CN101879820B - Ink-jet recording material used for full-face spray light box film - Google Patents
Ink-jet recording material used for full-face spray light box film Download PDFInfo
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- CN101879820B CN101879820B CN201010207732XA CN201010207732A CN101879820B CN 101879820 B CN101879820 B CN 101879820B CN 201010207732X A CN201010207732X A CN 201010207732XA CN 201010207732 A CN201010207732 A CN 201010207732A CN 101879820 B CN101879820 B CN 101879820B
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Abstract
The invention discloses an ink-jet recording material used for a full-face spray light box film, which comprises a support body, an ink fixing layer and an ink-absorbing covering layer. The ink fixing layer and the ink-absorbing covering layer respectively contain inorganic dyes, aqueous polymer emulsions, water-soluble high polymer resin and cationic fixing agents; the inorganic dyes in the ink-absorbing covering layer are silica with 0.5 to 10 micrometers by a precipitation method and titanium dioxide with 10 to 500 nanometers; the inorganic dye in the ink fixing layer is silica with 0.5 to 10 micrometers by a precipitation method; and the aqueous polymer emulsions in the ink fixing layer and the ink-absorbing covering layer are an aqueous biopolymer emulsion with an ethylene segment with self-plasticizing action and an aqueous polyurethane emulsion. The recording material has the advantages of good light fastness, weather resistance and scratch resistance, high image color saturation, good covering power and high light transmission.
Description
Technical field
The present invention relates to a kind of ink jet recording materials, particularly a kind of ink jet recording materials that is used for full-face spray light box film.
Background technology
In recent years, the development of advertising is at a tremendous pace, and nearly all enterprise and businessman all spare no effort to propagate to self and product.The form of advertising carrier is various day by day, and is also increasingly high to the quality requirement of advertising carrier simultaneously.In numerous advertising carriers, advantages such as the inkjet printing mode is cheap owing to its hardware, output is efficient and convenient, work noiselessness are widely used.Especially constantly perfect along with printer capability; Restricted in the past factor such as the output speed of inkjet printing range of application slow with problem such as picture quality shortcoming by solution well; Inkjet printing output speed and silver salt enlargement of color photos are very nearly the same now; Under the good situation of performance of ink-jet memorial material, picture quality is very good.Ink jet recording materials must have following character: (1) blotting speed is fast.Because the print speed of ink-jet printer is more and more faster, require the blotting speed of ink jet recording materials enough fast, dry immediately after could guaranteeing to print, ink droplet can not occur and assemble and the inhomogeneous situation of pattern color of formation; (2) bigger blotting amount.Ink jet recording materials must have enough spaces to hold the ink of accepting fully, oozes with laterally spreading and sinking in otherwise will occur floating China ink at the big density place of image, influences pattern quality; (3) good solid black ability.The solid black ability of ink jet recording medium is not good to show as the water proofing property difference and the prolongation appearance image blurring phenomenon of pattern along with standing time of printing the back pattern, and especially under laying temperature and humidity condition with higher, image blurring phenomenon is more obvious; (4) the pattern color saturation degree is good.Color saturation of image is by the reflection density and transmission density (the being applicable to transparent and translucent film) decision of pattern, and the visual sensation image of the pattern that color saturation is good is bright-coloured, lucid and lively; (5) fast light, the weather-proof and water resistance of recording medium is good.Whether fast light, the weather-proof and resistance to water of recording medium the scope of application of good decision recording medium, is the important performance of recording medium; (6) performances such as the scratch resistance performance on recording medium surface, glossiness, dimensional stability.
The ink-jet lamp box panel is divided into two kinds of the back of the body blowtorch box film and full-face spray light box films.Back of the body blowtorch box film is that print image is printed on ink receiving layer with the mirror image form; The transparent ink solidifying layer of ink infiltrate ink receiving layer between support and ink receiving layer forms image; When making lamp box that printing surface is inner towards lamp box, watch image from a side of support.Full-face spray light box film is that image is printed on the ink receiving layer of coating transparent support, and after image was printed and finished, printing surface was processed lamp box towards the outside, watches image from printing surface one side.The ink-jet lamp box film that uses as high-end advertisement has more special requirement than other ink jet recording mediums: 1.. and the lamp box film will have enough covering powers, can not see the shape of light source from the outside clearly after the lamp box manufacturing is good and influences the viewing effect of image; 2.. the light transmittance of lamp box film itself wants high, makes image color distincter; 3. the reflection of the pattern of lamp box panel output and transmission density want big, generally require the black density of max transmissive to surpass 3.0, so just can make lamp box image expressive force perfect, reach good result of use; 4. the surface gloss of lamp box film is lower than the glossiness of general ink jet recording materials, and general requirement will be lower than 10, avoids watching of specular reflections effect side as far as possible.
