CN1807524A - Thermosetting ink - Google Patents

Abstract

The invention provides a thermosetting ink comprising the following constituent (by weight portions): chloroethylene-vinyl acetate copolymerized paste resin 10-100 parts with 9-25% of vinyl acetate content, plasticizer 20-600 parts, heat stabilizing agent 0.2-100 parts, thickening flowing deformation agent 0.2-100 parts.

Description

A kind of heat-set ink

Technical field

The present invention relates to printing ink, particularly relate to a kind of heat-set ink.

Background technology

Heat-set ink is the stamp slurry on a kind of textiles, the leather, is pulpous state or paste under the normal temperature, has stronger yield value and thixotropy.Heat-set ink can reach traditional rubber cement, water slurry institute a counsel of perfection effect by lithographic plate silk screen printing and cold method of tearing hot transfer printing on textiles, leather.

Heat-set ink has the function of not stopping up half tone: also can not solidify last one year at half tone, non-scale.Water based emulsion slurry, water-based rubber glue and oil-based ink often stop up mesh on version, whole half tone will cancel during obstruction.The half tone that clogs is clashed at every turn, promptly lose time and waste printing ink, quality also is affected.

Heat-set ink has exquisite photo effect: heat-set ink can easily be printed very exquisite photo effect.Can accomplish four-colour chromatography, printing hiding rare height, the site that on dark lining, can print 0.2 millimeter lines or 60 lines.

Heat-set ink has three-dimensional stereo effect: three-dimensional stereo effect heat-set ink printing, effect are scraped, are printed once and finish, solid content 100% just as sculpture.

The heat-set ink feel is fabulous: heat-set ink has the feel of rubber, and elastic extension reaches more than 300%.The high elongation rebound resilience is fabulous, does not rupture, and washing fastness is fine, peels off the fastness height, and general rubber cement is incomparable.Heat-set ink crystal is transparent, glossiness is high.

The heat-set ink environment-protecting asepsis conforms to processing safety because of not containing volatile solvents such as formaldehyde, toluene.

Heat-set ink is near the price of rubber cement.Need not wash version, lid version, can save a lot of times and need not waste printing ink again.Rubber cement will have/0.32 square metre of 50-100 gram when washing each time edition slurry rinses out in vain, and is not included in an edition last peeling self cure slurry.From this point, heat-set ink is far superior to rubber cement, and the saving rate is more than 3 times of rubber cement.

Need 180-190 ℃ of process, 90-180 left and right sides second time to toast behind the common thermosetting ink printing, hinge or title solidify, plastify fully.

Adopt this homopolymer of pvc resin paste grade, be lower than under 176.7 ℃ the temperature, no matter the molecular weight size all can not reach plasticizing fully.Because plasticizer loading height in the heat-set ink prescription causes gelation, plastifying temperature all to improve in various degree.Therefore need 180-190 ℃ of process, 90-180 left and right sides second time to toast after the heat-set ink printing, could plastify fully.

Adverse consequencess such as a lot of textiless springy, composite PVC, PU leather can shrink in baking more than 130 ℃, distortion, variable color, foaming, feel are hardened.It also is to be out of shape that the heat resisting temperature of swimming suit cloth, woven dacron, chemical fibre, sweater etc. exceeds 155 ℃, and this has just limited the use range of heat-set ink.In order not damage stock, some processors to be being lower than plasticization temperature processing, but incomplete plastifying heat-set ink, and elasticity is not good easily to be broken, stripping strength is poor, washing fastness is poor, the transparency is poor, low in glossiness, surfaces of tacky.

After low-temperature curing on the existing market promptly plastifies heat-set ink printing, also need toast through 160 ℃, 90-180 left and right sides second time, the ability completely solidified promptly plastifies.

So-called low-temperature curing promptly plastifies the prescription of heat-set ink on the existing market: the paste resin (be called for short chlorine vinegar and stick with paste resin) that adopts the vinyl chloride-vinyl acetate copolymerization of vinyl acetate content 3-5%.

Theoretically, adopt vinyl acetate content to produce heat-set ink in the vinyl chloride-vinyl acetate copolymer paste resin of 9-25%, can be 120-140 ℃ of plasticizing fully.Shortcoming be add heat-set ink that softening agent and other additives be mixed with deposit viscosity stability variation (softening agent infiltrates resin particle inside and causes resin swelling to produce irreversible effect or nonvolatil viscosity increased), so product just began to enter gelation after under the environment of 30 ℃ of room temperatures 2-7 days, curing, caking phenomenon appear easily at normal temperatures.The human consumer buys heat-set ink after some months is placed by regular meeting even more than 1 year.Resolving and depositing viscosity stability is the key factor that solves the low-temperature plasticizing heat-set ink.The low temperature heat-set ink really can be produced in enormous quantities put on market, be used widely.

Summary of the invention

In order to solve the existing problem and shortage of above-mentioned existing heat-set ink, the invention provides a kind of novel thermosetting printing ink.

Technical scheme of the present invention is as follows:

The invention provides a kind of heat-set ink, the component that comprises and the weight part of each component are as follows:

Vinyl acetate content is the vinyl chloride-vinyl acetate copolymer paste resin 10-100 of 9-25% part

Softening agent 20-600 part

Thermo-stabilizer 0.1-100 part

Thickener rheology agent 0.1-100 part.

As optimization, the component that above-mentioned heat-set ink comprises and the weight part of each component are as follows:

Vinyl acetate content is the vinyl chloride-vinyl acetate copolymer paste resin 10-100 of 9-25% part

Softening agent 20-180 part

Thermo-stabilizer 0.1-40 part

Thickener rheology agent 0.1-40 part.

As optimization, the vinyl acetate content of above-mentioned vinyl chloride-vinyl acetate copolymer paste resin is 11-17%.

As optimization, the component of above-mentioned heat-set ink comprises that also vinyl acetate content is 20-200 part, vinyl acetate content a kind of or its combination in the vinyl chloride-vinyl acetate copolymer paste resin 10-100 of 3-5% part and pvc resin paste grade 10-80 part at the vinyl chloride-vinyl acetate copolymerization blending resin of 10-45%.

As optimization, the content of the vinyl acetate of described vinyl chloride-vinyl acetate copolymerization blending resin is 11-15%.

The used softening agent of above-mentioned heat-set ink is little in other words conj.or perhaps little to the resin dissolves power at normal temperatures softening agent of solvation, and thermo-stabilizer is one or more the combination in organic tin thermo-stabilizer and the liquid calcium/zinc composite stabilizer.

As further optimizing, above-mentioned softening agent is diisononyl phthalate (being called for short DINP), trioctyl trimellitate (being called for short TOTM), 4,5-epoxy tetrahydrophthalic acid two (the 2-ethyl is own) ester EPS, dioctyl sebacate (being called for short DOS), Di Iso Decyl Phthalate (being called for short DIDP), 2,2,4-trimethylammonium-1,3-pentanediol diisobutyrate (title TXIB softening agent), phenylformic acid two-thylhexoic acid trihydroxymethylpropanyl ester class, 1, the combination of one or more in 2-dicarboxyl diisononyl esters class, terephthalic acid two (2-ethylhexyl) class.

As optimization, a kind of or its combination of the inorganic modified derivatives class thickener rheology agent of optional aerosil of above-mentioned thickener rheology agent or Viscotrol C or association type Polyurethane thickener rheology agent or organobentonite thickener rheology agent.

Above-mentioned heat-set ink can also add photostabilizer, oxidation inhibitor, viscosity-depression agent, tinting material, mute photo etching, frosting agent, whipping agent, fine copper powder and one or more the combination in aluminium powder or the fines Wax.

As optimization, above-mentioned photostabilizer, oxidation inhibitor, viscosity-depression agent, tinting material, mute photo etching, frosting agent, whipping agent, fine copper powder and one or more the weight part of combination in aluminium powder or the fines Wax are 0.1-180 part.

The technique effect that the present invention realizes is as follows:

Heat-set ink provided by the present invention is that low-temperature curing is the plasticizing type heat-set ink, when keeping all heat-set ink advantages, make heat-set ink just can completely solidified promptly plastify (fusionization), textiles, the leather of undertaking the printing of be need not through 160-190 ℃ of high bake at 120-140 ℃.If with our low temperature heat-set ink printing, only need 120-125 ℃ of process, 90-180 left and right sides second time just can completely solidified promptly to plastify on some easy textiless that shrink, composite PVC, the PU leather.The adverse consequences of having avoided stock because high bake post shrinkage, distortion, variable color, foaming, feel are hardened etc.; Both can save cost, can raise the efficiency again; And under 30 ℃ of conditions, ink product provided by the present invention stability is strong, can long storage time more than 6 months; Under the high situation of plasticizer loading, have pseudo-plasticity, thixotropic fluid again, make printing easily.

