-44 and F-48.Described silicone antifoam agent is one or more in BYK-020, BYK-060N, BYK066N, BYK-077, BYK-085, TSA750S, DC62, DC65 and DC163.Described EFKA flow agent is one or more in EFKA-3500,3600,3037,3034,3033,3777,3772,3886,3236 and 3288.Described CH series hyper-dispersant is one or more in CH-5, CH-6, CH-3, CH-13, CH-10S and CH-10B.
A kind of benzoxazine modified epoxy glass ink, by above-mentioned preparation method, any one makes.
The application of described benzoxazine modified epoxy glass ink: benzoxazine modified epoxy glass ink, solidifying agent, coupling agent and thinner are directly printed onto on face glass after mix and blend 10-20 minute slaking, carry out crosslinking curing; The consumption of described solidifying agent, coupling agent and thinner is respectively 6%-12%, 1%-5% and the 10%-15% of benzoxazine modified epoxy glass ink quality;
Described solidifying agent is one or more in diethylenetriamine, triethylene tetramine, tetraethylene pentamine, two propylene triamines, trolamine, diamino methylcyclohexane, hexahydropyridine, alkane diamines in the Meng (MDA), isophorone diamine (IPDA), diamino-dicyclohexyl methane, m-xylene diamine, Dyhard RU 100;
Described coupling agent is one or more in Silane coupling agent KH550, KH560, KH570, KH792, DL602 and DL171; Described thinner is ethylene glycol monobutyl ether.
Described be printed onto on face glass be by compound after slaking through 200-300 order printing screen plate: described curing temperature is 120-180 DEG C, and the curing time is 20-60 minute.
Compared with prior art, tool has the following advantages and beneficial effect in the present invention:
(1) low temperature solidified glass printing ink relatively-high temperature sintered type ink energy consumption is low, and pigment is environmentally friendly, and starting material range of choice is extensive, can effectively reduce costs.
(2) the present invention has added the 3rd component benzoxazine; benzoxazine is open loop and epoxy resin copolymerization formation build polymer architecture in curing process, improve cross-linking density, and hydrogen bond action between fortified resin and glass, thereby improve the chemical-resistant of ink, strengthen the sticking power of ink, and reduced its production cost.
(3) improve the final performance of ink by benzoxazine and epoxy blend method, have technique simple, easy to operate, performance improves obvious feature, can also economize on resources.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
A) be 20-25 DEG C in temperature, relative humidity is under the cleaning ambient of 60% left and right, take 60 parts of epoxy resin E-20 and 10 parts of epoxy resin E-44s are put into mixer, add 18 parts of ethylene glycol monobutyl ethers and 12 parts of nylon acid dimethyl ester (DBE), after stirring, obtain liquid-state epoxy resin.
B) take 70 parts of liquid-state epoxy resins and 12 parts of phenol/diphenylmethane diamine type benzoxazines, be heated to 75 DEG C and stir 15 minutes, after uniform dissolution, obtain ink adhesive.
C) take b) 82 parts of gained ink adhesives of step, 10 parts of carbon blacks, dispersing agent C H-50.7 part, 2 parts of superfine alumina silicates, 0.8 part of defoamer BYK-020,2.5 parts of flow agent EFKA-3034,2 parts of thickening material aerosils, after mixing and stirring, grind until fineness reaches below 16 μ m through three-roller, obtain benzoxazine modified epoxy glass ink.
D) benzoxazine modified epoxy glass ink is placed two days later, get 20 parts of finished product ink, add 1.7 parts of solidifying agent diethylenetriamines, 0.4 part of coupling agent KH550 and 2.5 parts of thinner ethylene glycol monobutyl ethers, stir slaking in 15 minutes, by 300 order half tones by ink printing to sheet glass, room temperature was placed after 10 minutes, put into baking oven, solidified 20 minutes with 160 DEG C, finally obtain smooth surface, well behaved finished product.Specific performance detection case is as shown in table 1.
Embodiment 2
A) be 20-25 DEG C in temperature, relative humidity is under the cleaning ambient of 60% left and right, takes 60 parts of epoxy resin E-20 and 10 parts of epoxy resin E-44s are put into mixer, adds 30 parts of ethylene glycol monobutyl ethers, after stirring, obtains liquid-state epoxy resin.