Publication number is that the Chinese patent of CN 1970308A discloses a kind of front-spraying film for water-proof ink jetting; It comprises support, bottom, ink solidifying layer and ink leaking layer; Its improvement is that ink solidifying layer contains the high polymer and the inorganic pigment of chain type unsaturated bond structure, wherein; The particle diameter of inorganic pigment is 0.5～10 μ m, and the consumption of the high polymer of chain type unsaturated bond structure is with respect to 5～30 parts of 100 parts of inorganic pigments; Ink leaking layer contains benzene-olefines bipolymer inorganic pigment; Wherein, The particle diameter of inorganic pigment is 0.5～10 μ m, and the consumption of bipolymer is with respect to 5～40 parts of 100 parts of inorganic pigments, and it has solved, and ink-jet film water resistance is poor, the problem of ink absorption difference.But; There is following defective in this product: 1. this lamp box film since the bipolymer that adopted benzene-olefines as auxiliary film forming matter, under illumination and hot and humid condition, oxidation xanthochromia phenomenon can take place in the bipolymer of benzene-olefines very soon; Influence the service life of lamp box film; And can cause the fragility of film stronger, the bad mechanical property of coating surface is in scraping or have the phenomenon of " dry linting " when cutting; Since the ink solidifying layer of this lamp box film near supporting the side, when using paint ink to print, ink can not be fixed effectively, causes the water proofing property difference and the pattern density of image less; 3. owing to only adopt silica as inorganic pigment, the hiding lack of coating causes backlight to influence the problem of image-watching effect easily.
Summary of the invention
The technical problem that the present invention will solve is: provide a kind of fast light, weatherability is good, no xanthochromia, good covering power and good light transmittance, coating machine function admirable, dry linting not, the ink jet recording materials that is used for full-face spray light box film of inkjet printing function admirable.
For solving the problems of the technologies described above, the technical scheme that the present invention takes is:
A kind of ink jet recording materials that is used for full-face spray light box film comprises support, ink solidifying layer and blotting covering layer, contains inorganic pigment, aqueous polymer emulsion, water soluble polymer resin and cationic fixing agent in ink solidifying layer and the blotting covering layer respectively; Inorganic pigment in the said blotting covering layer is the titanium dioxide of 0.5 micron～10 microns precipitated silica and 10 nanometers～500 nanometers; Inorganic pigment is 0.5 micron～10 microns a precipitated silica in the said ink solidifying layer; Aqueous polymer emulsion in said ink solidifying layer and the blotting covering layer is water-based bipolymer emulsion and the aqueous polyurethane emulsion that has the ethene section of self-plasticizing action.
The above-mentioned ink jet recording materials that is used for full-face spray light box film, the precipitated silica in the said blotting covering layer and the weight ratio of titanium dioxide are 10～1: 1.
The above-mentioned ink jet recording materials that is used for full-face spray light box film, the consumption of the water-based bipolymer emulsion of said ethene section is 5～50% of an inorganic pigment weight.
The above-mentioned ink jet recording materials that is used for full-face spray light box film, the consumption of said aqueous polyurethane emulsion are the weight 2.5～20% of inorganic pigment.
The above-mentioned ink jet recording materials that is used for full-face spray light box film, the water-based bipolymer emulsion of said ethene section is the ethene-vinyl acetate polymer emulsion.
The above-mentioned ink jet recording materials that is used for full-face spray light box film, the consumption of said cationic fixing agent are 1～20% of inorganic pigment weight; Said cationic fixing agent is that mean molecule quantity is 5000～100000 dimethyl diallyl ammonium chloride copolymer.
Being fit to support of the present invention can be films such as PE film, TAC film, PET film, and this film is transparent,, considers from point of view of practicability that preferred used thickness is 100～200 microns a PET film to the not special restriction of its thickness.Be fit to be coated with the caking property bottom in advance on the support of the present invention, increase the fastness between support and blotting covering layer.
Ink solidifying layer, away from support, white, main effect with ink by in coating, prevent ink droplet in coating horizontal proliferation and cause image blurring, make image more bright-coloured and have a waterproof ability.Contain inorganic pigment, aqueous polymer emulsion, high molecular weight water soluble polymer and cationic fixing agent in the ink solidifying layer.
The blotting covering layer; Near support; Main effect is that the space between the inorganic pigment that relies in the coating absorbs the solvent among the ink droplet that is injected on the recording materials, makes the ink droplet can be dry immediately, avoids occurring that ink droplet gathers and the even phenomenon of density unevenness that causes in Da Mo amount part.Add the higher particle of hiding rare simultaneously, improve the mist degree of coating, avoid because of seeing that from the lamp box front shape of backlight influences viewing effect.The blotting covering layer contains inorganic pigment, aqueous polymer emulsion, high molecular weight water soluble polymer and cationic fixing agent.
Ink jet recording materials mainly relies on the coating of porous to reach sufficient ink absorption ability, and the adding of inorganic pigment granules in the coating forms the space between inorganic pigment granules, thereby reaches enough ink absorption ability.The kind of inorganic pigment, grain shape and size have direct influence to the ink absorption ability of coating; Reach satisfied ink absorption ability; The kind of inorganic pigment, grain shape and size should meet some requirements; In order to guarantee that material has enough ink absorption ability, need to use the bigger inorganic pigment of particle diameter to guarantee the voidage of coating.Among the present invention, the pigment that infiltration covering layer and ink solidifying layer are selected for use can be inorganic pigments such as calcium carbonate, barium sulfate, aluminium oxide, fumed silica, precipitated silica, titanium dioxide, china clay, kaolin.Because satisfy the requirement of the high absorbency of coating, so select the higher precipitated silica of empty capacity rate as main pigment, wherein preferably using particle diameter is 0.5 micron～10 microns precipitated silica.