By just can produce the heat-set ink of various effects to the adjustment of the various components in proportions in the printing ink and the additive that increases other, as foaming effect heat-set ink, right angle effect heat-set ink, round corners effect heat-set ink, frosted finish effect heat-set ink, quartzy transparent effect heat-set ink, ultrahard effect heat-set ink etc.

Thickener rheology agent role in the low temperature heat-set ink is considerable, and at the thickener rheology agent that does not have to add, the low temperature heat-set ink is then as the liquid water of flow, or presents another kind of dilatant fluid and promptly increase and cut retrogradation phenomenon under the power.The too low or dilatant fluid of viscosity all is not suitable for use in textile printing and uses, and at this moment, adds thickener rheology agent as required.

The adding of thickener rheology agent should make heat-set ink have thixotropy, pseudo-plasticity and the rheological characteristics of yield value is arranged, and along with the increase of add-on, viscosity increases, and thixotropy and yield value also increase.As have high low-shear viscosity and a low shear viscosity, when printing, under shearing force printing ink easily by under the mesh to textiles, " dropping down stream " or " sagging " just do not take place in the back above the leather, do not permeate the textiles behind.

As add the heat-set ink that different types of thickener rheology agent can obtain the different printing effect.As use aerosil class rheological agent and organobentonite class, and the melt viscosity in the time of can increasing the fusion of low temperature heat-set ink, even under sufficiently high plasticization temperature, low temperature heat-set ink melt does not flow.Printing ink profile after the plasticizing does not change, and can make right angle effect low temperature heat-set ink like this.

The WACKER N20 aerosil of Germany or to be called the consumption of the white carbon black of vapor phase process in the low temperature heat-set ink be 1-7%.And use association type Polyurethane thickener rheology agent or the inorganic modified derivatives class thickener rheology agent of Viscotrol C, as Thixatrol ST thickener rheology agent, low melt viscosity then appears in heat-set ink so, under plasticization temperature, melt has flowability, change has taken place in the printing ink profile after the plasticizing, so just can make low temperature round corners effect heat-set ink.

In order to make the heat-set ink surface anti sticking, increase slippery, can use the fines Wax.In order to reduce glossy black surface luster after the printing, can use the polyethylene micropowder wax of ultra-high molecular weight so to obtain that gentle velvet weavy grain mill yarn effect is arranged.Make the ink pellet surface after the printing have the matt effect extinction effect as needs, add fine flatting silica of silicon-dioxide or modified polypropylene waxes in the heat-set ink prescription so in the past.

Make heat-set ink reach foaming effect as needs, as make plasticizing back ink pellet surface form gas-solid bonded vesicular structure, can add the low-temp foaming agent to the inside so, be called for short the TSH obturator-type such as p-toluene sulfonyl hydrazide.Use the whipping agent of perforate effect, plasticizing back ink pellet surface is more coarse so, has gentle velvet weavy grain effect.

After heat-set ink is painted, can make the heat-set ink that enriches color,, and select tinting material according to the requirement of printing effect.Tinting material is generally selected pigment dyestuff and mineral dye.

The main look of heat-set inks such as redness, yellow, blueness, green, purple, orange, fluorescence color, generality is all selected pigment dyestuff, because it is bright in luster, tinting strength is big, the processibility of printing ink is not had much influences, environmentally-friendly sanitary.

White heat-set ink mineral dye is such as titanium dioxide (titanium dioxide), because the opacifying power of titanium dioxide is good, tinting strength is big, characteristics such as whiteness height.Along with the growth of titanium dioxide consumption, the opacifying power of heat-set ink strengthens, and the benefit of doing like this is printing or produce white pattern on dark textiles and leather easily, or makes things convenient for the heat-set ink of other weak opacifying power colors to print additional above it.

The black heat-set ink uses the mineral dye carbon black, and the carbon black opacifying power is good, tinting strength is big, the blackness height.After the heat-set ink plasticizing of the adding of unassured toner then is transparent, the heat-set ink outward appearance is oyster white or edematus when not plastifying, heat-set ink after painted is just the same with the color of tinting material, Yin Shua color as required, heat-set ink after painted is allocated on demand mutually, printed after being assigned to the color that needs.

Transparent if desired printing effect so directly prints with uncoloured heat-set ink.If white, black, redness, yellow, blueness, green, purple, various pigment such as orange are added a certain amount of connection material＜plasticizer-containing, stablizer, resin〉after, by obtaining the color of the quite high white of colorant content, black, redness, yellow, blueness, green, purple, color such as orange after grinding, disperseing, pigment content in the general color is 10-70%, can not contain resin in some connection material as required.Yin Shua color as required adds the color that needs with uncoloured heat-set ink and allocates mutually, prints after being assigned to the color that needs.

Easily remove hcl reaction during the heat-set ink heating plasticizing.The hydrogenchloride that removes has the catalysis booster action again to the degraded chain reaction, generates unsaturated conjugated polyenoid, causes goods variable color, hardening, burns.The ideal thermo-stabilizer should have following characteristics:

(1) thermally-stabilised usefulness excellence has synergistic effect;

(2) refer to that with tree consistency is good, volatility is little, does not distil, and does not move, and no blooming is not perspired, and resistant to extraction is good;

(3) proper lubrication is arranged, easily processing, lower melt viscosity;

(4) have no adverse reaction with other auxiliary agents, not by sulphur, copper staining;

(5) nontoxic, odorless, do not pollute;

(6) easy to process, cheap.

Heat-set ink selects preferably that smell is less for use, asepsis environment-protecting, the transparency better, the resin in the heat-set ink is not had obvious solvation, organic tin and liquid calcium/zinc stabilizer are more satisfactory selections.

The Lankrostat C19 of Britain

Type: Ca/Zn one package stabilizer

Outward appearance: liquid

Color and luster:＜3 (Gardners)

Proportion: 0.98

Be nontoxic liquid calcium zinc complex stabilizer in heat-set ink with 0.5-3% or cooperate shared with epoxy soybean oil.Resin in the low temperature heat-set ink there is not obvious solvation yet, thermally-stabilised usefulness excellence.

The BAEROSTAB OM 710N of Germany

Type: tin octylate thiolate stablizer

Form: clarified liq

Gardner's colourimetric number: maximum 2

Proportion: 1.08 ± 0.01

Specific refractory power: 1.500 ± 0.002

Tin content (%): 15.1 ± 0.2

Be octyl tin stabilizer, have inviscid and can not produce and separate out, low volatility, advantage such as smell is few use 0.5-2% in heat-set ink, purchase in Dongguan City imperial plastic material in morning Department of Trade.Purchase in Nanjing ancient cooking vessel chemistry in morning development in science and technology company limited.

Thiol-butyl tin

Proportion: 1.11-1.13g/ml

Form: clarification or little yellow liquor body

Tin content (%): 12-12.5

Resin in the heat-set ink there is not obvious solvation yet, thermally-stabilised usefulness excellence.

Dibutyl tin dilaurate

Product type: SC-101

Form: clarification or little butter shape liquid

Tin content (Sn) .%:18.0-19.2

Resin in the heat-set ink there is not obvious solvation yet, thermally-stabilised usefulness excellence.

The macromolecular material of heat-set ink is that the ultraviolet ray of 290 ~ 400mm is comparatively responsive to wavelength.The energy of UV-light is enough to destroy the chemical bond of macromolecular material, causes optical excitation and photo damage, causes the photo-oxidation process of light, oxygen associating, and heat-set ink is worn out because of photodegradation or by light-initiated photo-oxidative degradation.

UV-9

Chemical name 2-hydroxyl-4-methoxy benzophenone

Relative molecular mass 228.25.Fusing point 62-66 ℃

The consumption that has good stability in heat-set ink to photo-thermal has 0.1-1%

Manufacturer: the excessive additives for plastics of Shanghaiization uses company, auxiliary reagent factory, Shenyang, Liaoyang Organic Chemical Plant, auxiliary reagent factory, Wuhan, Hubei.

UV-326 chemical name (2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorination benzotriazole relative molecular mass 315.80.140 ~ 141 ℃ of fusing points.

As UV light absorber, the ultraviolet ray of absorbing wavelength 270 ~ 380mm consumingly.Be one of good stablizer kind, with oxidation inhibitor and with synergistic effect is arranged.

Manufacturer: Lik-Sang chemical plant, Tianjin.

In heat-set ink production, storage, processing, the use, all can oxygenizement take place because of self or extraneous factor, cause heat-set ink performance decrease or loss, aging.Oxidation inhibitor is a kind of chemical assistant that can suppress and delay heat-set ink oxidation and degraded.Can be divided into again by structure and to be subjected to phenols, amine, phosphorous acid class, thioesters class and other classes.

Antioxidant 1076

Chemical name: B-(4-hydroxyl-3,5-di-tert-butyl-phenyl) the positive octadecyl ester of propionic acid, relative molecular weight 530.87.

Fusing point 49-52 ℃, with UV light absorber and be used in synergistic effect is arranged in the heat-set ink.

