CN103897537B - Delustring Weak solvent phase paper coating composition - Google Patents
Delustring Weak solvent phase paper coating composition Download PDFInfo
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- CN103897537B CN103897537B CN201210577115.8A CN201210577115A CN103897537B CN 103897537 B CN103897537 B CN 103897537B CN 201210577115 A CN201210577115 A CN 201210577115A CN 103897537 B CN103897537 B CN 103897537B
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Abstract
The invention discloses a kind of delustring Weak solvent phase paper coating formulations, it comprises 20 30% self-crosslinking acrylic ester emulsions；20 30% ethylene-vinyl acetate copolymer emulsions；20 30% silica dispersions；Surplus is water.It uses bi-component mixing and micron order height hole silicon dioxide to improve blotting power, and the silicon dioxide being simultaneously introduced improves hardness and resistance to wiping.
Description
Technical field
The present invention relates to the coating formula of a kind of ink jet recording medium, be specifically related to the coating formula of the apparent absorbable Weak solvent ink of a kind of delustring.
Background technology
Ink-jet ink can be roughly divided into aqueous, solvent and UV by its main component and solidify ink.Solvent-based inks is mainly used in the exterior material such as lamp house cloth, PVC, and image quality is low but water-proof climate resisting good.Due to many containing esters and ketones solvent in solvent-based inks organic solvent, polluting and toxic is big, application can be subject to many limitations in the long run.Water-base ink precision is higher, environmental friendliness, but it is dried slow, and medium ink absorbing layer is required harshness, and after printing, picture needs aluminum coated steel again, and otherwise water proofing property and weatherability are very poor.
In order to combine both advantages, each printer manufacturer has released one after another Weak solvent ink spray drawing machine.Weak solvent ink uses harmless or that harm is less solvent such as lower alcohol, polylactic acid etc., the advantage having solvent inkjet ink and aqueous ink concurrently.The English name ECO-solvent of Weak solvent ink
Ink, ECO therein are considered as environmental protection (Environmentally
Safe), without coating ground (Uncoated media) and the abbreviation of outdoor weather resisteant (Outdoor durable), owing to Weak solvent prints, there is environmental protection, high accuracy and the advantage of outdoor weather resisteant, the most quickly instead of part wide cut aqueous ink wide format printer, especially in developed country markets such as America and Europes, more than 50 inches aqueous machine markets are almost replaced.
The strong kind solvents of ketone ester such as Ketohexamethylene, butanone, ethyl acetate are not used due to Weak solvent ink, not strong to the corrosion strength on output medium surface, need the coating (hereinafter referred to as Weak solvent coating) at media substrate surface coating absorbable Weak solvent ink.The defect that after the high light Weak solvent product of main flow generally exists surface hardness wiping low, resistance to difference and prints now, rate of drying is slow, product is single simultaneously.Delustring Weak solvent dielectric coated adds the silica filler of high hole, can further improve ink absorption ability and the surface hardness of Weak solvent coating, multiple Weak solvent ink printed equally it is applicable to high light Weak solvent product on the market, it can not only embody the high accuracy of indoor description file printing, property bright in luster, the advantage simultaneously well combining outdoor advertising materials, have without mounting film, good weatherability, the features such as deflection is preferable.
Summary of the invention
For the drawbacks described above overcoming prior art to exist, it is an object of the invention to, it is provided that a kind of delustring Weak solvent phase paper coating formulations, solve color effect after prior art prints bad, case hardness is low, and resistance to wiping is poor, and blotting speed is slow, the problem of top layer delustring.
The delustring Weak solvent phase paper coating formulations that the present invention provides, its component proportioning by mass percentage is:
Self-crosslinking acrylic ester emulsion 20-30%；
Ethene-vinyl acetate copolymer emulsion 20-30%；
Silica dispersions 20-30%；
Surplus is water.