The ink jet recording materials that is used for full-face spray light box film also should have enough covering powers and light transmittance except having good ink absorption ability.The covering power of coating can use the mist degree of coating or opacity to characterize, and the covering power of coating well then can be avoided the viewing effect because of the shape affects lamp box pattern of seeing backlight; The light transmittance of coating can use coating density to represent, the light transmittance height of coating then can make lamp box higher in the brightness of the situation hypograph of opening backlight, and image has better expressive force.In order to satisfy the requirement of covering power, also added the inorganic pigment of strong covering power in the blotting covering layer, wherein preferably use the good titanium dioxide granule of covering power.More in order under the situation that reaches the covering power requirement, to make coating also have light transmission preferably, more preferably using particle diameter is the superfine titanic oxide of 10 nanometers～500 nanometers.When the particle diameter of titanium dioxide during less than 10 nanometers, titanium dioxide granule shows stronger catalytic oxidation ability when absorbing ultraviolet ray, cause the xanthochromia phenomenon of material under illumination condition easily; When titanium dioxide granule particle diameter during greater than 500 nanometers, the dispersion of the titanium dioxide granule difficulty that becomes is difficult to obtain stable titanium dioxide dispersion system, and titanium oxide dispersion the layering and precipitating phenomenon very easily occurs and influences use.
In order to guarantee that material had both had enough ink absorption ability; Have enough covering powers and light transmittance again; Inorganic pigment in the blotting covering layer of the present invention adopts the combination of above-mentioned two kinds of inorganic pigments to use; Wherein: the weight ratio of precipitated silica and titanium dioxide is 10～1: 1, has solved the xanthochromia problem of product so preferably.
Precipitated silica is a porous type silica, adopts equipment such as high speed shear mulser, ultrasonic disperser, three-roll grinder, sand mill or high-pressure homogenizer to be dispersed into 0.5～10.0 micron particle to the silica dioxide granule of assembling.
Contain aqueous polymer emulsion in infiltration covering layer and the ink solidifying layer, its effect is a mechanical performance of improving coating, makes the scratch resistance ability of coating, pliability can both reach level preferably; Can improve simultaneously the waterproof ability of coating.Among the present invention, aqueous polymer emulsion is the water-based bipolymer emulsion that has the ethene section of self-plasticizing action, and its consumption is 5～50 weight % of inorganic pigment.The ethene section can rotate freely in the polymer; It plays the effect of self-plasticization to polymer; Such emulsion applications can make coating have good toughness in coating; Effectively prevent material in the phenomenon that cuts middle appearance " dry linting ", being fit to aqueous polymer emulsion of the present invention can be aqueous polyacrylamide yogurt liquid, water-based ethylene-vinyl acetate copolymer emulsion, water-based styrene-ethylene copolymers emulsion etc., owing to good fast light, the weather-proof ability that also has of ethylene-vinyl acetate copolymer itself; It can make fast light, the weatherability of coating strengthen greatly, so the present invention preferably makes the use ethylene-vinyl acetate copolymer emulsion.
Among the present invention, have the adding of water-based bipolymer emulsion of the ethene section of self-plasticizing action, make the coating of material have good toughness, effectively prevented the phenomenon of " dry linting " of material in cutting, still, the strength of coating of material is not enough.In order to make coating not only have good toughness but also have enough intensity; The present invention has also added aqueous polyurethane emulsion in infiltration covering layer and ink solidifying layer; Especially preferably add cation aqueous polyurethane emulsion, the consumption of aqueous polyurethane emulsion is that inorganic pigment is 2.5～20 weight %.The aqueous polyurethane emulsion addition is very few, and strength of coating increases not obvious, does not reach scratch resistant requirement; The aqueous polyurethane emulsion addition is too much, and then the ink absorption ability of coating can reduce greatly, influences the inkjet printing performance of coating.
Among the present invention, contain the aqueous high molecular resin in blotting covering layer and the ink solidifying layer.The effect of water soluble polymer resin is in the coating dry run, to form successional coating, hides material to blottings such as inorganic pigments and is fixed in the coating.The water soluble polymer resin can be one or more in the materials such as gelatin, CMC, carboxymethyl cellulose, starch, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol; Wherein preferably use polyvinyl alcohol; Particularly the degree of polymerization is the polyvinyl alcohol of 1700～5000 high polymerization degree; The degree of polymerization like pectin/polyvinyl alcohol is too small, and the disadvantage of crackle appears in coating easily; Can make the viscosity of coating fluid big if the degree of polymerization is excessive, thereby make coating process be difficult to control.
Among the present invention, contain color-fixing agent in blotting covering layer and the ink solidifying layer.Color-fixing agent also is modifier, mainly plays fixation and dispersed color.In aqueous dispersion; Owing to forming the silanol base, silica particles and water effect have negative electrical charge; Agglutination phenomenon takes place in the water soluble polymer resin in silanol base and the coating fluid because of hydrogen bond action; Thereby can't obtain the coating of good-looking, before forming coating fluid so silica dioxide granule needed to use cationic fixing agent that the silanol base of silica dioxide granule silicon face is shielded.After silica particles and cationic fixing agent combination; Silica particles has positive charge; After the ink droplet that has negative electrical charge was injected into coating surface, the silica dioxide granule of positively charged combined in colour developing group that has negative electrical charge in the ink and the coating, and ink is fixed in the coating; Thereby prevent ink droplet in coating horizontal proliferation and the image blurring disadvantage that causes makes image have water proofing property simultaneously.The consumption of control cationic fixing agent in ink solidifying layer and blotting covering layer can be fixed on ink in the ink solidifying layer as much as possible, thereby makes the pattern color saturation degree high, and image is bright-coloured.The condensation body salt that suitable cationic fixing agent of the present invention can be polymine and salt, polyvinylamine and salt thereof, polyallylamine and salt thereof, acrylamide copolymer, dicyandiamide analog copolymer, secondary amine and epihalohydrin etc.; The preferred mean molecule quantity that uses is 2000～200000 dimethyl diallyl ammonium chloride copolymer, more preferably 5000～100000.The consumption of cationic fixing agent is 1～20% of an inorganic pigment weight, more preferably 3～10%.