Manufacturer: Zhejiang Jin Haiyabao chemical industry company limited, the precious occasion chemical industry in Tianjin company limited, Liaoyang Organic Chemical Plant.

Nontoxic phosphorous acid ester

Outward appearance: water white transparency thick liquid

Phosphorus content %5.20-5.90

Viscosity (20 ℃) mpa.s≤300

Refractive index nD 1.4980-1.5000

Density (20 ℃ of ρ) g/cm3 0.96-0.98

With organotin stabilizer, Ca-Zn composite heat stabilizer good synergistic is arranged

Manufacturer: the strong additives for plastics of Shanghai intelligence company limited.

Add weighting agent, such as the lime carbonate class, as calcium carbonate superfine powder, nano-calcium carbonate.The benefit of doing like this is outside reducing cost, and falls end plasticization temperature in addition, can cooperate epoxy soybean oil to use together to improve the effect of heat-set ink thermostability, the general 5-30% of lime carbonate usage quantity in use.As the red lucky board that calcium carbonate superfine powder is made for Zhejiang water chestnutization Group Co.,Ltd, nano-calcium carbonate is Anyuan board that Pingxiang City Anyuan science and technology chemical industry Industrial Co., Ltd. makes.

Embodiment

Below heat-set ink provided by the present invention is described in detail, this part content only describes technical scheme of the present invention, and should not be considered as the qualification to technical scheme.

Embodiment 1:

Adopt following prescription, the weight part of each component is as follows in the prescription:

Vinyl acetate content is 100 parts of 15% vinyl chloride-vinyl acetate copolymer paste resin

120 parts in softening agent

7.6 parts of thermo-stabilizers

9.2 parts of thickener rheology agents

Vinyl chloride-vinyl acetate copolymer paste resin is the vinyl chloride-vinyl acetate copolymer paste resin PCL-15 of the vinyl acetate content 15% of Chinese Shenyang Chemical Co., Ltd. production.Character is as follows:

The polymerization degree 800 ± 100

Fugitive constituent, % ,≤1.0

Tap density, g/cm3 0.35～0.55

The content 15 ± 2% of vinyl acetate

Outward appearance is white fines.

Softening agent is the terephthalic acid two (2-ethylhexyl) of U.S. Yi Shiman EASTMAN company, is called for short 168 softening agent.80 parts of consumptions.Make heat-set ink soft more flexible, also play the effect of regulating viscosity, little under the normal temperature to resin dissolves power.

Softening agent is 2,2 of a U.S. Yi Shiman EASTMAN company, 4-trimethylammonium-1, and the 3-pentanediol diisobutyrate is called for short the TXIB softening agent.40 parts of consumptions.Can improve pollution resistance, the dry and comfortable property on the surface after printing ink plastifies.

Thermo-stabilizer is the dibutyl tin dilaurate of Nanjing ancient cooking vessel chemistry in morning development in science and technology company limited, product type: SC-101; Clarification or little butter shape liquid; Tin content (Sn) 18.0-19.2%.Resin in the heat-set ink there is not obvious solvation, thermally-stabilised usefulness excellence.Consumption is 2.6 parts.

Thermo-stabilizer is Britain Ai Ke Lankrostat C19,

Type: Ca/Zn one package stabilizer

Outward appearance: liquid

Color and luster:＜3 (Gardners)

Proportion: 0.98

Resin in the heat-set ink there is not obvious solvation, thermally-stabilised usefulness excellence.Consumption is 5 parts.

Thickener rheology agent is the N20 aerosil of German WACKER company, or is called the white carbon black of vapor phase process.Consumption is 9.2 parts.Use this thickener rheology agent can allow mobile printing ink not flow at normal temperatures, and have thixotropy, pseudo-plasticity.Melt viscosity when aerosil can increase the fusion of low temperature heat-set ink, even under sufficiently high plasticization temperature, low temperature heat-set ink melt does not flow.Can make right angle effect low temperature heat-set ink like this.

Process for preparation is as follows:

After earlier the ratio weighing of whole raw material consumptions being come out, the softening agent of all resins component and 50% is mediated with 4-10 rev/min speed at duplicate rows star stirrer, about 10 minutes kneading time.Keep the mixing of materials temperature below 30 ℃.

Add 10% softening agent again and stir with 20 rev/mins speed, churning time is about 3 minutes.

All the T40 aerosil thickener rheology agent of the German WACKER of adding company is mediated with 10 rev/mins speed again, about 10 minutes kneading time.

The remaining softening agent of whole again addings stirs with 40 rev/mins speed, and churning time is about 3 minutes.

The speed that all adds 40 rev/mins of all thermo-stabilizers again stirs, and churning time obtains finished product printing ink about 10 minutes.

Printing ink after making is to have more intense yield value, thixotropic pulpous state or paste, has been fit to printing.Printing ink by lithographic plate silk screen printing let us is stayed on the textiles.

The lithographic plate screen printing plate: grenadine 80 orders, screen cloth tension force 20N/cm2,0.2 millimeter of the thickness of photoresists, the printing net is apart from 5cm.

Scraper: the right angle rubber squeegee of hardness 70 degree.

Stock: common stretch lycra cloth.

The first step: after going up the printing ink that has mixed up by the lithographic plate screen printing plate that makes and scraping once with rubber squeegee is manual, printed figure was blown for 10 seconds with heat baking rifle 10cm distance, it is dried to reach the surface.

Second step: scrape by hand more for the second time, blew 3 seconds with heat baking rifle 10cm distance, reach the surface dried after.

Repeat to obtain after the program 6 times in above second step print thickness again and be 0.6 millimeter three dimensional ink graph layer.Allow it toast with 120-140 ℃ of 90-300 kind second then through the electric baking tunnel.

One, more satisfactory mode is 120 ℃ of bakings 5 minutes,

Two, more satisfactory mode is 130 ℃ of bakings 3 minutes,

Three, more satisfactory mode is 2 fens halfs of 140 ℃ of baking bakings.

More than one, two, any way can obtain plasticizing in three kind of mode.The cooling back obtains right angle effect printing finished product.

Annotate: fusion time also depends on the thickness of base cloth, because blocked up cloth makes temperature be difficult to be penetrated into ink lay.

Embodiment 2:

Adopt following prescription, the weight part of each component is as follows in the prescription:

Vinyl acetate content is 20 parts of 15% vinyl chloride-vinyl acetate copolymer paste resin

Vinyl acetate content is 200 parts of 14% vinyl chloride-vinyl acetate copolymerization blending resins

66 parts in softening agent

2.9 parts of thermo-stabilizers

5.8 parts of thickener rheology agents

0.1 part of photostabilizer

0.1 part in oxidation inhibitor

15 parts of viscosity-depression agents.

Vinyl chloride-vinyl acetate copolymer paste resin is the vinyl chloride-vinyl acetate copolymer paste resin PCL-15 of the vinyl acetate content about 15% of Chinese Shenyang Chemical Co., Ltd. production.Character is as follows:

The polymerization degree 800 ± 100

Fugitive constituent, % ,≤1.0

Tap density, g/cm3 0.35～0.55

The content 15 ± 2% of vinyl acetate

Outward appearance is white fines.

The vinyl chloride-vinyl acetate copolymerization blending resin of vinyl acetate content about 14% is German Vinnolit C1450.

The K value is 50

Vinyl acetate content is 14 ± 2%

The particle diameter of vinyl chloride-vinyl acetate copolymerization blending resin is greatly about the 20-80 micron, because vinyl chloride-vinyl acetate copolymerization blending resin suction softening agent rate is low, grain pattern is tight, good fluidity, have certain visbreaking effect in low temperature heat-set ink prescription, viscosity stability is better than vinyl chloride-vinyl acetate copolymer paste resin.Shortcoming is that its particle is too thick.Therefore also can carry out interworking and reach some special effects with the paste resin.

Softening agent is the trioctyl trimellitate (being called for short TOTM) of Tongxiang city chemical industry company limited.55 parts of consumptions.Comprehensive good softening agent.Its volatility is little, little to dissolving resin power under the normal temperature, anti-extractable is good.

Softening agent is the dioctyl sebacate (being called for short DOS) of Tongxiang city chemical industry company limited.12 parts of consumptions.Good winter hardiness is arranged, excellent viscosity stability.

Thermo-stabilizer is the BAEROSTAB OM 710N. of Germany

Type: tin octylate thiolate stablizer

Form: clarified liq

Gardner's colourimetric number: maximum 2

Proportion: 1.08 ± 0.01

Specific refractory power: 1.500 ± 0.002

Tin content (%): 15.1 ± 0.2

Be octyl tin stabilizer, have inviscid and difficult generation and separate out, low volatility, advantage such as smell is few is used 0.5-2% in heat-set ink.

