CN105331188B - Art printing ink for crystallized metal printing - Google Patents

Abstract

The invention belongs to the technical field of printing ink, and particularly relates to art printing ink for crystallized metal printing. The printing ink is prepared by, by mass, 50-80% of short oil alkyd resin, 1-15% of closed polyisocyanate, 5-20% of boiled tung oil, 1-5% of a solvent, 1-10% of phenylated amino resin, 0.05-2% of a first leveling agent, 0.3-1% of a dispersing agent, 1-3% of a second leveling agent, 0.05-5% of lubricant, 0.05-3% of a closed acid catalyst, 0.1-5% of filler and 0.1-2% of an adhesion promoter. Compared with the prior art, the printing ink can meet the requirement of local printing crystallized art printing ink of tinplate, and unique crystallized vision and tactile sense are provided. Besides, the printing ink is environmentally friendly, free of toxin and small in odor in the construction process, does not contain cobalt, manganese, bisphenol A and other matter restricted for use, and meets the requirement for environmental protection.

Description

A kind of crystallized tin graphed sheet fine arts ink

Technical field

The invention belongs to technical field of ink, more particularly to a kind of crystallized tin graphed sheet fine arts ink of environment-friendly type.

Background technology

Fine arts ink is the ink kind with special efficiency being made up of special material, belongs to industrial ink.With other Ink is the same, this ink is imprinted on body surface and can play the protective effect to object, except for the difference that after its ink film forming, applies Film can form or occur the pattern or decorative pattern of various beauties, and appearance colour is gorgeous, well arranged, elegant in appearance, with obvious High-decoration.

Crystallized ink is one kind of fine arts ink, is gained the name because of appearance of film likeness in form crystallization.It is its film clean mark, glittering Luminous, visual effect is unique, can act the effect covered to the flaw of ground, and with superpower dicoration, and sense of touch children is sliding, stereovision By force, but, do not occur crystallized tin graphed sheet fine arts ink in the market（Only coatings for tin plate printing）, this is because which is the industry One bottleneck for being difficult to break through.

Tin graphed sheet tank is primarily referred to as the tinplate for printing various patterns making variously-shaped iron flask.It is big by its purposes Cause can be divided into food cans, gift tank and chemical tank, common are moon cake tank, caddy, milk pot, wine tank, beverage can and chemical industry Bucket etc..The operation of tin graphed sheet tank is mainly at present：A coating is coated on tinplate first（Bottoming oil or white oil）, so Afterwards in coating surface printing-ink（First printing chalk, then print the color ink such as red, yellow, blue）, the then finishing oil on ink again（Light or Dumb light）, required shape is eventually fabricated, that is, obtains finished product.Wherein ink and coating are both needed to baking and curing or UV solidifications.

But, current tin printing ink and coating there is also following deficiency：

First, in addition to printed patterns difference, surface effect is dull, it is impossible to provide more visual tactile impressions, though can The artistic coatings such as print crystal coating are applied on printed document surface to improve product specification and added value, but are the roller coating of full version and printed, Just must can use on the premise of full version is printed, it is impossible to which satisfaction need to locally print wanting for crystallized fine arts ink on tinplate Ask, and due to the price of crystal coating it is higher than common gloss oil and mute oil several times and substantially increase printing cost.

Secondly, existing tin printing ink is mainly by Cortex cocois radiciss oil alkyd resin or soybean alkyd, epoxy resin and amino Resin is that binder grinding blended with various pigment and whole toner is formed, and formula contains cobalt, manganese class drier, not environmentally；

Again, the epoxy resin for being used for improving in formula adhesive force contains harmful material bisphenol-A.

In view of this, it is necessory to provide a kind of crystallized tin graphed sheet fine arts ink of environment-friendly type, which can meet tinplate office The requirement that printed by portion, there is provided unique crystallized vision and touch feeling, improves product specification and added value；And its formula is not contained Cobalt, manganese class drier, meet the requirement of environmental protection；Without harmful materials such as bisphenol-As in formula.

The content of the invention

It is an object of the invention to：For the deficiencies in the prior art, and provide a kind of crystallized tin graphed sheet artists' oil of environment-friendly type Ink, which can meet the requirement of tinplate local printing, there is provided unique crystallized vision and touch feeling, improve product specification and Added value；And its formula does not contain cobalt, manganese class drier, meet the requirement of environmental protection；It is harmful without bisphenol-A etc. in formula Material.