Among the present invention, can also add additives such as crosslinking agent, surfactant, fluorescent whitening agent, ultra-violet absorber, anti-oxidant, antifoaming agent, anticorrisive agent, pH value conditioning agent in the coating of material, the performance of adjustment coating coating fluid,
Among the present invention; The coating of material can realize through known coating method, like sliding pearl coating method, extrusion coated mode, airblade coating mode, scraper coating method etc., in order to improve coating efficiency; But the preferred mode that adopts multilayer once to be coated with is like the multilayer extrusion coated.
In order to improve adhesive force of coatings, before being coated with on the transparent support, can adopt modes such as discharge process, flame treatment, UV treatment or plasma treatment that the support surface is handled.
Ink jet recording materials provided by the invention can prepare through following method:
Preparation blotting covering layer coating fluid and ink solidifying layer coating fluid are coated with blotting covering layer and ink solidifying layer then on transparent support, cold wind is dry to coating cooling back, obtains ink jet recording materials of the present invention.
In the present invention, behind coating blotting covering layer and the ink solidifying layer, lead to cold wind coating is cooled to below 20 ℃, can effectively prevent in dry run, to occur disadvantages such as fine cracks, raising is also arranged for the ink absorption ability of coating.
Compared with prior art; Ink jet recording materials provided by the invention; The combination of the precipitated silica through 0.5～10 micron in the blotting covering layer and the titanium dioxide of 10～500 nanometers is used; Both guaranteed that material had enough ink absorption ability, guaranteed again that material had enough covering powers and light transmittance, solved the xanthochromia problem of product preferably; The water-based bipolymer emulsion of the ethene section through having self-plasticizing action in blotting covering layer and the ink solidifying layer and the combination of aqueous polyurethane emulsion are used, and efficiently solve the phenomenon of " dry linting " of material in cutting, and have guaranteed the inkjet printing performance of material.
The specific embodiment
Specify the present invention through embodiment below, but the content of invention does not receive the restriction of embodiment.Wherein part is represented weight portion.
Embodiment 1
The preparation of blotting covering layer coating fluid:
100 parts of precipitated silica (Beijing space flight Saden SD-520, about 2 microns of average grain diameter)
10 parts of dimethyl diallyl ammonium chloride copolymers (mean molecule quantity is 50000)
20 parts of polyvinyl alcohol (Kuraray pva235 saponification degree 88%, average degree of polymerization 3500)
5 parts of boric acid (reagent is learned in permanent Xinghua, Tianjin)
20 parts of titanium dioxide (about 10 nanometers of average grain diameter)
6 parts of water-based ethylene-vinyl acetate copolymer emulsions (Dalian, Taiwan chemistry DA-100L)
24 parts of aqueous polyurethane emulsions (first SUPERFLEX of Industrial Co., Ltd 650)
0.5 part of calgon (three subsidiary factories of Tianjin chemical reagent six factories)
0.5 part of OP-10 (Tianjin reagent in rich morning)
614 parts of deionized waters
Precipitated silica is dispersed into stable aqueous dispersions with high-shear emulsion machine, and the titanium dioxide solid adopts high-shear emulsion machine under the condition that adds calgon, to be dispersed into stable aqueous dispersions.Under stirring at low speed,, continue to add polyvinyl alcohol, water-based ethylene-vinyl acetate copolymer emulsion, aqueous polyurethane emulsion and other auxiliary agents with after two kinds of dispersion liquids mixing.Stirring at low speed is even, obtains blotting covering layer coating fluid, and is subsequent use.
The preparation of ink solidifying layer coating fluid:
100 parts of precipitated silica (Beijing space flight Saden SD-520, about 2 microns of average grain diameter)
10 parts of dimethyl diallyl ammonium chloride copolymers (mean molecule quantity is 50000)
20 parts of polyvinyl alcohol (Kuraray pva235 saponification degree 88%, average degree of polymerization 3500)
5 parts of boric acid (reagent is learned in permanent Xinghua, Tianjin)
5 parts of water-based ethylene-vinyl acetate copolymer emulsions (Dalian, Taiwan chemistry DA-100L)
20 parts of aqueous polyurethane emulsions (first SUPERFLEX of Industrial Co., Ltd 650)
0.5 part of calgon (three subsidiary factories of Tianjin chemical reagent six factories)
0.5 part of OP-10 (Tianjin reagent in rich morning)
634 parts of deionized waters
Precipitated silica is dispersed into stable aqueous dispersions with high-shear emulsion machine, under stirring at low speed, continues to add polyvinyl alcohol, water-based ethylene-vinyl acetate copolymer emulsion, aqueous polyurethane emulsion and other auxiliary agents.Stirring at low speed is even, obtains the ink solidifying layer coating fluid, and is subsequent use.