B) take 70 parts of liquid-state epoxy resins and 10 parts of dihydroxyphenyl propane/aniline type benzoxazines, be heated to 75 DEG C and stir 15 minutes, after uniform dissolution, obtain ink adhesive.
C) take b) 80 parts of gained ink adhesives of step, 12 parts of carbon blacks, dispersing agent C H-50.7 part, 2 parts of superfine alumina silicates, 0.8 part of defoamer BYK-066N, 3 parts of flow agent EFKA-3033,1.5 parts of thickening material aerosils, after mixing and stirring, grind until fineness reaches below 16 μ m through three-roller, obtain benzoxazine modified epoxy glass ink.
D) ink is placed two days later, get 20 parts of finished product ink, add 1.6 parts of solidifying agent diethylenetriamines, 0.2 part of coupling agent KH560 and 2.5 parts of thinner ethylene glycol monobutyl ethers, stir slaking in 15 minutes, by 300 order half tones by ink printing to sheet glass, room temperature was placed after 10 minutes, put into baking oven, solidified 30 minutes with 130 DEG C, finally obtain smooth surface, well behaved finished product.Specific performance detection case is as shown in table 1.
Embodiment 3
A) be 20-25 DEG C in temperature, relative humidity is under the cleaning ambient of 60% left and right, take 60 parts of epoxy resin E-20 and 10 parts of epoxy resin E-44s are put into mixer, add 18 parts of ethylene glycol monobutyl ethers and 12 parts of nylon acid dimethyl ester (DBE), after stirring, obtain liquid-state epoxy resin.
B) take 65 parts of liquid-state epoxy resins and 15 parts of dihydroxyphenyl propane/diphenylmethane diamine type benzoxazines, be heated to 75 DEG C and stir 15 minutes, after uniform dissolution, obtain ink adhesive.
C) take b) 80 parts of gained ink adhesives of step, 12 parts of carbon blacks, 1 part of dispersing agent C H-6,2 parts of superfine alumina silicates, 0.6 part of defoamer TSA750S, 2.4 parts of flow agent EFKA-3500,2 parts of thickening material aerosils, after mixing and stirring, grind until fineness reaches below 16 μ m through three-roller, obtain benzoxazine modified epoxy glass ink.
D) ink is placed two days later, get 20 parts of finished product ink, add 1.7 parts of solidifying agent diamino-dicyclohexyl methanes, 0.4 part of coupling agent KH550 and 2.2 parts of thinner ethylene glycol monobutyl ethers, stir slaking in 15 minutes, by 300 order half tones by ink printing to sheet glass, room temperature was placed after 10 minutes, put into baking oven, solidified 20 minutes with 160 DEG C, finally obtain smooth surface, well behaved finished product.Specific performance detection case is as shown in table 1.
Embodiment 4
A) be 20-25 DEG C in temperature, relative humidity is under the cleaning ambient of 60% left and right, take 60 parts of epoxy resin E-12 and 10 parts of epoxy resin E-51 put into mixer, add 18 parts of ethylene glycol ether acetates and 12 parts of nylon acid dimethyl ester (DBE), after stirring, obtain liquid-state epoxy resin.
B) take 70 parts of liquid-state epoxy resins and 15 parts of dihydroxyphenyl propane/diphenylmethane diamine type benzoxazines, be heated to 75 DEG C and stir 15 minutes, after uniform dissolution, obtain ink adhesive.
C) take b) 82 parts of gained ink adhesives of step, 10 parts of titanium dioxides, 0.7 part of dispersing agent C H-10S, 2 parts of talcum powder, 0.8 part of defoamer TSA750S, 2.5 parts of flow agent EFKA-3034,2 parts of thickening material aerosils, after mixing and stirring, grind until fineness reaches below 16 μ m through three-roller, obtain benzoxazine modified epoxy glass ink.
D) ink is placed two days later, get 20 parts of finished product ink, add 1.7 parts of solidifying agent triethylene tetramines, 0.4 part of coupling agent DL602 and 2.5 parts of thinner ethylene glycol monobutyl ethers, stir slaking in 15 minutes, by 300 order half tones by ink printing to sheet glass, room temperature was placed after 10 minutes, put into baking oven, solidified 20 minutes with 160 DEG C, finally obtain smooth surface, well behaved finished product.Specific performance detection case is as shown in table 1.