Thickener rheology agent is a Subsidiary Company of public sharp foreign firm of International Trading Company Ltd of Shanghai Micron Technology＜US business〉the inorganic modified derivatives class Thixatrol of the Viscotrol C ST thickener rheology agent sold.Use this thickener rheology agent can allow mobile printing ink not flow at normal temperatures, and have thixotropy, pseudo-plasticity.Because its fusing point relatively hangs down at 80-100 ℃.Step on, fuse in its structure spring of back of being heated, guaranteed the low viscosity of round corners effect low temperature heat-set ink solution when fusion, the printing ink melt has flowability again under the plastifying fusion temperature, so just can make low temperature round corners effect heat-set ink.2.9 parts of consumptions.

Thickener rheology agent is 7250 association type Polyurethane thickener rheology agents of AM General GE company or claims modified urea solution, for liquid.

Use this thickener rheology agent can allow mobile printing ink not flow at normal temperatures, and have thixotropy, pseudo-plasticity.In thickened systems, form three-dimensional structure, in the jump low viscosity of solution when having stepped on, having guaranteed that round corners effect low temperature heat-set ink is in fusion of its structure of back of being heated.Melt has flowability again under the plastifying fusion temperature, so just can make low temperature round corners effect heat-set ink.2.9 parts of consumptions.

Photostabilizer is the UV-9 that Wenzhou grand chemical building material company limited sells.

Chemical name: 2-hydroxyl-4-methoxy benzophenone

Relative molecular mass 228.25.Fusing point 62-66 ℃

Oxidation inhibitor is the nontoxic phosphorous acid ester DB-1500 of the strong additives for plastics of Shanghai intelligence company limited, has with organotin stabilizer, Ca-Zn composite heat stabilizer good synergistic is arranged.

Viscosity-depression agent is the D80 of U.S. Mobil Oil Corp., and auspicious precious building material company limited buys from Shanghai.

Viscosity-depression agent plays and can effectively reduce dispensing viscosity and keep the stable viscosity of long period in the heat-set ink system, can increase the consumption of filler (as lime carbonate), the heat-set ink surface anti-stain characteristic after the final order plasticizing better, more smooth tack-free.15 parts of consumptions.

Owing to only use a spot of softening agent to make that the feel after the printing ink plasticizing is hard especially, but also have round corners effect (transparency is good).

Process for preparation is as follows:

After earlier the ratio weighing of whole raw material consumptions being come out,, mediate with 4-10 rev/min speed at duplicate rows star stirrer, about 10 minutes kneading time all resins component and whole DOS softening agent, 30 parts of TOTM softening agent, 8 portions of D80 viscosity-depression agents.Keep the mixing of materials temperature below 30 ℃.

All Thixatrol ST thickener rheology agents of 2.9 parts are placed in all 25 softening agent and all 7 portions of D80 viscosity-depression agents, disperse in advance, grind and make pre-gelled, help its best efficient of thickener rheology agent performance like this with three rod machines.

Add the pre-gelled that all have made again, churning time is about 10 minutes.

Add all 7250 association type Polyurethane thickener rheology agents of 2.9 parts again.About churning time 10 minutes.

All add all again Photostabilizer,The speed that oxidation inhibitor, thermally-stabilised usefulness are 40 rev/mins stirs, and vacuumizes, and 20 minutes time length obtained finished product printing ink always.

Printing ink after making is to have more intense yield value, thixotropic pulpous state or paste, has been fit to printing, because the plasticizers content of prescription the inside is few, so have hard especially feel after the printing ink plasticizing.

Adopt the leather engraving method of biting:

Can on leather, print off the figure that stereoscopic sensation is very strong, ink film thickness is high with the low temperature heat-set ink with special artistic effect.Owing to almost do not have decrement after the plasticizing of low temperature heat-set ink, be fit to very much the seal stereoeffect.The sheet material smooth with the plastic cement of 0.5-2 mm thick goes out required figure by computer photograph, carves out figure (must carve sheet material) with computer mechanical engraving equipment then.The plastic sheet that to carve is pasted on the lithography screen frame then.

Cut after making is positioned over and waits on the leather of undertaking the printing of, and goes up and has made printing ink, with manual the scraping on the leather of right angle rubber squeegee of hardness 70 degree.Take cut then away, solid figure has just been stayed on the leather.

Allow it toast with 120-140 ℃ of 90-300 kind second then through the electric baking tunnel.

One, more satisfactory mode is 120 ℃ of bakings 5 minutes,

Two, more satisfactory mode is 130 ℃ of bakings 3 minutes,

Three, more satisfactory mode is 2 fens halfs of 140 ℃ of baking bakings.

More than one, two, any way can obtain plasticizing in three kind of mode.The cooling back obtains ultrahard round corners effect printing finished product.

Annotate: fusion time also depends on the thickness of base leather, because blocked up leather makes temperature be difficult to be penetrated into ink lay.

Embodiment 3:

Adopt following prescription, the weight part of each component is as follows in the prescription:

Vinyl acetate content is 100 parts of 15% vinyl chloride-vinyl acetate copolymer paste resin

Vinyl acetate content is 200 parts of 12% vinyl chloride-vinyl acetate copolymerization blending resins

600 parts in softening agent

100 parts of thermo-stabilizers

100 parts of thickener rheology agents

180 parts of tinting materials

Vinyl chloride-vinyl acetate copolymer paste resin is the vinyl chloride-vinyl acetate copolymer paste resin PCL-9 of the vinyl acetate content about 15% of Chinese Shenyang Chemical Co., Ltd. production.Character is as follows:

The polymerization degree 800 ± 100

Fugitive constituent, % ,≤1.0

Tap density, g/cm3 0.35～0.55

The content 9 ± 2% of vinyl acetate

Outward appearance is white fines.

Vinyl chloride-vinyl acetate copolymerization blending resin C1262, German Vinnolit, the K value is 62, vinyl acetate content is 12 ± 2%.

The particle diameter of vinyl chloride-vinyl acetate copolymerization blending resin is greatly about the 20-80 micron, because vinyl chloride-vinyl acetate copolymerization blending resin suction softening agent rate is low, grain pattern is tight, good fluidity, have certain visbreaking effect in low temperature heat-set ink prescription, viscosity stability is better than vinyl chloride-vinyl acetate copolymer paste resin.Shortcoming is that its particle is too thick.Therefore also can carry out interworking and reach some special effects with the paste resin.

C1450 vinyl chloride-vinyl acetate copolymerization blending resin in C1262 vinyl chloride-vinyl acetate copolymerization blending resin and the prescription 2 is compared, because C1262 is a little less than C1450 on vinyl acetate content, so on plasticization temperature, can omit height a bit, but the K value of C1262 is than C1450 height, the elasticity of the low temperature heat-set ink of preparation will be got well, and tensile elongation is better.

Softening agent is the Lgflex BET softening agent that the sharp LG Corp of South Korea that gets International Trading Company Ltd's sale of ancient India in Shanghai is produced.

Composition belongs to: formic acid two-thylhexoic acid trihydroxymethylpropanyl ester class.400 parts of consumptions.

Softening agent is 2,2 of a U.S. Yi Shiman EASTMAN company, 4-trimethylammonium-1, and the 3-pentanediol diisobutyrate is called for short the TXIB softening agent.Can improve pollution resistance, the dry and comfortable property on the surface after printing ink plastifies.200 parts of consumptions

Thickener rheology agent is the N20 aerosil of German WACKER company, or is called the white carbon black of vapor phase process.Melt viscosity when aerosil can increase the fusion of low temperature heat-set ink, even under sufficiently high plasticization temperature, low temperature heat-set ink melt does not flow.Can make right angle effect low temperature heat-set ink like this.

Thermo-stabilizer is purchased in Nanjing ancient cooking vessel chemistry in morning development in science and technology company limited.

Thiol-butyl tin

Proportion: 1.11-1.13g/ml

Form: clarification or little yellow liquor body

Tin content (%): 12-12.5

Resin in the heat-set ink there is not obvious solvation yet, thermally-stabilised usefulness excellence.

Tinting material: titanium dioxide (titanium dioxide) (the prosperous pigment in Wenzhou firm sells).

Process for preparation is as follows:

After earlier the ratio weighing of whole raw material consumptions being come out, the softening agent of all resins component and 50% is mediated with 4-10 rev/min speed at duplicate rows star stirrer, about 10 minutes kneading time.Keep the mixing of materials temperature below 30 ℃.

Add 10% softening agent again and stir with 20 rev/mins speed, churning time is about 3 minutes.

All the T40 aerosil thickener rheology agent of the German WACKER of adding company is mediated with 10 rev/mins speed again, about 10 minutes kneading time.

The remaining softening agent of whole again addings stirs with 40 rev/mins speed, and churning time is about 3 minutes.

The speed that all adds 40 rev/mins of all thermo-stabilizers again stirs, and churning time obtains finished product printing ink about 10 minutes.

All add 40 rev/mins all speed again and stir, churning time obtains finished product printing ink about 10 minutes.

Printing ink after making is to have more intense yield value, thixotropic pulpous state or paste, has been fit to printing.

Owing to used the aerosil thickener rheology agent, be the right angle effect that profile can not change after the printing ink plasticizing.