The clear PET tablet of band caking property priming coat that uses 170 micron thick is as support, adopt slope stream extrusion coated mode disposable on support coating blotting covering layer and ink solidifying layer.After with 8 ℃ of cold wind coating being cooled off 45 seconds, get in the dry road of 60 ℃ of temperature, relative humidity 15%～20% and carry out obtaining the ink jet recording materials sample after the drying.Two-layer coating gross dry weight is 25 gram/square meters.
The ink jet recording materials sample of processing with said method is carried out following several kinds of performance test evaluations, and the result sees table 1.
Embodiment 2
The preparation of blotting covering layer coating fluid:
100 parts of precipitated silica (Beijing space flight Saden SD-960, about 10 microns of average grain diameter)
12 parts of dimethyl diallyl ammonium chloride copolymers (mean molecule quantity is 50000)
20 parts of polyvinyl alcohol (Kuraray pva235 saponification degree 88%, average degree of polymerization 3500)
5 parts of boric acid (reagent is learned in permanent Xinghua, Tianjin)
20 parts of titanium dioxide (about 100 nanometers of average grain diameter)
15 parts of water-based ethylene-vinyl acetate copolymer emulsions (Dalian, Taiwan chemistry DA-100L)
24 parts of aqueous polyurethane emulsions (first SUPERFLEX of Industrial Co., Ltd 650)
0.5 part of calgon (three subsidiary factories of Tianjin chemical reagent six factories)
0.5 part of OP-10 (Tianjin reagent in rich morning)
614 parts of deionized waters
Precipitated silica is dispersed into stable aqueous dispersions with high-shear emulsion machine, and the titanium dioxide solid adopts high-shear emulsion machine under the condition that adds calgon, to be dispersed into stable aqueous dispersions.Under stirring at low speed,, continue to add polyvinyl alcohol, water-based ethylene-vinyl acetate copolymer emulsion, aqueous polyurethane emulsion and other auxiliary agents with after two kinds of dispersion liquids mixing.Stirring at low speed is even, obtains blotting covering layer coating fluid, and is subsequent use.
The preparation of ink solidifying layer coating fluid:
100 parts of precipitated silica (Beijing space flight Saden SD-960, about 10 microns of average grain diameter)
10 parts of dimethyl diallyl ammonium chloride copolymers (mean molecule quantity is 50000)
20 parts of polyvinyl alcohol (Kuraray pva235 saponification degree 88%, average degree of polymerization 3500)
5 parts of boric acid (reagent is learned in permanent Xinghua, Tianjin)
12.5 parts of water-based ethylene-vinyl acetate copolymer emulsions (Dalian, Taiwan chemistry DA-100L)
20 parts of aqueous polyurethane emulsions (first SUPERFLEX of Industrial Co., Ltd 650)
0.5 part of calgon (three subsidiary factories of Tianjin chemical reagent six factories)
0.5 part of OP-10 (Tianjin reagent in rich morning)
634 parts of deionized waters
Precipitated silica is dispersed into stable aqueous dispersions with high-shear emulsion machine, under stirring at low speed, continues to add polyvinyl alcohol, water-based ethylene-vinyl acetate copolymer emulsion, aqueous polyurethane emulsion and other auxiliary agents.Stirring at low speed is even, obtains the ink solidifying layer coating fluid, and is subsequent use.
Employing such as embodiment 1 said mode prepare the ink jet recording materials sample, and carry out test evaluation, and the result sees table 1.
Embodiment 3
The preparation of blotting covering layer coating fluid:
100 parts of precipitated silica (Gray Si P-508, about 0.5 micron of average grain diameter)
3.6 parts of dimethyl diallyl ammonium chloride copolymers (mean molecule quantity is 50000)
20 parts of polyvinyl alcohol (Kuraray pva235 saponification degree 88%, average degree of polymerization 3500)
5 parts of boric acid (reagent is learned in permanent Xinghua, Tianjin)
20 parts of titanium dioxide (rice in the average grain diameter about 500)
60 parts of water-based ethylene-vinyl acetate copolymer emulsions (Dalian, Taiwan chemistry DA-100L)
24 parts of aqueous polyurethane emulsions (first SUPERFLEX of Industrial Co., Ltd 650)
0.5 part of calgon (three subsidiary factories of Tianjin chemical reagent six factories)
0.5 part of OP-10 (Tianjin reagent in rich morning)
614 parts of deionized waters
Precipitated silica is dispersed into stable aqueous dispersions with high-shear emulsion machine, and the titanium dioxide solid adopts high-shear emulsion machine under the condition that adds calgon, to be dispersed into stable aqueous dispersions.Under stirring at low speed,, continue to add polyvinyl alcohol, water-based ethylene-vinyl acetate copolymer emulsion, aqueous polyurethane emulsion and other auxiliary agents with after two kinds of dispersion liquids mixing.Stirring at low speed is even, obtains blotting covering layer coating fluid, and is subsequent use.