In order to achieve the above object, the present invention is adopted the following technical scheme that：A kind of crystallized tin graphed sheet fine arts ink, by quality hundred Divide than meter, including following components：

Short oil-ity alcohol acid resin 50%～80%；

Enclosed type polyisocyanate 1%～15%；

Boiled wood oil 5%～20%；

Solvent 1%～5%；

Benzene is for amino resins 1%～10%；

Leveling auxiliary agent 0.05%～2%；

Dispersant 0.3%～1%；

Auxiliary rheological agents 1%～3%；

Increase sliding auxiliary agent 0.05%～5%；

Enclosed type acid catalyst 0.05%～3%；

Filler 0.1%～5%；

Adhesion promoter 0.1%～2%.

Wherein, short oil-ity alcohol acid resin gloss height, brushability, good leveling property, and its release to solvent is very fast, is dried Performance is good；Enclosed type polyisocyanate is to react the room temperature that generates under stable with sealer by the NCO group of polyisocyanate Polymer, enclosed type polyisocyanate are coordinated with polyol resin, can obtain ink stable under room temperature, and the ink is in baking Under the conditions of, sealer is dissociated at high temperature, discharges NCO group, so as to polyisocyanate is crosslinked with polyol resin component Reaction, forms film.Enclosed type polyisocyanate is easily operated, and insensitive to atmospheric humidity.Oleum Verniciae fordii is a kind of excellent band Dry vegetable oil, with fast drying, light specific gravity, glossiness is good, adhesive force is strong, heat-resisting, acidproof, alkaline-resisting, anti-corrosion, antirust, do not lead The characteristics such as electricity, it is of many uses.Which is divided into two kinds of raw Oleum Verniciae fordii and boiled wood oil again, and boiled wood oil is processed by Oleum Verniciae fordii is given birth to, and boiled wood oil is again It is divided into two kinds, one kind is ripe pure Oleum Verniciae fordii, another is mixing boiled wood oil, wherein, the extracting process of skillful Oleum Verniciae fordii is by the seeds of a tung oil tree Oil expression is fried, is not artificially added any chemical composition, and it is then by 20% varnish, 20% Colophonium and 60% to mix boiled wood oil After Oleum Verniciae fordii is blent, heating boils to 260 DEG C and makes.The boiled wood oil taste of mixing is big, has the breath of strong paint, therefore, this Bright boiled wood oil is preferably ripe pure Oleum Verniciae fordii, and the ink stability for adding boiled wood oil is good, fast drying, using the bad spy of its pollution resistance Point, is placed in the air of the dirt gas such as sulfur dioxide, it becomes possible to form obvious crystallized, and lines is clear, light, whiteness It is good.

Solvent is used to dissolve other materials so as to which its material is uniformly dispersed therein.Benzene is for amino resins and various thermosettings Property resin it is compatible good, and water-tolerant, good luster, pliability be good, salt spray resistance, chemical-resistance are good, is particularly moving It is more excellent to colouring in terms of transfer.Enclosed type acid catalyst is used to play catalytic action, improves short oil-ity alcohol acid resin and closing The speed of cross-linking reaction between type polyisocyanate, reduce solidification temperature, shorten hardening time, the hardness for improving ink, gloss, Moisture resistance and corrosion resistance, the mechanical performance for improving ink.The effect of adhesion promoter be increase substantially film layer with The adhesive force of base material, and the moisture resistance of film, resistance to saltfog energy and heat resistance, and minimum consumption can be improved, you can The ductility and resistance to impact that obtain high-strength adhesive force and be bonded power, film can be promoted, high-temperature baking invariant color, and not shadow Ring the weatherability of film.

Filler can cause the viscosity of ink to increase, and filler is needed through processed before addition, to avoid consuming portion Divide isocyanates.Filler effectively can be spread out by dispersant, prevent filler from reuniting so that the thickening effect of filler is everywhere It is homogeneous.Auxiliary rheological agents are the key components of ink, and it can control the delicate nature and feature of fluid product, not have these media Ink is easy for sagging, ink in coating process will splashes, covering power diminishes, and the pot-life can also contract It is short, using the mobility of the adjustable ink of auxiliary rheological agents, reduce the drippage and splashing occurred during roller coat or brushing, ink Viscosity is quick and controllably increases, and so as to improve sag resistance, during ink is transported or stored, auxiliary rheological agents can be prevented Pigment sedimentation in formula, it is ensured that the concordance of final products, reaches the flat of rationality between durability and good coating characteristics Weighing apparatus.