Owing to used white tinting material, can be the chromatic effect of white after the printing ink plasticizing.

The lithographic plate screen printing plate: grenadine 80 orders, screen cloth tension force 20N/cm2,0.2 millimeter of the thickness of photoresists, the printing net is apart from 5cm.

Scraper: the right angle rubber squeegee of hardness 70 degree.

Stock: common stretch lycra cloth.

The first step: after going up the printing ink that has mixed up by the lithographic plate screen printing plate that makes and scraping once with rubber squeegee is manual, printed figure was blown for 10 seconds with heat baking rifle 10cm distance, it is dried to reach the surface.

Second step: scrape by hand more for the second time, blew 3 seconds with heat baking rifle 10cm distance, reach the surface dried after.

Repeat to obtain after the program 6 times in above second step print thickness again and be 0.6 millimeter three dimensional ink graph layer.Allow it toast with 120-140 ℃ of 90-300 kind second then through the electric baking tunnel.

One, more satisfactory mode is 120 ℃ of bakings 5 minutes,

Two, more satisfactory mode is 130 ℃ of bakings 3 minutes,

Three, more satisfactory mode is 2 fens halfs of 140 ℃ of baking bakings.

More than one, two, any way can obtain plasticizing in three kind of mode.The cooling back obtains right angle effect printing finished product.

Annotate: fusion time also depends on the thickness of base cloth, because blocked up cloth makes temperature be difficult to be penetrated into ink lay.

Process is as follows:

After earlier the ratio weighing of whole raw material consumptions being come out, the softening agent of all resins component and 150 parts is mediated with 4-10 rev/min speed at duplicate rows star stirrer, about 10 minutes kneading time.Keep the mixing of materials temperature below 30 ℃.

The softening agent that adds 50 parts again stirs with 20 rev/mins speed, and churning time is about 3 minutes.

All the N20 aerosil thickener rheology agent of the German WACKER of adding company is mediated with 10 rev/mins speed again, about 10 minutes kneading time.

The remaining softening agent of whole again addings stirs with 40 rev/mins speed, and churning time is about 3 minutes.

The speed that all adds 40 rev/mins of all tinting materials again stirs, and churning time obtains finished product printing ink about 10 minutes.

Printing ink after making is to have more intense yield value, thixotropic pulpous state or paste, has been fit to printing.

The lithographic plate screen printing plate: grenadine 80 orders, screen cloth tension force 20N/cm2,0.2 millimeter of the thickness of photoresists, the printing net is apart from 5cm.

Scraper: the right angle rubber squeegee of hardness 70 degree.

Stock: common stretch lycra cloth.

The first step: after going up the printing ink that has mixed up by the lithographic plate screen printing plate that makes and scraping once with rubber squeegee is manual, printed figure was blown for 10 seconds with heat baking rifle 10cm distance, it is dried to reach the surface.

Second step: scrape by hand more for the second time, blew 3 seconds with heat baking rifle 10cm distance, reach the surface dried after.

Repeat to obtain after the program 6 times in above second step print thickness again and be 0.6 millimeter three dimensional ink graph layer.Allow it toast with 120-140 ℃ of 90-300 kind second then through the electric baking tunnel.

One, more satisfactory mode is 120 ℃ of bakings 5 minutes,

Two, more satisfactory mode is 130 ℃ of bakings 3 minutes,

Three, more satisfactory mode is 2 fens halfs of 140 ℃ of baking bakings.

More than one, two, any way can obtain plasticizing in three kind of mode.The cooling back obtains right angle effect printing finished product.

Annotate: fusion time also depends on the thickness of base cloth, because blocked up cloth makes temperature be difficult to be penetrated into ink lay.

Embodiment 4:

Adopt following prescription, the weight part of each component is as follows in the prescription:

Vinyl acetate content is 10 parts of 15% vinyl chloride-vinyl acetate copolymer paste resin

Vinyl acetate content is 10 parts of 3% vinyl chloride-vinyl acetate copolymer paste resin

20 parts in softening agent

0.1 part of thermo-stabilizer

0.1 part of thickener rheology agent

1.2 parts of tinting materials

0.1 part of photostabilizer

0.1 part in oxidation inhibitor

4 parts of weighting agents

1.2 parts of epoxy soybean oils (ESO)

Vinyl chloride-vinyl acetate copolymer paste resin is the vinyl chloride-vinyl acetate copolymer paste resin PCL-15 of the vinyl acetate content about 15% of Chinese Shenyang Chemical Co., Ltd. production.Character is as follows:

The polymerization degree 800 ± 100

Fugitive constituent, % ,≤1.0

Tap density, g/cm3 0.35～0.55

The content 9 ± 2% of vinyl acetate

Outward appearance is white fines.

Vinyl acetate content is at the vinyl chloride-vinyl acetate copolymerization blending resin PCMA-12 of 3-5%, and Chinese Shenyang Chemical Co., Ltd. produces, and outward appearance is white fines.

Because the content of its vinyl acetate is at 3-5%, if produce the low temperature heat-set ink with this vinyl chloride-vinyl acetate copolymer paste resin fully, its plasticization temperature does not reach the desired 120-140 of low temperature heat-set ink ℃ plasticization temperature generally at 155-175 ℃ under the high situation of plasticizer loading.So the content of vinyl acetate this vinyl chloride-vinyl acetate copolymer paste resin of 3-5% can with vinyl acetate content than higher, as using than higher the mixing as vinyl chloride-vinyl acetate copolymerization blending resin in the vinyl acetate content of 9-25% in the vinyl chloride-vinyl acetate copolymer paste resin of the vinyl acetate content of 9-25% or vinyl acetate content.

Softening agent is the diisononyl phthalate (being called for short DINP) of Shandong, Shandong softening agent limited-liability company.Low price.

Thickener rheology agent is the organobentonite class BP-186 that Hangzhou Ward company sells.

Use this thickener rheology agent can allow mobile printing ink not flow at normal temperatures, and have thixotropy, pseudo-plasticity.Make under sufficiently high plasticization temperature, low temperature heat-set ink melt does not flow.Can make right angle effect low temperature heat-set ink like this.Low price.

Thermo-stabilizer is the dibutyl tin dilaurate of Nanjing ancient cooking vessel chemistry in morning development in science and technology company limited, product type: SC-101; Clarification or little butter shape liquid; Tin content (Sn) 18.0-19.2%.Resin in the heat-set ink there is not obvious solvation, thermally-stabilised usefulness excellence.Resin in the heat-set ink there is not obvious solvation yet, thermally-stabilised usefulness excellence.

The red lucky board calcium carbonate superfine powder that weighting agent is made for Zhejiang water chestnutization Group Co.,Ltd.The benefit of doing like this is outside reducing cost, and falls end plasticization temperature in addition, and the printing ink of convection cell shape has the thickening thixotropic transformation.Can cooperate epoxy soybean oil to use together in use to improve the effect of heat-set ink thermostability.Low price.

Epoxy soybean oil (ESO) and lime carbonate use together to improve the effect of heat-set ink thermostability.

Photostabilizer is the UV-9 that Wenzhou grand chemical building material company limited sells.

Chemical name: 2-hydroxyl-4-methoxy benzophenone

Relative molecular mass 228.25.Fusing point 62-66 ℃

Oxidation inhibitor is the nontoxic phosphorous acid ester DB-1500 of the strong additives for plastics of Shanghai intelligence company limited, has with organotin stabilizer, Ca-Zn composite heat stabilizer good synergistic is arranged.

Process for preparation is as follows:

After earlier the ratio weighing of whole raw material consumptions being come out, the softening agent of all resins component and 10 parts is mediated with 4-10 rev/min speed at duplicate rows star stirrer, about 10 minutes kneading time.Keep the mixing of materials temperature below 30 ℃.

The softening agent that adds 5 parts again stirs with 20 rev/mins speed, and churning time is about 3 minutes.All add the organobentonite thickener rheology agent again and be placed in 5 parts of softening agent, disperse in advance, grind and make pre-gelled, help its best efficient of thickener rheology agent performance like this with three rod machines.

All add all pre-gelleds of making again and stir with 40 rev/mins speed, churning time is about 3 minutes.

All add all thermo-stabilizers again and stir churning time 10 minutes with 40 rev/mins speed.

All add all photostabilizers again and stir churning time 10 minutes with 40 rev/mins speed.

The speed that all adds 40 rev/mins of all oxidation inhibitor agent again stirs, churning time 10 minutes.

All add all weighting agents again and stir with 40 rev/mins speed, churning time obtains finished product printing ink about 10 minutes.

Printing ink after making is to have more intense yield value, thixotropic pulpous state or paste, has been fit to printing.

The lithographic plate screen printing plate: grenadine 80 orders, screen cloth tension force 20N/cm2,0.2 millimeter of the thickness of photoresists, the printing net is apart from 5cm.

Scraper: the right angle rubber squeegee of hardness 70 degree.

Stock: common stretch lycra cloth.