The preparation of ink solidifying layer coating fluid:
100 parts of precipitated silica (Gray Si P-508, about 0.5 micron of average grain diameter)
3 parts of dimethyl diallyl ammonium chloride copolymers (mean molecule quantity is 50000)
20 parts of polyvinyl alcohol (Kuraray pva235 saponification degree 88%, average degree of polymerization 3500)
5 parts of boric acid (reagent is learned in permanent Xinghua, Tianjin)
50 parts of water-based ethylene-vinyl acetate copolymer emulsions (Dalian, Taiwan chemistry DA-100L)
20 parts of aqueous polyurethane emulsions (first SUPERFLEX of Industrial Co., Ltd 650)
0.5 part of calgon (three subsidiary factories of Tianjin chemical reagent six factories)
0.5 part of OP-10 (Tianjin reagent in rich morning)
634 parts of deionized waters
Precipitated silica is dispersed into stable aqueous dispersions with high-shear emulsion machine, under stirring at low speed, continues to add polyvinyl alcohol, water-based ethylene-vinyl acetate copolymer emulsion, aqueous polyurethane emulsion and other auxiliary agents.Stirring at low speed is even, obtains the ink solidifying layer coating fluid, and is subsequent use.
Employing such as embodiment 1 said mode prepare the ink jet recording materials sample, and carry out test evaluation, and the result sees table 1.
Embodiment 4
The preparation of blotting covering layer coating fluid:
100 parts of precipitated silica (Beijing space flight Saden SD-520, about 2 microns of average grain diameter)
10 parts of dimethyl diallyl ammonium chloride copolymers (mean molecule quantity is 5000)
20 parts of polyvinyl alcohol (Kuraray pva235 saponification degree 88%, average degree of polymerization 3500)
5 parts of boric acid (reagent is learned in permanent Xinghua, Tianjin)
20 parts of titanium dioxide (about 10 nanometers of average grain diameter)
6 parts of water-based ethylene-vinyl acetate copolymer emulsions (Dalian, Taiwan chemistry DA-100L)
3 parts of aqueous polyurethane emulsions (first SUPERFLEX of Industrial Co., Ltd 650)
0.5 part of calgon (three subsidiary factories of Tianjin chemical reagent six factories)
0.5 part of OP-10 (Tianjin reagent in rich morning)
614 parts of deionized waters
Precipitated silica is dispersed into stable aqueous dispersions with high-shear emulsion machine, and the titanium dioxide solid adopts high-shear emulsion machine under the condition that adds calgon, to be dispersed into stable aqueous dispersions.Under stirring at low speed,, continue to add polyvinyl alcohol, water-based ethylene-vinyl acetate copolymer emulsion, aqueous polyurethane emulsion and other auxiliary agents with after two kinds of dispersion liquids mixing.Stirring at low speed is even, obtains blotting covering layer coating fluid, and is subsequent use.
The preparation of ink solidifying layer coating fluid:
100 parts of precipitated silica (Beijing space flight Saden SD-520, about 2 microns of average grain diameter)
10 parts of dimethyl diallyl ammonium chloride copolymers (mean molecule quantity is 5000)
20 parts of polyvinyl alcohol (Kuraray pva235 saponification degree 88%, average degree of polymerization 3500)
5 parts of boric acid (reagent is learned in permanent Xinghua, Tianjin)
5 parts of water-based ethylene-vinyl acetate copolymer emulsions (Dalian, Taiwan chemistry DA-100L)
2.5 parts of aqueous polyurethane emulsions (first SUPERFLEX of Industrial Co., Ltd 650)
0.5 part of calgon (three subsidiary factories of Tianjin chemical reagent six factories)
0.5 part of OP-10 (Tianjin reagent in rich morning)
634 parts of deionized waters
Precipitated silica is dispersed into stable aqueous dispersions with high-shear emulsion machine, under stirring at low speed, continues to add polyvinyl alcohol, water-based ethylene-vinyl acetate copolymer emulsion, aqueous polyurethane emulsion and other auxiliary agents.Stirring at low speed is even, obtains the ink solidifying layer coating fluid, and is subsequent use.
Employing such as embodiment 1 said mode prepare the ink jet recording materials sample, and carry out test evaluation, and the result sees table 1.
Embodiment 5
The preparation of blotting covering layer coating fluid:
100 parts of precipitated silica (Beijing space flight Saden SD-520, about 2 microns of average grain diameter)
10 parts of dimethyl diallyl ammonium chloride copolymers (mean molecule quantity is 100000)
20 parts of polyvinyl alcohol (Kuraray pva235 saponification degree 88%, average degree of polymerization 3500)
5 parts of boric acid (reagent is learned in permanent Xinghua, Tianjin)
20 parts of titanium dioxide (about 10 nanometers of average grain diameter)
6 parts of water-based ethylene-vinyl acetate copolymer emulsions (Dalian, Taiwan chemistry DA-100L)
10 parts of aqueous polyurethane emulsions (first SUPERFLEX of Industrial Co., Ltd 650)
0.5 part of calgon (three subsidiary factories of Tianjin chemical reagent six factories)
0.5 part of OP-10 (Tianjin reagent in rich morning)
614 parts of deionized waters
Precipitated silica is dispersed into stable aqueous dispersions with high-shear emulsion machine, and the titanium dioxide solid adopts high-shear emulsion machine under the condition that adds calgon, to be dispersed into stable aqueous dispersions.Under stirring at low speed,, continue to add polyvinyl alcohol, water-based ethylene-vinyl acetate copolymer emulsion, aqueous polyurethane emulsion and other auxiliary agents with after two kinds of dispersion liquids mixing.Stirring at low speed is even, obtains blotting covering layer coating fluid, and is subsequent use.