Additionally, in the present invention content of solvent seldom, only 1%-5%, along with the potent thickening power of filler, because This, the present invention is especially sticky, therefore in process, it is accordingly required in particular to leveling auxiliary agent.Leveling auxiliary agent is dynamically or statically Under the conditions of, surface tension can be reduced, increases wettability, improve the auxiliary agent of levelling effect.If levelling is bad, Fructus Citri tangerinae will be caused Skin, shrinkage cavity, brush mark etc. paint film defect, and the addition of appropriate leveling auxiliary agent can then improve these paint film defects, promote oil Ink forms a smooth, smooth, uniform film during drying and forming-film.After ink is coated on body surface, increases cunning and help Agent can float over film coated surface, reduce the surface tension of ink, make film reduce the coefficient of friction on second surface, keep away film Exempt to scratch, can also improve the workability of the industrial coating of the serialization of ink.

Improve as one kind of crystallized tin graphed sheet fine arts ink of the present invention, by mass percentage, including following components：

Short oil-ity alcohol acid resin 60%～70%；

Enclosed type polyisocyanate 3%～12%；

Boiled wood oil 7%～15%；

Solvent 2%～4%；

Benzene is for amino resins 3%～7%；

Leveling auxiliary agent 0.2%～1.5%；

Dispersant 0.5%～0.8%；

Auxiliary rheological agents 1.5%～2.5%；

Increase sliding auxiliary agent 0.5%～3%；

Enclosed type acid catalyst 0.2%～2%；

Filler 0.5%～3%；

Adhesion promoter 0.5%～1.5%.

Improve as one kind of crystallized tin graphed sheet fine arts ink of the present invention, the short oil-ity alcohol acid resin is by polyhydric alcohol, neighbour Phthalate anhydride and fatty acid condensation are polymerized, and wherein the mass percent of fatty acid is less than 40%.

As crystallized tin graphed sheet fine arts ink of the present invention one kind improve, the polyhydric alcohol be glycerol, trimethylolpropane, three At least one in hydroxymethyl ethane, tetramethylolmethane, ethylene glycol, 1,2-PD and 1,3-PD；The fatty acid is Asia Fructus Cannabis oil, Oleum Glycines, Oleum Gossypii semen, Oleum Ricini, dehydrated castor oil, Oleum Cocois, Oleic acid, linoleic acid, Petiolus Trachycarpi oil, Oleum Arachidis hypogaeae semen and soybean oil In at least one.

Improve as one kind of crystallized tin graphed sheet fine arts ink of the present invention, the enclosed type polyisocyanate is by polyisocyanate Ester reacts the polymer for generating with sealer, and the sealer is ethylene glycol monobutyl ether, caprolactam, imidazoles and 2-methylimidazole In at least one, oneself is two different by toluene di-isocyanate(TDI), methyl diphenylene diisocyanate and 1,6- for the polyisocyanate At least one addition in cyanate.Aliphatic polymeric isocyanate has more preferable color inhibition than aromatic poly-isocyanate Performance, and the film that aromatic poly-isocyanate reaction is produced is harder.Both can guarantee that film had after the two polymerization preferably resistance to Xanthochromia performance, can guarantee that film has larger hardness again.

Improve as one kind of crystallized tin graphed sheet fine arts ink of the present invention, the solvent is containing benzene solvent, esters solvent, ethers At least one in solvent and alcohols solvent, described is at least one in toluene, dimethylbenzene and 1-Phenylethanone. containing benzene solvent；It is described Esters solvent be ethyl acetate, butyl acetate and ethylene glycol ether acetate at least one, the ether solvent be ether, At least one in diethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether and dimethyl ether；The alcohols is molten Agent is at least one in ethanol, ethylene glycol, methanol, normal propyl alcohol, isopropanol and n-butyl alcohol.Short oil-ity alcohol acid resin is molten at these Dissolubility in agent is larger.

As crystallized tin graphed sheet fine arts ink of the present invention one kind improve, the benzene for amino resins be methyl-etherified benzene for amino At least one in resin and the etherification benzene substituted amino resins of fourth；The leveling auxiliary agent is esters of acrylic acid, organic silicon modified by polyether At least one of class and hydroxyl alkyl modified organic silicon apoplexy due to endogenous wind；The auxiliary rheological agents are polyurethane, polyethers, aerosil and have At least one in machine bentonite；It is described to increase sliding auxiliary agent at least one in wax liquor and wax powder.Wax powder can substantially reduce offset printing During heap ink or brush in embossed lacquer phenomenon, particle diameter is little, and good dispersion, caking performance are good, and can provide splendid anti scuffing with Excellent extinction, the transparency and feel.The median particle diameter for increasing sliding auxiliary agent is 50nm～20 μm.