The first step: after going up the printing ink that has mixed up by the lithographic plate screen printing plate that makes and scraping once with rubber squeegee is manual, printed figure was blown for 10 seconds with heat baking rifle 10cm distance, it is dried to reach the surface.

Second step: scrape by hand more for the second time, blew 3 seconds with heat baking rifle 10cm distance, reach the surface dried after.

Repeat to obtain after the program 6 times in above second step print thickness again and be 0.6 millimeter three dimensional ink graph layer.Allow it toast with 120-140 ℃ of 90-300 kind second then through the electric baking tunnel.

One, more satisfactory mode is 120 ℃ of bakings 5 minutes,

Two, more satisfactory mode is 130 ℃ of bakings 3 minutes,

Three, more satisfactory mode is 2 fens halfs of 140 ℃ of baking bakings.

More than one, two, any way can obtain plasticizing in three kind of mode.The cooling back obtains right angle effect printing finished product.

Annotate: fusion time also depends on the thickness of base cloth, because blocked up cloth makes temperature be difficult to be penetrated into ink lay.

Embodiment 5:

Adopt prescription as follows:

Vinyl acetate content is 100 parts of 9% vinyl chloride-vinyl acetate copolymer paste resin

120 parts in softening agent

7.6 parts of thermo-stabilizers

9.2 parts of thickener rheology agents

Vinyl chloride-vinyl acetate copolymer paste resin is the vinyl chloride-vinyl acetate copolymer paste resin PCL-9 of the vinyl acetate content about 9% of Chinese Shenyang Chemical Co., Ltd. production.Character is as follows:

The polymerization degree 800 ± 100

Fugitive constituent, % ,≤1.0

Tap density, g/cm3 0.35～0.55

The content 9 ± 2% of vinyl acetate

Outward appearance is white fines.

Softening agent is German BASF BASF Hexamoll Dinch softening agent, and composition belongs to: 1, and 2-dicarboxyl diisononyl esters class, the plasticising superior performance makes heat-set ink soft more flexible, also plays the effect of regulating viscosity, and is little to resin dissolves power under the normal temperature.

Softening agent is 2,2 of a U.S. Yi Shiman EASTMAN company, 4-trimethylammonium-1, and the 3-pentanediol diisobutyrate is called for short the TXIB softening agent.20 parts of consumptions.Can improve pollution resistance, the dry and comfortable property on the surface after printing ink plastifies.

Thermo-stabilizer is the dibutyl tin dilaurate of Nanjing ancient cooking vessel chemistry in morning development in science and technology company limited, product type: SC-101; Clarification or little butter shape liquid; Tin content (Sn) 18.0-19.2%.Resin in the heat-set ink there is not obvious solvation, thermally-stabilised usefulness excellence.Consumption is 2.6 parts.

Thermo-stabilizer is Britain Ai Ke Lankrostat C19,

Type: Ca/Zn one package stabilizer

Outward appearance: liquid

Color and luster:＜3 (Gardners)

Proportion: 0.98

Resin in the heat-set ink there is not obvious solvation, thermally-stabilised usefulness excellence.Consumption is 5 parts.

Thickener rheology agent is a Subsidiary Company of public sharp foreign firm of International Trading Company Ltd of Shanghai Micron Technology＜US business〉the inorganic modified derivatives class Thixatrol of the Viscotrol C ST thickener rheology agent sold.Use this thickener rheology agent can allow mobile printing ink not flow at normal temperatures, and have thixotropy, pseudo-plasticity.Because its fusing point relatively hangs down at 80-100 ℃.Step on, fuse in its structure spring of back of being heated, guaranteed the low viscosity of round corners effect low temperature heat-set ink solution when fusion, the printing ink melt has flowability again under the plastifying fusion temperature, so just can make low temperature round corners effect heat-set ink.

Process for preparation is as follows:

After earlier the ratio weighing of whole raw material consumptions being come out, the softening agent of all resins component and 50 parts is mediated with 4-10 rev/min speed at duplicate rows star stirrer, about 10 minutes kneading time.Keep the mixing of materials temperature below 30 ℃.

The softening agent that adds 10 parts again stirs with 20 rev/mins speed, and churning time is about 3 minutes.All add Thixatrol ST thickener rheology agent again and be placed in 60 parts of softening agent, disperse in advance, grind and make pre-gelled, help its best efficient of thickener rheology agent performance like this with three rod machines.

All add all pre-gelleds of making again and stir with 40 rev/mins speed, churning time is about 3 minutes.

All add all thermo-stabilizers again and stir with 40 rev/mins speed, churning time obtains finished product printing ink about 10 minutes.

Printing ink after making is to have more intense yield value, thixotropic pulpous state or paste, has been fit to printing.Printing ink by lithographic plate silk screen printing let us is stayed on the textiles.

The lithographic plate screen printing plate: grenadine 80 orders, screen cloth tension force 20N/cm2,0.2 millimeter of the thickness of photoresists, the printing net is apart from 5cm.

Scraper: the right angle rubber squeegee of hardness 70 degree.

Stock: common stretch lycra cloth.

The first step: after going up the printing ink that has mixed up by the lithographic plate screen printing plate that makes and scraping once with rubber squeegee is manual, printed figure was blown for 10 seconds with heat baking rifle 10cm distance, it is dried to reach the surface.

Second step: scrape by hand more for the second time, blew 3 seconds with heat baking rifle 10cm distance, reach the surface dried after.

Repeat to obtain after the program 6 times in above second step print thickness again and be 0.6 millimeter three dimensional ink graph layer.Allow it toast with 120-140 ℃ of 90-300 kind second then through the electric baking tunnel.

One, more satisfactory mode is 130 ℃ of bakings 5 minutes,

Two, more satisfactory mode is 140 ℃ of bakings 3 minutes,

Three, more satisfactory mode is 2 fens halfs of 145 ℃ of baking bakings.

More than one, two, any way can obtain plasticizing in three kind of mode.The cooling back obtains right angle effect printing finished product.

Annotate: fusion time also depends on the thickness of base cloth, because blocked up cloth makes temperature be difficult to be penetrated into oil.

Embodiment 6:

Adopt following prescription, the weight part of each component is as follows in the prescription:

Vinyl acetate content is 80 parts of 5% vinyl chloride-vinyl acetate copolymer paste resin

Vinyl acetate content is 20 parts of 25% vinyl chloride-vinyl acetate copolymerization blending resins

120 parts in softening agent

7.6 parts of thermo-stabilizers

9.2 parts of thickener rheology agents

8.9 parts of mute photo etchings

6.5 parts of frosting agents

Vinyl acetate content is at the vinyl chloride-vinyl acetate copolymerization blending resin PCMA-12 of 3-5%, and Chinese Shenyang Chemical Co., Ltd. produces.

Since its-content of vinyl acetate is at 3-5%, if produce the low temperature heat-set ink with this vinyl chloride-vinyl acetate copolymer paste resin fully, its plasticization temperature does not reach the desired 120-140 of low temperature heat-set ink ℃ plasticization temperature generally at 155-175 ℃ under the high situation of plasticizer loading.So the content of vinyl acetate this vinyl chloride-vinyl acetate copolymer paste resin of 3-5% can with vinyl acetate content than higher, as using than higher the mixing as vinyl chloride-vinyl acetate copolymerization blending resin in the vinyl acetate content of 7-25% in the vinyl chloride-vinyl acetate copolymer paste resin of the vinyl acetate content of 9-25% or vinyl acetate content.

COZ025 vinyl acetate content that multiple commerce and trade company limited sells is adopted at 25% vinyl chloride-vinyl acetate copolymerization blending resin in Shanghai.

Softening agent is 4 of Tianjin solvent factory production, 5-epoxy tetrahydrophthalic acid two (the 2-ethyl is own) ester EPS.Combination is good, and volatility is little, and transport property is little, and anti-extractable is good.Can allow ink pellet surface not have the oil sample sense of touch and ooze out phenomenon.

Thickener rheology agent is the N20 aerosil of German WACKER company, or is called the white carbon black of vapor phase process.Consumption is 9.2 parts.Use this thickener rheology agent can allow mobile printing ink not flow at normal temperatures, and have thixotropy, pseudo-plasticity.Melt viscosity when aerosil can increase the fusion of low temperature heat-set ink, even under sufficiently high plasticization temperature, low temperature heat-set ink melt does not flow.Can make right angle effect low temperature heat-set ink like this.

Thermo-stabilizer is the dibutyl tin dilaurate of Nanjing ancient cooking vessel chemistry in morning development in science and technology company limited, product type: SC-101; Clarification or little butter shape liquid; Tin content (Sn) 18.0-19.2%.Resin in the heat-set ink there is not obvious solvation, thermally-stabilised usefulness excellence.

Mute photo etching is the mute light powder of CONTINENT that Xiamen Kang Dilong trade Co., Ltd sells.Composition belongs to: the fine powder of silicon-dioxide.Along with the increase of add-on, the gloss of the ink pellet surface after the plasticizing descends, and more makes the surface have matt effect, extinction effect, even frosted finish effect occurs.