Described self-crosslinking acrylic ester emulsion is water-based room temperature crosslinking acrylic acid ester emulsion；Described self-crosslinking acrylic ester emulsion contains N-[2-(2-methyl-4-oxopentyl) (DAAM) function monomer；Described self-crosslinking acrylic ester emulsion contains ammonia, volatile amine compounds, and ammonia, volatile amine compounds are single kind；Described self-crosslinking acrylic ester emulsion contains ammonia, volatile amine compounds, and ammonia, volatile amine compounds are several mixture；Described self-crosslinking acrylic ester emulsion contains adipic dihydrazide (ADH)；Described self-crosslinking acrylic ester emulsion solid content 30-60%；Described ethene-vinyl acetate copolymer emulsion solid content 40-70%；Described silica dispersions raw material components and proportion by weight thereof be: silicon dioxide 20 parts, (10%) 10 part of nitric acid, 70 parts of water；Described silicon dioxide is precipitated silica；Described silicon dioxide pore volume 1.2-2.5
Ml/g, dispersion liquid aggregate particle size 1-25um；N-[2-(2-methyl-4-oxopentyl) in described self-crosslinking acrylic ester emulsion is as function monomer, adipoyl hydrazine (ADH) is as cross-linking agent, volatilizable amine is as nertralizer, adding adipic dihydrazide in described self-crosslinking acrylic ester emulsion, when storage at normal temperature, emulsion keeps neutrality, and ketone carbonyl does not reacts with hydrazide group, and emulsion when being dried due to the volatilization of amine, system pH declines, and under the catalysis of acid, ketone carbonyl produces cross-linking reaction with hydrazide group, makes room temperature self-crosslinking acrylic ester emulsion.
The aggregate particle size of silica dispersions is defined as follows: be dispersed in pure water by silicon dioxide, and the mass concentration of silicon dioxide is 10%.This dispersion liquid with laser particle size analyzer (such as Malvern Zetasizer 3000HS,
Malvern Instruments Ltd., UK) test with dynamic light scattering method.
Synthetic silica can be made by wet method and gas phase legal system.The commercial varieties of wet silica substantially has: (1) precipitated silica (precipitated silica): sodium silicate and sulphuric acid are reacted in the basic conditions, silica dioxide granule is assembled and precipitates, its granular size constantly increases, it is then passed through filtering, cleans, is dried, grinds and classification processes, make finished product.Precipitated silica surface is faintly acid, and particle diameter is typically from l～50um, and surface area is from 30～800m2/ g, precipitated silica has internal porosity, and oil factor is high, is 175～320ml/100g, and specific surface comprises 5～8/nm2 of silicone hydroxyl group, and silicone hydroxyl gives precipitated silica water-wet behavior.Precipitated silica low cost, has different specific surface area, pore volume, the product of pore-size distribution all have merchandise sales, such as TOSOH
The Nipsil, K.K. of SILICA CORP. (Japanese)
TOKUYAMA(day Bender mountain) Tokusil, China Aerospace Saden SD series etc..(2) gel silica (silica gel): gel silica can be reacted in acid condition by sodium silicate and sulphuric acid and manufacture, in the method, little silica dioxide granule is dissolved in ageing process, and again precipitate between the primary granule that other volume is bigger, so that primary granule is joined to each other, therefore, structure clearly primary granule disappears, and is formed and has the agglomerated particle that internal pore structure is relatively hard.Commercial products has TOSOH
The Nipgel, Grace of SILICA CORP. (Japanese)
Syloid, Sylojet etc. of Davision.(3) Ludox (silica gel): Ludox is the ultramicron of silicic acid dispersion in water, and preparation method has ion exchange (Bird method), silica flour one one-step hydrolysis method, silane hydrolyzate method (Stober method) etc..Bird legal system obtains Ludox low cost of manufacture, but purity difference, surface hydroxyl hyperactivity, about 5/nm2 of silicone hydroxyl density, easily occur to reunite with adhesive, dispersant or other component in using and react.The commercial products of Ludox has Japanese Nissan
The Snowtex of Chemical Industries, Ltd., the Ludox etc. of U.S. Du pont.