Improve as one kind of crystallized tin graphed sheet fine arts ink of the present invention, described filler is nano-aluminium oxide granule, receives Rice antimony oxide granule, nano-calcium carbonate particles, nano oxidized magnesium granules, nanometer silicon dioxide particle and nano titanium oxide At least one in granule；Nano level filler can not only play a part of thickening, and fineness is good, and good processability is described Dispersant is at least one in waterglass, sodium tripolyphosphate, sodium pyrophosphate, Oleic acid and Polyethylene Glycol.

As crystallized tin graphed sheet fine arts ink of the present invention one kind improve, the enclosed type acid catalyst be p-methyl benzenesulfonic acid and At least one in DBSA；The adhesion promoter is amino silicone, alkylsiloxane and propyl group front three At least one in epoxide siloxanes.

Improve as one kind of crystallized tin graphed sheet fine arts ink of the present invention, its preparation method is comprised the following steps：

The first step, short oil-ity alcohol acid resin, benzene is added in dispersion cylinder for amino resins, solvent and dispersant, side stirring Side adds filler, after disperseing at a high speed, adds enclosed type polyisocyanate, boiled wood oil, leveling auxiliary agent, auxiliary rheological agents, increasing cunning and helps Agent, enclosed type acid catalyst and adhesion promoter continue dispersion, until being uniformly dispersed；

Second step, is pressed 2-10 time with three-roller so as to which fineness reaches less than 10 μm and obtains final product crystallized tin graphed sheet fine arts ink.

When the crystallized tin graphed sheet fine arts ink is applied on coated article, by the crystallized tin graphed sheet fine arts by the way of offset printing Ink is passed on coated article, 2min～10min is then dried at 60 DEG C～90 DEG C, then is dried at 130 DEG C～155 DEG C 6min～15min., so that solvent is vapored away gradually, there is crystallized in first cold drying, is then dried with higher temperature again, can To form obvious, well-regulated, uniform crystallized.

Relative to prior art, the present invention has following advantage：

First, the requirement that crystallized fine arts ink is printed in tinplate local can be met, there is provided unique crystallized vision and touch Feel impression, which there can be clean mark, glittering film is ensured, can act the effect covered to the flaw of ground, with superpower Dicoration, improve product specification and added value, product cost be greatly lowered；And the present invention is sliding in sense of touch children, stereovision is strong On the premise of, due to formulation stability it is good, therefore, it is possible to extend the storage time of ink to meet the needs of production in enormous quantities, and And baking time can be shortened, practice have shown that：The present invention is toasted under conditions of 60 DEG C～160 DEG C 8～25 minutes just can be completely Solidification, such that it is able to greatly improve curing efficiency.

Second, environment-protecting asepsis limit the material for using without cobalt, manganese, bisphenol-A etc., and in work progress, abnormal smells from the patient is little, environment friend It is good, meet the requirement of environmental protection；

3rd, can be to be coated with using offset lithographic mode, loss is low, and can greatly improve production efficiency.

Additionally, the crystallized tin graphed sheet fine arts ink of the present invention is transparent, various pigment or dyestuff can be added to present which Go out shades of colour.

Specific embodiment

Embodiment 1

A kind of crystallized tin graphed sheet fine arts ink that the present embodiment is provided, by mass percentage, including following components：

Short oil-ity alcohol acid resin 65%；

Enclosed type polyisocyanate 10%；

Boiled wood oil 10%；

Dimethylbenzene 3%；

Methyl-etherified benzene is for amino resins 5%；

Hydroxyl alkyl modified organic silicon class 0.5%；

Polyethylene Glycol 0.5%；

Polyurethane 2%；

Wax liquor 1%；

P-methyl benzenesulfonic acid 1%；

Nano silicon 1%；

Amino silicone 1%.

Wherein, short oil-ity alcohol acid resin is formed by glycerol, phthalic anhydride and Oleum Glycines condensation polymerization, wherein, Oleum Glycines Mass percent be 35%, the mass percent of phthalic anhydride is 30%.Enclosed type polyisocyanate is by polyisocyanate Ester reacts the polymer for generating with ethylene glycol monobutyl ether, wherein, polyisocyanate is by toluene di-isocyanate(TDI), diphenyl methane two Isocyanates and 1, hexamethylene-diisocyanate is according to molar ratio 1：1：1 addition.The median particle diameter of wax liquor is 5 μm.Wherein Boiled wood oil be ripe pure Oleum Verniciae fordii, its extracting process is that the seeds of a tung oil tree are fried oil expression, does not artificially add any chemical composition.Nano-silica The mean diameter of SiClx is 100nm.