Embodiment 5
A) be 20-25 DEG C in temperature, relative humidity is under the cleaning ambient of 60% left and right, takes 55 parts of epoxy resin E-12 and 15 parts of epoxy resin E-44s are put into mixer, adds 30 parts of ethylene glycol monobutyl ethers, after stirring, obtains liquid-state epoxy resin.
B) take 70 parts of liquid-state epoxy resins and 12 parts of phenol/3,5-xylidine type benzoxazine, is heated to 75 DEG C and stir 15 minutes, obtains ink adhesive after uniform dissolution.
C) take b) 82 parts of gained ink adhesives of step, 10 parts of titanium dioxides, 1 part of dispersing agent C H-13,2 parts of talcum powder, 0.5 part of defoamer DC-163,2.5 parts of flow agent EFKA-3236,2 parts of thickening material aerosils, after mixing and stirring, grind until fineness reaches below 16 μ m through three-roller, obtain benzoxazine modified epoxy glass ink.
D) ink is placed two days later, get 20 parts of finished product ink, add 1.8 parts of solidifying agent isophorone diamines, 0.3 part of coupling agent KH550 and 2.5 parts of thinner ethylene glycol monobutyl ethers, stir slaking in 15 minutes, by 300 order half tones by ink printing to sheet glass, room temperature was placed after 10 minutes, put into baking oven, solidified 25 minutes with 160 DEG C, finally obtain smooth surface, well behaved finished product.Specific performance detection case is as shown in table 1.
Embodiment 6
A) be 20-25 DEG C in temperature, relative humidity is under the cleaning ambient of 60% left and right, take 60 parts of epoxy resin E-12 and 10 parts of epoxy resin E-51 put into mixer, add 18 parts of ethylene glycol monobutyl ethers and 12 parts of nylon acid dimethyl ester (DBE), after stirring, obtain liquid-state epoxy resin.
B) take 70 parts of liquid-state epoxy resins and 10 parts of phenol/3,5-xylidine type benzoxazine, is heated to 75 DEG C and stir 15 minutes, obtains ink adhesive after uniform dissolution.
C) take b) 80 parts of gained ink adhesives of step, 12 parts of carbon blacks, 1 part of dispersing agent C H-5,2 parts of superfine alumina silicates, 1 part of defoamer BYK-085,2 parts of flow agent EFKA-3034,2 parts of thickening material aerosils, after mixing and stirring, grind until fineness reaches below 16 μ m through three-roller, obtain benzoxazine modified epoxy glass ink.
D) ink is placed two days later, get 20 parts of finished product ink, add 1.6 parts of solidifying agent, two propylene triamines, 0.2 part of coupling agent KH560 and 2.5 parts of thinner ethylene glycol monobutyl ethers, stir slaking in 15 minutes, by 300 order half tones by ink printing to sheet glass, room temperature was placed after 10 minutes, put into baking oven, solidified 30 minutes with 130 DEG C, finally obtain smooth surface, well behaved finished product.Specific performance detection case is as shown in table 1.
Embodiment 7
A) be 20-25 DEG C in temperature, relative humidity is under the cleaning ambient of 60% left and right, take 60 parts of epoxy resin E-20 and 10 parts of epoxy resin E-44s are put into mixer, add 18 parts of ethylene glycol monobutyl ethers and 12 parts of diacetone alcohols, after stirring, obtain liquid-state epoxy resin.
B) take 65 parts of liquid-state epoxy resins and 15 parts of phenol/diaminodiphenylsulfone(DDS) base benzoxazines, be heated to 75 DEG C and stir 15 minutes, after uniform dissolution, obtain ink adhesive.
C) take b) 80 parts of gained ink adhesives of step, 12 parts of titanium dioxides, 0.7 part of dispersing agent C H-10B, 2 parts of talcum powder, 0.8 part of defoamer TSA750S, 2.5 parts of flow agent EFKA-3500,2 parts of thickening material aerosils, after mixing and stirring, grind until fineness reaches below 16 μ m through three-roller, obtain benzoxazine modified epoxy glass ink.