Frosting agent is the GUR X128 frosting agent that the auspicious rich trading firm in Guangzhou sells.Composition belongs to: the polyethylene micropowder wax of ultra-high molecular weight.The glossy black surface luster of reducing after printing has gentle velvet weavy grain mill yarn effect with acquisition.

Process for preparation is as follows:

After earlier the ratio weighing of whole raw material consumptions being come out, the softening agent of all resins component and 60 parts is mediated with 4-10 rev/min speed at duplicate rows star stirrer, about 10 minutes kneading time.Keep the mixing of materials temperature below 30 ℃.

Add 10 softening agent again and stir with 20 rev/mins speed, churning time is about 3 minutes.

All the N20 aerosil thickener rheology agent of the German WACKER of adding company is mediated with 10 rev/mins speed again, about 10 minutes kneading time.

The remaining softening agent of whole again addings stirs with 40 rev/mins speed, and churning time is about 3 minutes.

The speed with 40 rev/mins that all adds mute photo etching, frosting agent stirs again, and churning time is about 3 minutes

The speed that all adds 40 rev/mins of all thermo-stabilizers again stirs, and churning time obtains finished product printing ink about 10 minutes.

The printing ink that makes has been owing to used vinyl acetate content to mix at 25% vinyl chloride-vinyl acetate copolymerization blending resin in the vinyl chloride-vinyl acetate copolymer paste resin of 3-5% and vinyl acetate content to use, and more importantly is and to have added behind mute photo etching, the frosting agent the mute light of plasticizing back ink pellet surface and frosted finish effect more obvious.

Printing ink after making is to have more intense yield value, thixotropic pulpous state or paste, has been fit to printing.

The lithographic plate screen printing plate: grenadine 80 orders, screen cloth tension force 20N/cm2,0.2 millimeter of the thickness of photoresists, the printing net is apart from 5cm.

Scraper: the right angle rubber squeegee of hardness 70 degree.

Stock: common stretch lycra cloth.

The first step: after going up the printing ink that has mixed up by the lithographic plate screen printing plate that makes and scraping once with rubber squeegee is manual, printed figure was blown for 10 seconds with heat baking rifle 10cm distance, it is dried to reach the surface.

Second step: scrape by hand more for the second time, blew 3 seconds with heat baking rifle 10cm distance, reach the surface dried after.

Repeat to obtain after the program 6 times in above second step print thickness again and be 0.6 millimeter three dimensional ink graph layer.Allow it toast with 120-140 ℃ of 90-300 kind second then through the electric baking tunnel.

One, more satisfactory mode is 120 ℃ of bakings 5 minutes,

Two, more satisfactory mode is 130 ℃ of bakings 3 minutes,

Three, more satisfactory mode is 2 fens halfs of 140 ℃ of baking bakings.

More than one, two, any way can obtain plasticizing in three kind of mode.The cooling back obtains the mute tarry matter sand effect printing in right angle finished product.

Annotate: fusion time also depends on the thickness of base cloth, because blocked up cloth makes temperature be difficult to be penetrated into ink lay.

Embodiment 7:

Adopt following prescription, the weight part of each component is as follows in the prescription:

Vinyl acetate content is 50 parts of 25% vinyl chloride-vinyl acetate copolymer paste resin

80 parts of resins are stuck with paste in the polyvinyl chloride homopolymerization

180 parts in softening agent

5.8 parts of thermo-stabilizers

11.5 parts of thickener rheology agents

17.2 parts of whipping agents

16.5 parts of tinting materials

LU-25 vinyl acetate content that multiple commerce and trade company limited sells is adopted in 25% vinyl chloride-vinyl acetate copolymer paste resin in Shanghai.

The polyvinyl chloride homopolymerization is stuck with paste the resin polyvinyl chloride homopolymerization and is stuck with paste resin PSH-10, and Chinese Shenyang Chemical Co., Ltd. produces.

Because it does not contain-vinyl acetate, produce the low temperature heat-set ink if stick with paste resin with this polyvinyl chloride homopolymerization fully, its plasticization temperature does not reach the desired 120-140 of low temperature heat-set ink ℃ plasticization temperature fully generally at 180-190 ℃ under the high situation of plasticizer loading.But because of its viscosity stability good, so carry out interworking with the vinyl chloride-vinyl acetate copolymer paste resin of it and high vinyl acetate content.

Softening agent is the Lgflex BET softening agent that the sharp LG Corp of South Korea that gets International Trading Company Ltd's sale of ancient India in Shanghai is produced, and composition belongs to: formic acid two-thylhexoic acid trihydroxymethylpropanyl ester class.80 parts of consumptions

Softening agent is 2,2 of a U.S. Yi Shiman EASTMAN company, 4-trimethylammonium-1, and the 3-pentanediol diisobutyrate is called for short the TXIB softening agent.Can improve pollution resistance, the dry and comfortable property on the surface after printing ink plastifies.60 parts of consumptions

Softening agent is the Di Iso Decyl Phthalate (being called for short DIDP) that multiple commerce and trade company limited is adopted in Shanghai, provides good winter hardiness, excellent viscosity stability.

Thickener rheology agent is 7250 association type Polyurethane thickener rheology agents of AM General GE company or claims modified urea solution, for liquid.

Use this thickener rheology agent can allow mobile printing ink not flow at normal temperatures, and have thixotropy, pseudo-plasticity.In thickened systems, form three-dimensional structure, in the jump low viscosity of solution when having stepped on, having guaranteed that round corners effect low temperature heat-set ink is in fusion of its structure of back of being heated.Melt has flowability again under the plastifying fusion temperature, so just can make low temperature round corners effect heat-set ink.

Thermo-stabilizer is the BAEROSTAB OM 710N of Germany, type: tin octylate thiolate stablizer

Form: clarified liq

Gardner's colourimetric number: maximum 2

Proportion: 1.08 ± 0.01

Specific refractory power: 1.500 ± 0.002

Tin content (%): 15.1 ± 0.2

Be octyl tin stabilizer, have inviscid and can not produce and separate out, low volatility, advantage such as smell is few.

Whipping agent is that the p-toluene sulfonyl hydrazide that Hangzhou marine rainbow chemical industry company limited produces is called for short the TSH closed pore.Make plasticizing back ink pellet surface form gas-solid bonded vesicular structure, plasticizing back ink pellet surface is more coarse so, has gentle velvet weavy grain effect.Belong to the low-temp foaming agent.Plasticizing back ink pellet surface is more coarse so, has gentle velvet weavy grain effect.

Tinting material: pthalocyanine blue P.B.15:3 (the prosperous pigment in Wenzhou firm sells)

Process for preparation is as follows:

After earlier the ratio weighing of whole raw material consumptions being come out, the softening agent of all resins component and 70 parts is mediated with 4-10 rev/min speed at duplicate rows star stirrer, about 10 minutes kneading time.Keep the mixing of materials temperature below 30 ℃.

Add 10% softening agent again and stir with 20 rev/mins speed, churning time is about 3 minutes.

The remaining softening agent of whole again addings stirs churning time 3 minutes with 40 rev/mins speed.

The remaining tinting material of whole again addings stirs churning time 3 minutes with 40 rev/mins speed.

The remaining whipping agent of whole again addings stirs churning time 3 minutes with 40 rev/mins speed.

The speed that all adds 40 rev/mins of all thermo-stabilizers again stirs, churning time 10 minutes.

The speed that all adds 40 rev/mins of all thickener rheology agents again stirs, and churning time obtains finished product printing ink about 10 minutes.

Printing ink after making is to have more intense yield value, thixotropic pulpous state or paste, has been fit to printing.Owing to use the fillet foaming effect heat-set ink of blue color.

The lithographic plate screen printing plate: grenadine 80 orders, screen cloth tension force 20N/cm2,0.2 millimeter of the thickness of photoresists, the printing net is apart from 5cm.

Scraper: the right angle rubber squeegee of hardness 70 degree.

Stock: common stretch lycra cloth.

The first step: after going up the printing ink that has mixed up by the lithographic plate screen printing plate that makes and scraping once with rubber squeegee is manual, printed figure was blown for 10 seconds with heat baking rifle 10cm distance, it is dried to reach the surface.

Second step: scrape by hand more for the second time, blew 3 seconds with heat baking rifle 10cm distance, reach the surface dried after.

Repeat to obtain after the program 6 times in above second step print thickness again and be 0.6 millimeter three dimensional ink graph layer.Allow it toast with 120-140 ℃ of 90-300 kind second then through the electric baking tunnel.

One, more satisfactory mode is 120 ℃ of bakings 5 minutes,

Two, more satisfactory mode is 130 ℃ of bakings 3 minutes,

Three, more satisfactory mode is 2 fens halfs of 140 ℃ of baking bakings.

More than one, two, any way can obtain plasticizing in three kind of mode.The cooling back obtains the fillet foaming effect printing finished product of white colour.