Its preparation method is comprised the following steps：

Short oil-ity alcohol acid resin, methyl-etherified benzene are added dispersion cylinder for amino resins, dimethylbenzene and Polyethylene Glycol by the first step In, nano silicon is added while stirring, after disperseing at a high speed, is added enclosed type polyisocyanate, boiled wood oil, hydroxyl alkyl and is changed Property silicone, polyurethane, wax liquor, p-methyl benzenesulfonic acid and amino silicone continue dispersion, until being uniformly dispersed；

Second step, is pressed 3 times with three-roller so as to which fineness reaches less than 10 μm and obtains final product crystallized tin graphed sheet fine arts ink.

Embodiment 2

A kind of crystallized tin graphed sheet fine arts ink that the present embodiment is provided, by mass percentage, including following components：

Short oil-ity alcohol acid resin 59%；

Enclosed type polyisocyanate 5%；

Boiled wood oil 15%；

Ethanol 1.5%；

Ethyl acetate 1%；

The etherification benzene substituted amino resins of fourth 8%；

Organic silicon modified by polyether class 0.8%；

Waterglass 0.7%；

Aerosil 1.5%；

Wax powder 3%；

DBSA 2%；

Nano-aluminium oxide 2%；

Alkylsiloxane 0.5%.

Wherein, short oil-ity alcohol acid resin is formed by ethylene glycol, phthalic anhydride and Oleic acid condensation polymerization, wherein, oil The mass percent of acid is 38%, and the mass percent of phthalic anhydride is 28%.Enclosed type polyisocyanate is by poly- isocyanide Acid esters and caprolactam react the polymer for generating, wherein, polyisocyanate is by oneself two isocyanides of toluene di-isocyanate(TDI) and 1,6- Acid esters is according to molar ratio 1：1 addition.The median particle diameter of wax powder is 15 μm.Boiled wood oil therein is ripe pure Oleum Verniciae fordii, its squeezing The method of taking is that the seeds of a tung oil tree are fried oil expression, does not artificially add any chemical composition.The mean diameter of nano-aluminium oxide is 200nm。

Its preparation method is comprised the following steps：

The first step, short oil-ity alcohol acid resin, the etherification benzene substituted amino resins of fourth, ethanol, ethyl acetate and waterglass are added In dispersion cylinder, add nano-aluminium oxide while stirring, after disperseing at a high speed, add enclosed type polyisocyanate, boiled wood oil, Organic silicon modified by polyether class, aerosil, wax powder, DBSA and alkylsiloxane continue dispersion, until point Dissipate uniform；

Second step, is pressed 5 times with three-roller so as to which fineness reaches less than 10 μm and obtains final product crystallized tin graphed sheet fine arts ink.

Embodiment 3

A kind of crystallized tin graphed sheet fine arts ink that the present embodiment is provided, by mass percentage, including following components：

Short oil-ity alcohol acid resin 70.5%；

Enclosed type polyisocyanate 8%；

Boiled wood oil 6%；

Normal propyl alcohol 2%；

Butyl acetate 2%；

The etherification benzene substituted amino resins of fourth 2%；

Hydroxyl alkyl modified organic silicon class 0.6%；

Sodium tripolyphosphate 0.4%；

Polyethers 2.5%；

Wax powder 0.5%；

DBSA 0.5%；

Nano oxidized magnesium granules 3.5%；

Propyl trimethoxy siloxanes 1.5%.

Wherein, short oil-ity alcohol acid resin is formed by tetramethylolmethane, phthalic anhydride and Oleum Ricini condensation polymerization, its In, the mass percent of Oleum Ricini is 36%, and the mass percent of phthalic anhydride is 35%.Enclosed type polyisocyanate be by Polyisocyanate reacts the polymer for generating with imidazoles, wherein, polyisocyanate is by methyl diphenylene diisocyanate and 1,6- Hexamethylene diisocyanate is according to molar ratio 1：1 addition.The median particle diameter of wax powder is 500nm.Boiled wood oil therein is ripe pure Oleum Verniciae fordii, its extracting process are that the seeds of a tung oil tree are fried oil expression, artificially do not add any chemical composition.The average grain of nano oxidized magnesium granules Footpath is 300nm.