Although gel silica pore volume is higher, internal void is harder, but cost exceeds much than the sedimentation method.Ludox and emulsion components in formula react and cause flocculation.Therefore the preferred precipitated silica of the present invention, further preferred pore volume 1.2-2.5
Ml/g, the precipitated silica of dispersion liquid aggregate particle size 1-25um.
Silicon dioxide pore volume is the highest, and the capillary action that its porosity is brought is the biggest, more can improve the absorption to solvent inkjet ink.But porosity is too high, the easy efflorescence of coating, the viscosity of coating fluid rises too fast being difficult to control to simultaneously.Pore volume is the least, then be difficult to improve the absorbability to solvent inkjet ink.
The particle diameter of silicon dioxide is crossed too, and the roughness of coating is too big, and when coating fluid is deposited, the sedimentation velocity of silicon dioxide easily settles layering too soon.Particle diameter is the least, the easy efflorescence of coating, and the viscosity of coating fluid rises too fast being difficult to control to.
The precipitated silica related in the present invention, owing to granularity is moderate, it it is again porous material, coating sink slowly, still have during coating surface drying and much stay surface, formed small uneven, make incident illumination become diffuse-reflectance at random, glossiness declines, but does not affect planarization and the feel of appearance of coat.
The delustring Weak solvent phase paper coating formulations that the present invention provides, it has the beneficial effects that, it uses bi-component mixing and micron order height hole silicon dioxide to improve blotting power, and the silicon dioxide being simultaneously introduced improves hardness and resistance to wiping.
Detailed description of the invention
Below in conjunction with six embodiments, the delustring Weak solvent phase paper coating formulations providing the present invention is described in detail.
The raw material preparing water-based room temperature crosslinking acrylic acid ester emulsion is shown in Table one.
Table one
The formula of water-based room temperature crosslinking acrylic acid ester emulsion is shown in Table two.
Table two
The synthesis technique of water-based room temperature crosslinking acrylic acid ester emulsion:
(1) prepared by pre-emulsion
In equipped with the 500ml four-necked bottle of motor stirrer, thermometer, condensing tube and Dropping funnel, add first paragraph monomer, emulsifying agent and deionized water, at 54 ± 2 DEG C of stir about 10min, obtain pre-emulsion.
(2) prepared by seed emulsion
Take 1/4 pre-emulsion in four-necked bottle, be warming up to 74 ± 2 DEG C, then drip 1/4 APS solution, react about 30min, prepare seed emulsion.
(3) prepared by core emulsion
Remaining APS liquid being divided into four parts, keeps reaction temperature constant, add a APS liquid in reaction bulb, and drip residue 3/4 pre-emulsion, 1h drips off, and wherein adds a APS liquid every 30min.
(4) prepared by shell emulsion
Second segment monomer, emulsifying agent and deionized water is added in equipped with the 500ml four-necked bottle of motor stirrer, thermometer, condensing tube and Dropping funnel, at 54 ± 2 DEG C of stir about 10min, obtain pre-emulsion, the most slowly drip in above-mentioned core emulsion, drip in 1h, insulation reaction 2h, wherein add a APS liquid every 30min, be warming up to 80 ± 1 DEG C, react 2h, it is down to room temperature, and it is slowly added to 10% ADH aqueous solution, it is neutralized to neutrality with ammonia, filters, discharging, obtains a kind of milky emulsion in blue light.
Embodiment 1
Prepared by silica dispersions:
Under room temperature, take silicon dioxide (SD-520, Beijing Space Saden powder technology company limited, pore volume 1.6-1.8ml/g, particle diameter 4um) 20 parts, (10%) 10 part of nitric acid, add dispersion machine high speed after the mixing of 70 parts of water and disperse 1 hour, be configured to silica dispersions.