Annotate: fusion time also depends on the thickness of base cloth, because blocked up cloth makes temperature be difficult to be penetrated into ink lay.

Embodiment 8:

Adopt following prescription, the weight part of each component is as follows in the prescription:

Vinyl acetate content is 100 parts of 15% vinyl chloride-vinyl acetate copolymer paste resin

Vinyl acetate content is 100 parts of 5% vinyl chloride-vinyl acetate copolymer paste resin

300 parts in softening agent

40 parts of thermo-stabilizers

40 parts of thickening stream agent

30 parts of copper powders

Vinyl chloride-vinyl acetate copolymer paste resin is the vinyl chloride-vinyl acetate copolymer paste resin PCL-15 of the vinyl acetate content about 15% of Chinese Shenyang Chemical Co., Ltd. production.Character is as follows:

The polymerization degree 800 ± 100

Fugitive constituent, % ,≤1.0

Tap density, g/cm3 0.35～0.55

The content 15 ± 2% of vinyl acetate

Outward appearance is white fines.

Vinyl acetate content is at the vinyl chloride-vinyl acetate copolymerization blending resin PCMA-12 of 3-5%, and Chinese Shenyang Chemical Co., Ltd. produces.

Since its-content of vinyl acetate is at 3-5%, if produce the low temperature heat-set ink with this vinyl chloride-vinyl acetate copolymer paste resin fully, its plasticization temperature does not reach the desired 120-140 of low temperature heat-set ink ℃ plasticization temperature generally at 155-175 ℃ under the high situation of plasticizer loading.So the content of vinyl acetate this vinyl chloride-vinyl acetate copolymer paste resin of 3-5% can with vinyl acetate content than higher, as using than higher the mixing as vinyl chloride-vinyl acetate copolymerization blending resin in the vinyl acetate content of 9-25% in the vinyl chloride-vinyl acetate copolymer paste resin of the vinyl acetate content of 9-25% or vinyl acetate content.

Softening agent is the Lgflex BET softening agent that the sharp LG Corp of South Korea that gets International Trading Company Ltd's sale of ancient India in Shanghai is produced, and composition belongs to: formic acid two-thylhexoic acid trihydroxymethylpropanyl ester class.400 parts of consumptions.

Softening agent is 2,2 of a U.S. Yi Shiman EASTMAN company, 4-trimethylammonium-1, and the 3-pentanediol diisobutyrate is called for short the TXIB softening agent.Can improve pollution resistance, the dry and comfortable property on the surface after printing ink plastifies.200 parts of consumptions.

Thermo-stabilizer is the dibutyl tin dilaurate of Nanjing ancient cooking vessel chemistry in morning development in science and technology company limited, product type: SC-101; Clarification or little butter shape liquid; Tin content (Sn) 18.0-19.2%.Resin in the heat-set ink there is not obvious solvation, thermally-stabilised usefulness excellence.

Thickener rheology agent is the N20 aerosil of German WACKER company, or is called the white carbon black of vapor phase process.

Copper powder is that the prosperous pigment marketing in Wenzhou is sold, and particle diameter is the 200-1200 order.

Release agent is the 9610F wear-resisting scratch-resisting agent that the auspicious rich trading firm in Guangzhou sells, and is the fines Wax, in order to make the heat-set ink surface anti sticking, increases slippery.

Process for preparation is as follows:

After earlier the ratio weighing of whole raw material consumptions being come out, the softening agent of all resins component and 100 parts is mediated with 4-10 rev/min speed at duplicate rows star stirrer, about 10 minutes kneading time.Keep the mixing of materials temperature below 30 ℃.

The softening agent that adds 20 parts again stirs with 20 rev/mins speed, and churning time is about 3 minutes.

All the N20 aerosil thickener rheology agent of the German WACKER of adding company is mediated with 10 rev/mins speed again, about 10 minutes kneading time.

All add all again Copper powder with40 rev/mins speed stirs, churning time 10 minutes.

All add all release agents again and stir churning time 10 minutes with 40 rev/mins speed

The remaining softening agent of whole again addings stirs with 40 rev/mins speed, and churning time is about 3 minutes.

The speed that all adds 40 rev/mins of all thermo-stabilizers again stirs, and churning time obtains finished product printing ink about 10 minutes.

Printing ink after making is to have more intense yield value, thixotropic pulpous state or paste, has been fit to printing,

Make right angle gold effect heat-set ink

The lithographic plate screen printing plate: grenadine 80 orders, screen cloth tension force 20N/cm2,0.2 millimeter of the thickness of photoresists, the printing net is apart from 5cm.

Scraper: the right angle rubber squeegee of hardness 70 degree.

Stock: common stretch lycra cloth.

The first step: after going up the printing ink that has mixed up by the lithographic plate screen printing plate that makes and scraping once with rubber squeegee is manual, printed figure was blown for 10 seconds with heat baking rifle 10cm distance, it is dried to reach the surface.

Second step: scrape by hand more for the second time, blew 3 seconds with heat baking rifle 10cm distance, reach the surface dried after.

Repeat to obtain after the program 6 times in above second step print thickness again and be 0.6 millimeter three dimensional ink graph layer.Allow it toast with 120-140 ℃ of 90-300 kind second then through the electric baking tunnel.

One, more satisfactory mode is 120 ℃ of bakings 5 minutes,

Two, more satisfactory mode is 130 ℃ of bakings 3 minutes,

Three, more satisfactory mode is 2 fens halfs of 140 ℃ of baking bakings.

More than one, two, any way can obtain plasticizing in three kind of mode.The cooling back obtains to make right angle gold effect printing finished product.

Claims (10)

1. heat-set ink is characterized in that: the component that described heat-set ink comprises and the weight part of each component are as follows:

Vinyl acetate content is the vinyl chloride-vinyl acetate copolymer paste resin 10-100 of 9-25% part

Softening agent 20-600 part

Thermo-stabilizer 0.1-100 part

Thickener rheology agent 0.1-100 part.

2. heat-set ink according to claim 1 is characterized in that: the component that described heat-set ink comprises and the weight part of each component are as follows:

Vinyl acetate content is the vinyl chloride-vinyl acetate copolymer paste resin 10-100 of 9-25% part

Softening agent 20-180 part

Thermo-stabilizer 0.1-40 part

Thickener rheology agent 0.1-40 part.

3. heat-set ink according to claim 2 is characterized in that: the vinyl acetate content of described vinyl chloride-vinyl acetate copolymer paste resin is 11-17%.

4. heat-set ink according to claim 3 is characterized in that: the component of described heat-set ink comprises that also vinyl acetate content is in the vinyl chloride-vinyl acetate copolymerization blending resin 20-200 of 10-45% part, vinyl acetate content a kind of or its combination in the vinyl chloride-vinyl acetate copolymer paste resin 10-100 of 3-5% part and pvc resin paste grade 10-80 part.

5. heat-set ink according to claim 4 is characterized in that: the content of the vinyl acetate of described vinyl chloride-vinyl acetate copolymerization blending resin is 11-15%.

6. heat-set ink according to claim 5, it is characterized in that: described softening agent is little in other words conj.or perhaps little to the resin dissolves power at normal temperatures softening agent of solvation, and described thermo-stabilizer is one or more the combination in organic tin thermo-stabilizer and the liquid calcium/zinc composite stabilizer.

7. heat-set ink according to claim 6, it is characterized in that: described softening agent is a diisononyl phthalate, be called for short DINP, trioctyl trimellitate, be called for short TOTM, 4,5-epoxy tetrahydrophthalic acid diester, be called for short EPS, dioctyl sebacate, be called for short DOS, Di Iso Decyl Phthalate, be called for short DIDP, phenylformic acid two-thylhexoic acid trihydroxymethylpropanyl ester class, dioctyl terephthalate class, 1,2-dicarboxyl diisononyl esters class, 2,2,4-trimethylammonium-1, the 3-pentanediol diisobutyrate, the combination of one or more among the abbreviation TXIB.

8. according to claim 3 or 4 described arbitrary heat-set inks, it is characterized in that: described thickener rheology agent is a kind of or its combination of the inorganic modified derivatives class thickener rheology agent of aerosil class thickener rheology agent or Viscotrol C or association type Polyurethane thickener rheology agent or organobentonite thickener rheology agent.

9. according to claim 3 or 4 described arbitrary heat-set inks, it is characterized in that: described heat-set ink also contains photostabilizer, oxidation inhibitor, epoxy soybean oil (ESO), viscosity-depression agent, tinting material, mute photo etching, frosting agent, whipping agent, fine copper powder and one or more the combination in aluminium powder or the fines Wax.

10. heat-set ink according to claim 9 is characterized in that: described photostabilizer, oxidation inhibitor, viscosity-depression agent, tinting material, mute photo etching, frosting agent, whipping agent, fine copper powder and one or more the weight part of combination in aluminium powder or the fines Wax are 0.1-180 part.