D) ink is placed two days later, get 20 parts of finished product ink, add 1.8 parts of solidifying agent alkane in Meng diamines, 0.3 part of coupling agent KH792 and 2.5 parts of thinner ethylene glycol monobutyl ethers, stir slaking in 15 minutes, by 300 order half tones by ink printing to sheet glass, room temperature was placed after 10 minutes, put into baking oven, solidified 30 minutes with 160 DEG C, finally obtain smooth surface, well behaved finished product.Specific performance detection case is as shown in table 1.
Embodiment 8
A) be 20-25 DEG C in temperature, relative humidity is under the cleaning ambient of 60% left and right, take 55 parts of epoxy resin E-12 and 15 parts of epoxy resin E-51 put into mixer, add 18 parts of ethylene glycol monobutyl ethers and 12 parts of nylon acid dimethyl ester (DBE), after stirring, obtain liquid-state epoxy resin.
B) take 70 parts of liquid-state epoxy resins and 15 parts of bisphenol S/aniline type benzoxazines, be heated to 75 DEG C and stir 15 minutes, after uniform dissolution, obtain ink adhesive.
C) take b) 82 parts of gained ink adhesives of step, 10 parts of carbon blacks, 0.7 part of dispersing agent C H-13,2 parts of superfine alumina silicates, 0.8 part of defoamer DC-62,2.5 parts of flow agent EFKA-3034,2 parts of thickening material aerosils, after mixing and stirring, grind until fineness reaches below 16 μ m through three-roller, obtain benzoxazine modified epoxy glass ink.
D) ink is placed two days later, get 20 parts of finished product ink, add 1.7 parts of solidifying agent, two propylene triamines, 0.4 part of coupling agent KH570 and 2.5 parts of thinner ethylene glycol monobutyl ethers, stir slaking in 15 minutes, by 300 order half tones by ink printing to sheet glass, room temperature was placed after 10 minutes, put into baking oven, solidified 25 minutes with 160 DEG C, finally obtain smooth surface, well behaved finished product.Specific performance detection case is as shown in table 1.
Embodiment 9
A) be 20-25 DEG C in temperature, relative humidity is under the cleaning ambient of 60% left and right, takes 65 parts of epoxy resin E-12 and 15 parts of epoxy resin E-51 put into mixer, adds 30 parts of ethylene glycol monobutyl ethers, after stirring, obtains liquid-state epoxy resin.
B) take step a) in 80 parts of liquid-state epoxy resins, 12 parts of carbon blacks, 0.7 part of dispersing agent C H-5,2 parts of superfine alumina silicates, 0.8 part of defoamer TSA750S, 2.5 parts of flow agent EFKA-3034,2 parts of thickening material aerosils, after mixing and stirring, grind until fineness reaches below 16 μ m through three-roller, obtain benzoxazine modified epoxy glass ink.
C) ink is placed two days later, get 20 parts of finished product ink, add 1.7 parts of solidifying agent triethylene tetramines, 0.3 part of coupling agent KH550 and 2.5 parts of thinner ethylene glycol monobutyl ethers, stir slaking in 15 minutes, by 300 order half tones by ink printing to sheet glass, room temperature was placed after 10 minutes, put into baking oven, with 160 DEG C solidify 20 minutes, the finished product specific performance detection case finally obtaining is as shown in table 1.
Sticking power grading: 0-5B in table 1; Wherein, 5B represents splendid; 4B represents fine; 3B represents well; 2B represents enough; 1B represents poor; 0B represents very poor.
Table 1 is the benzoxazine modified epoxy glass ink the performance test results of embodiment 1～8 preparation, embodiment 9 is the glass ink performance without benzoxazine modification, from table, Data Comparison is found out, benzoxazine modified epoxy glass ink of the present invention is through rational formulating of recipe, after being printed onto glass surface, over-all properties increases substantially, due to significantly improving of benzoxazine open loop in ink solidification process and epoxy resin crosslinking copolymerization density, make glass ink sticking power splendid, hardness is good, and solvent resistance is good.The use benzoxazine of novelty of the present invention is applied in the middle of glass ink, has significantly improved glass ink sticking power, chemical-resistant and has reduced its production cost.