The preparation of ink solidifying layer coating fluid:
100 parts of precipitated silica (Beijing space flight Saden SD-520, about 2 microns of average grain diameter)
10 parts of dimethyl diallyl ammonium chloride copolymers (mean molecule quantity is 100000)
20 parts of polyvinyl alcohol (Kuraray pva235 saponification degree 88%, average degree of polymerization 3500)
5 parts of boric acid (reagent is learned in permanent Xinghua, Tianjin)
5 parts of water-based ethylene-vinyl acetate copolymer emulsions (Dalian, Taiwan chemistry DA-100L)
8.3 parts of aqueous polyurethane emulsions (first SUPERFLEX of Industrial Co., Ltd 650)
0.5 part of calgon (three subsidiary factories of Tianjin chemical reagent six factories)
0.5 part of OP-10 (Tianjin reagent in rich morning)
634 parts of deionized waters
Precipitated silica is dispersed into stable aqueous dispersions with high-shear emulsion machine, under stirring at low speed, continues to add polyvinyl alcohol, water-based ethylene-vinyl acetate copolymer emulsion, aqueous polyurethane emulsion and other auxiliary agents.Stirring at low speed is even, obtains the ink solidifying layer coating fluid, and is subsequent use.
Employing such as embodiment 1 said mode prepare the ink jet recording materials sample, and carry out test evaluation, and the result sees table 1.
Comparative example 1
The precipitated silica (Beijing space flight Saden SD-520, about 2 microns of average grain diameter) of blotting covering layer coating fluid among the embodiment 1 and ink solidifying layer coating fluid is replaced by fumed silica, and (primary particle diameter 14 nanometers of Degussa A-200, specific area is 200m
2/ g).Other conditions are with embodiment 1.Obtain comparative example 1 ink jet recording medium, evaluation result is seen table 1.
Comparative example 2
The water-based ethylene-vinyl acetate copolymer emulsion (Dalian, Taiwan chemistry DA-100L) of blotting covering layer coating fluid among the embodiment 1 and ink solidifying layer coating fluid is replaced by aqueous acrylic emulsion (federal chemical industry A-298).Other conditions are with embodiment 1.Obtain comparative example 2 ink jet recording mediums, evaluation result is seen table 1.
Comparative example 3
The aqueous polyurethane emulsion (first SUPERFLEX of Industrial Co., Ltd 650) of blotting covering layer coating fluid among the embodiment 1 and ink solidifying layer coating fluid is removed.Other conditions are with embodiment 1.Obtain comparative example 3 ink jet recording mediums, evaluation result is seen table 1.
Table 1: sample performance test data contrast
The method of testing of each item performance in the table 1 is following:
1. the method for testing of white sheet transmission density:
Ink jet recording medium is cut into the A4 specimen page, with X-Rite 361 its transmission densities of type densimeter measurement, gets 5 parallel determinations, its result gets its mean value.
2. the method for testing of white sheet covering power:
Ink jet recording medium is cut into the A4 specimen page, uses MJSB-WD-A photoelectricity haze meter to measure the mist degree of blank print, get 5 parallel determinations, its result gets its mean value.
Excellent: mist degree＞85%;
Very: 85%≤mist degree＜75%;
Difference: mist degree≤75%
3. the method for testing of water proofing property:
The side that ink jet recording medium is cut into 10cm * 10cm is fast, and the water of putting into 25 ℃ soaked 60 seconds, and the drying box that hangs on 80 ℃ is dry, treat the medium bone dry after, estimate the crackle bar number of its appearance.Estimate according to criterion.
√: crackle do not occur.
: crackle 1-3 bar occurs.
△: crackle 4-10 bar occurs.
*: crackle appears more than 10.
4. the method for testing of scratch resistance ability:
At ambient temperature ink jet recording medium is carried out the scratch resistance experiment with the scratch resistance appearance, write down critical counterweight quality in table 1.
5. the method for testing of ink absorption property:
Ink jet recording medium is used the HPZ6100 ink-jet printer; Adopt original-pack HP paint ink, print 100% cyan, article look, yellow, redness, green, blueness and black color lump respectively, after just printing has finished; Overlapping with paper at printing portion with PPC; Applying light, visual observations copy to PPC and duplicate degree with the printing ink on the paper, estimate by following standard.
√: do not duplicate fully.
△: duplicate slightly.
*: massive duplication.
6. the method for testing of color saturation:
Ink jet recording medium is used the HPZ6100 ink-jet printer; Adopt original-pack HP paint ink to print 100% black color lump; Printing finishes the back in 25 ± 2 ℃, 45 ± 2% damp condition drying 30 minutes down; With X-Rite 361 type densimeter measurements its black color lump transmission density and reflection density, respectively get 5 parallel determinations, its result gets its mean value.
7. the method for testing of anti-ultraviolet ability:
Use the X-RITE colorimeter to measure the Lab value of blank print, it is 10W that blank print is placed power, and wavelength is that the uviol lamp of 330 nanometers shines after 3 days down, re-uses the Lab value of X-RITE colorimeter measuring light according to the blank print in back, uses formula Δ E
2=(L-L*)
2+ (a-a*)
2+
2+ (b-b*)
2Calculate Δ E value.
Excellent: Δ E≤0.2;
Very: 0.2＜Δ E≤0.5;
Difference: Δ E＞0.5.
8. the method for testing of high-temp resisting high-humidity resisting performance:
Use the X-RITE colorimeter to measure the Lab value of blank print, it is 50 ℃ that blank print is placed temperature, aging after 3 days in the climatic chamber of humidity 80%, re-uses the Lab value that the X-RITE colorimeter is measured the blank print in aging back, uses formula Δ E
2=(L-L*)
2+ (a-a*)
2+
2+ (b-b*)
2Calculate Δ E value.