Its preparation method is comprised the following steps：

The first step, by short oil-ity alcohol acid resin, the etherification benzene substituted amino resins of fourth, normal propyl alcohol, butyl acetate and tripolyphosphate During sodium adds dispersion cylinder, nano magnesia is added while stirring, after disperseing at a high speed, enclosed type polyisocyanate, ripe paulownia is added Oil, hydroxyl alkyl modified organic silicon class, polyethers, wax powder, DBSA and propyl trimethoxy siloxanes continue dispersion, directly To being uniformly dispersed；

Second step, is pressed 4 times with three-roller so as to which fineness reaches less than 10 μm and obtains final product crystallized tin graphed sheet fine arts ink.

Embodiment 4

A kind of crystallized tin graphed sheet fine arts ink that the present embodiment is provided, by mass percentage, including following components：

Short oil-ity alcohol acid resin 54%；

Enclosed type polyisocyanate 12%；

Boiled wood oil 18%；

Diethylene glycol monomethyl ether 1%；

Ethylene glycol ether acetate 2.5%；

Methyl-etherified benzene is for amino resins 2%；

Hydroxyl alkyl modified organic silicon class 1.6%；

Sodium pyrophosphate 0.4%；

Organobentonite 1.5%；

Wax liquor 1.8%；

P-methyl benzenesulfonic acid 1.2%；

Titanium dioxide nanoparticle 2.8%；

Amino silicone 1.2%.

Wherein, short oil-ity alcohol acid resin is formed by 1,2-PD, phthalic anhydride and Petiolus Trachycarpi oil condensation polymerization, its In, the mass percent of Petiolus Trachycarpi oil is 36%, and the mass percent of phthalic anhydride is 36%.Enclosed type polyisocyanate be by Polyisocyanate reacts the polymer for generating with 2-methylimidazole, wherein, polyisocyanate is by toluene di-isocyanate(TDI) and 1,6- Hexamethylene diisocyanate is according to molar ratio 1：3 additions.The median particle diameter of wax liquor is 1 μm.Boiled wood oil therein is ripe pure paulownia Oil, its extracting process are that the seeds of a tung oil tree are fried oil expression, artificially do not add any chemical composition.The average grain of titanium dioxide nanoparticle Footpath is 150nm.

Its preparation method is comprised the following steps：

The first step, by short oil-ity alcohol acid resin, methyl-etherified benzene for amino resins, diethylene glycol monomethyl ether, ethylene glycol During acetate and sodium pyrophosphate add dispersion cylinder, nano titanium oxide is added while stirring, after disperseing at a high speed, enclosed type is added Polyisocyanate, boiled wood oil, hydroxyl alkyl modified organic silicon class, organobentonite, wax liquor, p-methyl benzenesulfonic acid and amino silicone after Continuous dispersion, until being uniformly dispersed；

Second step, is pressed 7 times with three-roller so as to which fineness reaches less than 10 μm and obtains final product crystallized tin graphed sheet fine arts ink.

Embodiment 5

A kind of crystallized tin graphed sheet fine arts ink that the present embodiment is provided, by mass percentage, including following components：

Short oil-ity alcohol acid resin 61%；

Enclosed type polyisocyanate 3%；

Boiled wood oil 16.2%；

Propylene glycol monomethyl ether 1.8%；

Methyl-etherified benzene is for amino resins 3%；

The etherification benzene substituted amino resins of fourth 3.2%；

Hydroxyl alkyl modified organic silicon class 0.4%；

Organic silicon modified by polyether class 0.4%；

Oleic acid 0.9%；

Polyurethane 0.5%；

Polyethers 0.6%；

Wax liquor 1%；

Wax powder 1.9%；

P-methyl benzenesulfonic acid 1%；

DBSA 1.1%；

Nanmeter antimong trioxide granule 1.7%；

Nano-calcium carbonate particles 2%；

Amino silicone 0.1%；

Propyl trimethoxy siloxanes 0.2%.

Wherein, short oil-ity alcohol acid resin is formed by trimethylolethane, phthalic anhydride and Oleum Gossypii semen condensation polymerization, Wherein, the mass percent of Oleum Gossypii semen is 32%, and the mass percent of phthalic anhydride is 33%.Enclosed type polyisocyanate is The polymer for generating is reacted by polyisocyanate and 2-methylimidazole, wherein, polyisocyanate is by toluene di-isocyanate(TDI), hexichol Dicyclohexylmethane diisocyanate and 1, hexamethylene-diisocyanate is according to molar ratio 1：2：1 addition.The median particle diameter of wax powder is 3 μm.The median particle diameter of wax liquor is 2 μm.Boiled wood oil therein is ripe pure Oleum Verniciae fordii, and its extracting process is that the seeds of a tung oil tree are fried oil expression, not people To add any chemical composition.The mean diameter of nanmeter antimong trioxide granule be 250nm, the average grain of nano-calcium carbonate particles Footpath is 120nm.