Prepared by coating fluid:
Under room temperature, take described self-crosslinking acrylic ester emulsion 20-30 part, ethylene-ethyl acetate copolymer emulsion EP765S(VINNAPAS, Wa Ke Shanghai company limited, solid content 59.5%) 20-30 part, silica dispersions 20-30 part, surfactant (TX-10) 1-5 part, residue use water polishing mixing, prepares delustring Weak solvent printing paper coating fluid by 30 minutes mechanical agitation.
Above-mentioned coating fluid is coated on RC paper substrate with 150g by bar coating machine, then, coated carrier is dried at a temperature of 65 DEG C 60 minutes prepared samples.Test sample blotting speed is 2-3 minute, it is achieved that i.e. beat the most dry effect；60 ° of angle of incidence Portable vancometer test glossiness are 2-5.
Embodiment 2
Prepared by silica dispersions:
Under room temperature, take silicon dioxide (SD-520 Beijing Space Saden powder technology company limited, pore volume 1.6-1.8ml/g, particle diameter 4um) 20 parts, (10%) 10 part of nitric acid, add dispersion machine high speed after the mixing of 70 parts of water and disperse 1 hour, be configured to silica dispersions；
Prepared by coating fluid:
Under room temperature, take the pure-acrylic emulsion (HX337-6 that concentration is 40%, Shanghai is to haze chemical industry) 20-30 part, concentration is EVA emulsion 4500(VINNAPAS of 40%, Wa Ke Shanghai company limited, solid content 59.5%) 20-30 part, described silica dispersions 20-30 part, surfactant (TX-10) 1-5 part, residue use water polishing mixing, prepare delustring Weak solvent printing paper coating fluid by 30 minutes mechanical agitation.
Above-mentioned coating fluid is coated on RC paper substrate with 150g by bar coating machine, then, coated carrier is dried at a temperature of 65 DEG C 60 minutes prepared samples.Test sample blotting speed is 2 minutes, it is achieved that i.e. beat the most dry effect；60 ° of angle of incidence Portable vancometer test glossiness are 2-5.
Embodiment 3
Prepared by silica dispersions:
Under room temperature, take silicon dioxide (SD-640, Beijing Space Saden powder technology company limited, pore volume 1.4-1.6ml/g, particle diameter 2um) 20 parts, (10%) 10 part of nitric acid, add dispersion machine high speed after the mixing of 70 parts of water and disperse 1 hour, be configured to silica dispersions.
Coating fluid is prepared with embodiment 1.
Above-mentioned coating fluid is coated on RC paper substrate with 150g by bar coating machine, then, coated carrier is dried at a temperature of 65 DEG C 60 minutes prepared samples.Test sample blotting speed is 2 minutes, it is achieved that i.e. beat the most dry effect；60 ° of angle of incidence Portable vancometer test glossiness are 1-4.
Embodiment 4
Prepared by silica dispersions:
Under room temperature, take silicon dioxide (SD-640, Beijing Space Saden powder technology company limited, pore volume 1.4-1.6ml/g, particle diameter 2um) 20 parts, (10%) 10 part of nitric acid, add dispersion machine high speed after the mixing of 70 parts of water and disperse 1 hour, be configured to silica dispersions.
Coating fluid is prepared with embodiment 2.
Above-mentioned coating fluid is coated on RC paper substrate with 150g by bar coating machine, then, coated carrier is dried at a temperature of 65 DEG C 60 minutes prepared samples.Test sample blotting speed is 2 minutes, it is achieved that i.e. beat the most dry effect；60 ° of angle of incidence Portable vancometer test glossiness are 1-4.
Embodiment 5
Prepared by silica dispersions:
Under room temperature, take silicon dioxide (SD-690, Beijing Space Saden powder technology company limited, pore volume 1.4-1.6ml/g, particle diameter 2um) 20 parts, (10%) 10 part of nitric acid, add dispersion machine high speed after the mixing of 70 parts of water and disperse 1 hour, be configured to silica dispersions.
Coating fluid is prepared with embodiment 1.