Excellent: Δ E≤0.2;
Very: 0.2＜Δ E≤0.5;
Difference: Δ E＞0.5.
Claims (5)
1. ink jet recording materials that is used for full-face spray light box film; It comprises support, ink solidifying layer and blotting covering layer; Contain inorganic pigment, aqueous polymer emulsion, water soluble polymer resin and cationic fixing agent in ink solidifying layer and the blotting covering layer respectively; It is characterized in that the inorganic pigment in the said blotting covering layer is the titanium dioxide of 0.5～10 micron precipitated silica and 10～500 nanometers; Inorganic pigment is 0.5～10 micron a precipitated silica in the said ink solidifying layer; Aqueous polymer emulsion in said ink solidifying layer and the blotting covering layer is water-based bipolymer emulsion and the aqueous polyurethane emulsion that has the ethene section of self-plasticizing action;
The precipitated silica in the said blotting covering layer and the weight ratio of titanium dioxide are 10～1: 1;
Said cationic fixing agent is the condensation body salt of polymine and salt, polyvinylamine and salt thereof, polyallylamine and salt thereof, acrylamide copolymer, dicyandiamide analog copolymer, secondary amine or epihalohydrin.
2. ink jet recording materials according to claim 1 is characterized in that, the consumption of the water-based bipolymer emulsion of said ethene section is 5～50% of an inorganic pigment weight.
3. ink jet recording materials according to claim 2 is characterized in that, the consumption of said aqueous polyurethane emulsion is 2.5～20% of an inorganic pigment weight.
4. ink jet recording materials according to claim 3 is characterized in that, the water-based bipolymer emulsion of said ethene section is the ethene-vinyl acetate polymer emulsion.
5. ink jet recording materials according to claim 4 is characterized in that, the consumption of said cationic fixing agent is 1～20% of an inorganic pigment weight; Said cationic fixing agent is that mean molecule quantity is 5000～100000 dimethyl diallyl ammonium chloride copolymer.
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| CN102152684A (en) * | 2010-12-29 | 2011-08-17 | 天津海华科技发展有限公司 | Full-transparent ink-jet printing film for improving absorbency on pigment ink |
| CN102729682A (en) * | 2012-07-16 | 2012-10-17 | 江苏泰特尔化工有限公司 | Anti-aging, highlight and waterproof ahead-spraying lamp-house piece |
| CN102991174A (en) * | 2012-12-27 | 2013-03-27 | 天津海华科技发展有限公司 | Front spraying light box film with efficient pigment ink absorbability |
| CN103897537B (en) * | 2012-12-27 | 2016-12-28 | 青岛佳艺影像新材料技术有限公司 | Delustring Weak solvent phase paper coating composition |
| CN103897517A (en) * | 2012-12-27 | 2014-07-02 | 青岛佳艺影像新材料技术有限公司 | Preparation method of front-spraying backlit inkjet film coating liquid |
| CN103897518B (en) * | 2012-12-27 | 2016-06-01 | 青岛佳艺影像新材料技术有限公司 | The preparation method of acid full-face spray light box film coating fluid |
| CN105818561A (en) * | 2015-05-27 | 2016-08-03 | 中山市有道化工科技有限公司 | Information record sheet material used for printing |
| CN105601969A (en) * | 2015-11-12 | 2016-05-25 | 合肥瑞旗精密涂层有限公司 | Waterproof ultraviolet-resistant oxidation-resistant front light inkjet film, and preparation method thereof |
| CN107699067B (en) * | 2016-08-04 | 2020-02-11 | 上海艾乐影像材料有限公司 | Release agent, release film, composite film, ink-jet printing medium, and preparation method and application thereof |
| CN106585155A (en) * | 2016-11-28 | 2017-04-26 | 江苏格美高科技发展有限公司 | Inkjet printing Chinese art paper and preparation process thereof |
| CN106590223A (en) * | 2016-11-28 | 2017-04-26 | 南通华润新材料有限公司 | Matte, waterproof and ink-absorbing coating and preparation method thereof |
| CN113500864B (en) * | 2021-07-10 | 2023-01-17 | 衡水鸿御科技有限公司 | Smooth type high accuracy film for drawing printout |
| CN115450066B (en) * | 2022-10-28 | 2023-05-30 | 江苏万宝瑞达高新技术有限公司 | Ink-jet synthetic paper and manufacturing method thereof |
| CN116285456B (en) * | 2023-03-08 | 2024-05-31 | 湖南肆玖科技有限公司 | Printable lettering film and preparation method thereof |
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| CN2417489Y (en) * | 2000-03-24 | 2001-01-31 | 深圳市大陆旭科技有限公司 | PVC back-spraying transparent film for color ink-jet printing |
| US20020037395A1 (en) * | 2000-07-21 | 2002-03-28 | Qiping Zhong | Ink jet recording medium |
| JP3902558B2 (en) * | 2003-03-07 | 2007-04-11 | 信越化学工業株式会社 | Silicone rubber sheet for thermocompression bonding |
| CN1539652A (en) * | 2003-10-27 | 2004-10-27 | 石深泉 | Film with mask of digital information and fabricating method |
| CN100471688C (en) * | 2006-11-30 | 2009-03-25 | 中国乐凯胶片集团公司 | Front-spraying film for water-proof ink jetting |
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