Its preparation method is comprised the following steps：

The first step, by short oil-ity alcohol acid resin, methyl-etherified benzene for amino resins, the etherification benzene substituted amino resins of fourth, Propylene Glycol During methyl ether and Oleic acid add dispersion cylinder, nanmeter antimong trioxide granule, nano-calcium carbonate particles are added while stirring, is disperseed at a high speed Afterwards, add enclosed type polyisocyanate, boiled wood oil, hydroxyl alkyl modified organic silicon class, organic silicon modified by polyether class, polyurethane, Polyethers, wax liquor, wax powder, p-methyl benzenesulfonic acid, DBSA, amino silicone and propyl trimethoxy siloxanes continue to divide Dissipate, until being uniformly dispersed；

Second step, is pressed 6 times with three-roller so as to which fineness reaches less than 10 μm and obtains final product crystallized tin graphed sheet fine arts ink.

The crystallized tin graphed sheet fine arts ink of embodiment 1 to 5 is transferred using offset lithographic machine, the part table of pressure rolling to tinplate On face, specifically：The crystallized tin graphed sheet fine arts ink of embodiment 1 to 5 is passed to into the part table of tinplate by the way of offset printing On face, be then dried 5min at 80 DEG C so that solvent is vapored away gradually, and forms crystallized, then respectively 160 DEG C, 155 DEG C, 150 DEG C, toast 10 points of the above-mentioned film being presented on the part surface of tinplate respectively under conditions of 155 DEG C and 160 DEG C Clock, 11 minutes, 11 minutes, 10 minutes, 11 minutes, as a result show, film layer it is cured completely, and define significantly, have Rule, uniform crystallized, and there is not the phenomenon of yellowing in film layer.

Acquired results are shown in Table 1 to be detected to the film layer for being formed by the method for ink national Specification.

Table 1：The test of the crystallized film that embodiment 1 to 5 and commercially available crystallized tin graphed sheet fine arts ink are formed on tinplate As a result.

Detection project	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Commercially available crystallized coatings for tin plate printing
							Outward appearance, range estimation	Crystallized effect is good	Crystallized effect is good	Crystallized effect is good	Crystallized effect is good	Crystallized effect is good	Crystallized effect is general
60 ° of gloss, %	82	85	87	89	84	40
							Adhesive force, level	1	1	1	1	1	3
Impact resistance/J	3.01	3.21	3.53	3.15	3.67	2.5
							Dryness/min	10	11	9	12	13	20
Fineness/μm	10	12	9	11	8	15
							Boiling resistance/level	5	5	5	5	5	3
Thermostability/level	5	5	5	5	5	3
							Tinplate local whether can be met to print	Energy	Energy	Energy	Energy	Energy	It is no
Whether cobalt, manganese, bisphenol-A are contained	It is no	It is no	It is no	It is no	It is no	It is
							Pencil hardness	1H	1H	1H	1H	1H	0.5H
Thickness	6μm	8μm	7μm	10μm	9μm	12μm

As shown in Table 1, compared with commercially available crystallized coatings for tin plate printing, the crystallized tin graphed sheet fine arts ink not only crystallized effect of the present invention Good, not yellowing, glossiness are high, and adhesive force is high, and pliability is good, and impact strength is also high.And, solid content of the present invention is high, solidification speed Degree block, solvent are few, more environmentally friendly, and thinner coating can be obtained by the way of offset printing.

Tinplate to scribbling above-mentioned film layer carries out punching press and stretching, then observes the crystallized coating, as a result finds：Using The film layer that the crystallized tin graphed sheet fine arts ink of embodiment 1 to 5 is formed does not find the defects such as crackle, and adopts commercially available crystallized to print The film layer that ferrum fine arts ink is formed then is found that obvious crackle.This shows the crystallized tin graphed sheet fine arts ink shape using the present invention Into film layer there is more preferable aft-loaded airfoil performance.

In a word, the present invention can meet the requirement that crystallized fine arts ink is printed in tinplate local, there is provided unique crystallized is regarded Feel and touch feeling, improve product specification and added value, product cost is greatly lowered；And environment-protecting asepsis, without cobalt, manganese, Bisphenol-A etc. limits the material for using.

Each component in the present invention can be obtained by commercial channel, without the need for separately synthesized or purified, therefore, this Each composition of invention is readily available, such that it is able to reduce manufacturing cost.