Table 1 embodiment 1～9 the performance test results
Claims (10)
1. a preparation method for benzoxazine modified epoxy glass ink, is characterized in that comprising the steps:
A) epoxy resin is dissolved in organic solvent, after stirring, obtains liquid-state epoxy resin; Described organic solvent is one or more in nylon acid dimethyl ester, isophorone, ethylene glycol monobutyl ether, ethylene glycol ether acetate, pimelinketone and diacetone alcohol;
B) in mass fraction, by liquid-state epoxy resin 60 ?80 parts and benzoxazine 8 ?20 parts of blend, and by its 60 ?at 80 DEG C heated and stirred 10 ?25 minutes, after uniform dissolution, obtain ink adhesive; Described benzoxazine is phenylol monocycle benzoxazine, dihydric phenols benzoxazine, binary amine benzoxazine, aphthols benzoxazine and containing one or more in unsaturated link(age) class benzoxazine;
C) in mass fraction, by step b) gained ink adhesive, defoamer 0.1 ?2 parts, flow agent 1 ?4 parts, thickening material 1 ?3 parts, mineral dye 8 ?15 parts, dispersion agent 0.1 ?1 part and inorganic fillings 1 ?after 5 parts of mixing and stirring, grind until fineness reaches below 16 μ m, obtain finished product ink; Described defoamer is silicone antifoam agent; Described flow agent is EFKA flow agent; Described thickening material is aerosil thickening material; Described mineral dye is one or more in titanium dioxide, carbon black, cobalt blue, chromoxide green, red iron oxide and lead-chrome yellow; Described dispersion agent is one or more in CH series hyper-dispersant; Described inorganic fillings is superfine alumina silicate and/or talcum powder.
The preparation method of benzoxazine modified epoxy glass ink according to claim 1, it is characterized in that: described phenylol monocycle benzoxazine is phenol/aniline type benzoxazine, phenol/benzene methanamine type benzoxazine or phenol/3,5 ?xylidine type benzoxazine; Described dihydric phenols benzoxazine is dihydroxyphenyl propane/aniline type benzoxazine, bisphenol S/aniline type benzoxazine or Bisphenol F/benzene methanamine type benzoxazine; Described binary amine benzoxazine is phenol/diphenylmethane diamine type benzoxazine, dihydroxyphenyl propane/diphenylmethane diamine type benzoxazine or phenol/diaminodiphenylsulfone(DDS) base benzoxazine; Described aphthols benzoxazine is naphthols/aniline type benzoxazine, naphthols/benzene methanamine type benzoxazine or naphthols/3,5 ?xylidine type benzoxazine; Described is o-allyl phenol/ADP methylmethane type benzoxazine, o-allyl phenol/aniline type benzoxazine or o-allyl phenol/benzene methanamine type benzoxazine containing unsaturated link(age) class benzoxazine.
3. the preparation method of benzoxazine modified epoxy glass ink according to claim 1, is characterized in that: described epoxy resin and organic solvent mass ratio be 2:1 ?3:1; Described grinding is until fineness reaches 16 μ m below for grinding until fineness reaches below 16 μ m through three-roll grinder.
4. the preparation method of benzoxazine modified epoxy glass ink according to claim 1, is characterized in that: described epoxy resin be E ?03, E ?04, E ?06, E ?12, E ?14, E ?20, E ?31, E ?35, E ?42, E ?44, E ?51, E ?55, F ?41, F ?44 and F ?one or more mixture in 48.
5. the preparation method of benzoxazine modified epoxy glass ink according to claim 1, is characterized in that: described silicone antifoam agent be BYK ?020, BYK ?060N, BYK066N, BYK ?077, BYK ?085, one or more in TSA750S, DC62, DC65 and DC163.
6. the preparation method of benzoxazine modified epoxy glass ink according to claim 1, is characterized in that: described EFKA flow agent be EFKA ?one or more in 3500,3600,3037,3034,3033,3777,3772,3886,3236 and 3288.
7. the preparation method of benzoxazine modified epoxy glass ink according to claim 1, is characterized in that: described CH series hyper-dispersant be CH ?5, CH ?6, CH ?3, CH ?13, CH ?10S and CH ?one or more in 10B.
8. a benzoxazine modified epoxy glass ink, is characterized in that it is by preparation method described in claim 1 ?7, any one makes.
9. the application of benzoxazine modified epoxy glass ink described in claim 8, it is characterized in that: by benzoxazine modified epoxy glass ink, solidifying agent, coupling agent and thinner through mix and blend 10 ?be directly printed onto on face glass after slaking in 20 minutes, carry out crosslinking curing; The consumption of described solidifying agent, coupling agent and thinner be respectively benzoxazine modified epoxy glass ink quality 6% ?12%, 1% ?5% and 10% ?15%;
Described solidifying agent is one or more in diethylenetriamine, triethylene tetramine, tetraethylene pentamine, two propylene triamines, trolamine, diamino methylcyclohexane, hexahydropyridine, alkane diamines in the Meng (MDA), isophorone diamine (IPDA), diamino-dicyclohexyl methane, m-xylene diamine, Dyhard RU 100;
Described coupling agent is one or more in Silane coupling agent KH550, KH560, KH570, KH792, DL602 and DL171; Described thinner is ethylene glycol monobutyl ether.
10. the application of benzoxazine modified epoxy glass ink according to claim 9, it is characterized in that: described in be printed onto on face glass be by compound after slaking through 200 ?300 order printing screen plates: described curing temperature be 120 ?180 DEG C, the curing time be 20 ?60 minutes.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018213161A1 (en) | 2017-05-15 | 2018-11-22 | Alpha Assembly Solutions Inc. | Dielectric ink composition |
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| CN103555052A (en) * | 2013-10-30 | 2014-02-05 | 合肥市华美光电科技有限公司 | High-lubricity printing ink and preparation method thereof |
| CN104789112B (en) * | 2015-04-17 | 2017-02-22 | 苏州太湖电工新材料股份有限公司 | High-voltage motor insulating impregnating varnish and preparation method thereof |
| CN105824192A (en) * | 2016-04-05 | 2016-08-03 | 浙江康尔达新材料股份有限公司 | Infrared sensitive composition and printing plate precursors prepared by composition |
| CN108359312B (en) * | 2018-03-12 | 2021-08-03 | 江门市阪桥电子材料有限公司 | High-temperature-resistant UV-LED ink-jet printing solder resist ink and preparation method and application thereof |
| CN108864812B (en) * | 2018-08-01 | 2021-05-25 | 佛山市高明绿色德化工有限公司 | Laminated glass ink and preparation method thereof |
| CN109439068A (en) * | 2018-11-08 | 2019-03-08 | 珠海君奥新材料科技有限公司 | Ink jet ink composition applied to color crystal glass |
| CN114106626A (en) * | 2020-08-31 | 2022-03-01 | 洛阳尖端技术研究院 | Ink composition, ink, preparation method of ink and reflective film |
| CN114478427A (en) * | 2022-02-18 | 2022-05-13 | 四川金象赛瑞化工股份有限公司 | High-performance thermosetting resin curing agent/diluent and preparation method thereof |
| CN116656172A (en) * | 2023-06-21 | 2023-08-29 | 雅昌文化(集团)有限公司 | High-adhesiveness fragrant ink and preparation and printing methods thereof |
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| CN101809099A (en) * | 2007-10-01 | 2010-08-18 | 霍尼韦尔国际公司 | New organic fluorescent sulfonyl ureido benzoxazinone pigments |
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| TW200413467A (en) * | 2003-01-16 | 2004-08-01 | Chang Chun Plastics Co Ltd | Resin composition without containing halogen |
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| CN101809099A (en) * | 2007-10-01 | 2010-08-18 | 霍尼韦尔国际公司 | New organic fluorescent sulfonyl ureido benzoxazinone pigments |
| CN102358810A (en) * | 2011-09-14 | 2012-02-22 | 哈尔滨大东方卷烟材料科技开发有限责任公司 | Environment-friendly type water-based intaglio ink used for package printing and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018213161A1 (en) | 2017-05-15 | 2018-11-22 | Alpha Assembly Solutions Inc. | Dielectric ink composition |
| CN110832039A (en) * | 2017-05-15 | 2020-02-21 | 阿尔法装配解决方案公司 | Dielectric ink composition |
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