The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party Formula is changed and is changed.Therefore, specific embodiment disclosed and described above is the invention is not limited in, to the present invention's Some modifications and changes should also be as falling in the scope of the claims of the present invention.Although additionally, used in this specification Some specific terms, but these terms are merely for convenience of description, do not constitute any restriction to the present invention.

Claims (10)

1. a kind of crystallized tin graphed sheet fine arts ink, it is characterised in that by mass percentage, including following components：

2. crystallized tin graphed sheet fine arts ink according to claim 1, it is characterised in that by mass percentage, including following Component：

3. crystallized tin graphed sheet fine arts ink according to claim 1 and 2, it is characterised in that：The short oil-ity alcohol acid resin is It is polymerized by polyhydric alcohol, phthalic anhydride and fatty acid condensation, wherein the mass percent of fatty acid is less than 40%.

4. crystallized tin graphed sheet fine arts ink according to claim 3, it is characterised in that：The polyhydric alcohol is glycerol, three hydroxyl first At least one in base propane, trimethylolethane, tetramethylolmethane, ethylene glycol, 1,2-PD and 1,3-PD；The fat Fat acid is Semen Lini oil, Oleum Glycines, Oleum Gossypii semen, Oleum Ricini, dehydrated castor oil, Oleum Cocois, Oleic acid, linoleic acid, Petiolus Trachycarpi oil, Oleum Arachidis hypogaeae semen With at least one in soybean oil.

5. crystallized tin graphed sheet fine arts ink according to claim 1 and 2, it is characterised in that：The enclosed type polyisocyanate It is that the polymer for generating is reacted by polyisocyanate and sealer, the sealer is ethylene glycol monobutyl ether, caprolactam, imidazoles With at least one in 2-methylimidazole, the polyisocyanate is by toluene di-isocyanate(TDI), methyl diphenylene diisocyanate With 1, at least one addition in hexamethylene-diisocyanate.

6. crystallized tin graphed sheet fine arts ink according to claim 1 and 2, it is characterised in that：The solvent is containing benzene solvent, ester At least one in class solvent, ether solvent and alcohols solvent, it is described containing benzene solvent be toluene, dimethylbenzene and 1-Phenylethanone. in extremely Few one kind；The esters solvent is at least one in ethyl acetate, butyl acetate and ethylene glycol ether acetate, the ethers Solvent is at least in ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether and dimethyl ether Kind；The alcohols solvent is at least one in ethanol, ethylene glycol, methanol, normal propyl alcohol, isopropanol and n-butyl alcohol.

7. crystallized tin graphed sheet fine arts ink according to claim 1 and 2, it is characterised in that：The benzene is first for amino resins At least one in etherification benzene substituted amino resins and the etherification benzene substituted amino resins of fourth；The leveling auxiliary agent is esters of acrylic acid, gathers At least one of ether modified organic silicon class and hydroxyl alkyl modified organic silicon apoplexy due to endogenous wind；The auxiliary rheological agents are polyurethane, polyethers, gas phase At least one in silicon dioxide and organobentonite；It is described to increase sliding auxiliary agent at least one in wax liquor and wax powder.

8. crystallized tin graphed sheet fine arts ink according to claim 1 and 2, it is characterised in that：Described filler is aoxidized for nanometer three Two alumina particles, nanmeter antimong trioxide granule, nano-calcium carbonate particles, nano oxidized magnesium granules, nanometer silicon dioxide particle and At least one in titanium dioxide nanoparticle；The dispersant is waterglass, sodium tripolyphosphate, sodium pyrophosphate, Oleic acid and gathers At least one in ethylene glycol.

9. crystallized tin graphed sheet fine arts ink according to claim 1 and 2, it is characterised in that：The enclosed type acid catalyst is At least one in p-methyl benzenesulfonic acid and DBSA；The adhesion promoter is amino silicone, alkyl silica At least one in alkane and propyl trimethoxy siloxanes.

10. crystallized tin graphed sheet fine arts ink according to claim 1 and 2, it is characterised in that its preparation method includes following step Suddenly：

The first step, by short oil-ity alcohol acid resin, benzene for amino resins, solvent and dispersant add dispersion cylinder in, while stirring plus Enter filler, after disperseing at a high speed, add enclosed type polyisocyanate, boiled wood oil, leveling auxiliary agent, auxiliary rheological agents, the sliding auxiliary agent of increasing, envelope Closed form acid catalyst and adhesion promoter continue dispersion, until being uniformly dispersed；

Second step, is pressed 2-10 time with three-roller so as to which fineness reaches less than 10 μm and obtains final product crystallized tin graphed sheet fine arts ink.