Above-mentioned coating fluid is coated on RC paper substrate with 150g by bar coating machine, then, coated carrier is dried at a temperature of 65 DEG C 60 minutes prepared samples.Test sample blotting speed is 2 minutes, it is achieved that i.e. beat the most dry effect；60 ° of angle of incidence Portable vancometer test glossiness are 1-4.
Embodiment 6
Prepared by silica dispersions:
Under room temperature, take silicon dioxide (SD-520, Beijing Space Saden powder technology company limited, pore volume 1.8-2.5ml/g, particle diameter 2um) 20 parts, (10%) 10 part of nitric acid, add dispersion machine high speed after the mixing of 70 parts of water and disperse 1 hour, be configured to silica dispersions.
Coating fluid is prepared with embodiment 2.
Above-mentioned coating fluid is coated on RC paper substrate with 150g by bar coating machine, then, coated carrier is dried at a temperature of 65 DEG C 60 minutes prepared samples.Test sample blotting speed is 2 minutes, it is achieved that i.e. beat the most dry effect；60 ° of angle of incidence Portable vancometer test glossiness are 1-4.
Comparative example 1
Under room temperature, take described self-crosslinking acrylic ester emulsion 20-30 part, ethylene-ethyl acetate copolymer emulsion EP765S(VINNAPAS, Wa Ke Shanghai company limited, solid content 59.5%) 20-30 part, described silica dispersions 20-30 part, surfactant (TX-10) 1-5 part, residue use water polishing mixing, prepares delustring Weak solvent printing paper coating fluid by 30 minutes mechanical agitation.
Above-mentioned coating fluid is coated on RC paper substrate with 150g by bar coating machine, then, coated carrier is dried at a temperature of 65 DEG C 60 minutes prepared samples.Test sample blotting speed is 20-30 minute, and rate of drying is slow；60 ° of angle of incidence Portable vancometer test glossiness are 28-30.
Comparative example 2
Under room temperature, take the pure-acrylic emulsion (HX337-6 that concentration is 40%, Shanghai is to haze chemical industry) 20-30 part, concentration is EVA emulsion 4500(VINNAPAS of 40%, Wa Ke Shanghai company limited, solid content 59.5%) 20-30 part, described silica dispersions 20-30 part, surfactant (TX-10) 1-5 part, residue use water polishing mixing, prepare delustring Weak solvent printing paper coating fluid by 30 minutes mechanical agitation.
Above-mentioned coating fluid is coated on RC paper substrate with 150g by bar coating machine, then, coated carrier is dried at a temperature of 65 DEG C 60 minutes prepared samples.Test sample blotting speed is 20-30 minute, and rate of drying is slow；60 ° of angle of incidence Portable vancometer test glossiness are 25-28.
Claims (9)
1. a delustring Weak solvent phase paper coating composition, it is characterised in that: its component proportioning by mass percentage is: self-crosslinking
Acrylic acid ester emulsion 20-30%, ethene-vinyl acetate copolymer emulsion 20-30%, silica dispersions 20-30%, surface activity
Agent TX-10 1-5%, surplus is water；Described silica dispersions raw material components and proportion by weight thereof be: silicon dioxide 20
Part, concentration is 10 parts of the nitric acid of 10%, 70 parts of water；Described silicon dioxide pore volume 1.2-2.5 mL/g, dispersion liquid aggregate particle size 1-25
μm。
Delustring Weak solvent phase paper coating composition the most according to claim 1, it is characterised in that: described self-crosslinking propylene
Acid esters emulsion is water-based room temperature crosslinking acrylic acid ester emulsion.
Delustring Weak solvent phase paper coating composition the most according to claim 1, it is characterised in that: described self-crosslinking propylene
Acid esters emulsion contains N-[2-(2-methyl-4-oxopentyl) function monomer.
Delustring Weak solvent phase paper coating composition the most according to claim 1, it is characterised in that: described self-crosslinking propylene
Acid esters emulsion contains ammonia, volatile amine compounds, and described ammonia, volatile amine compounds are single kind.
Delustring Weak solvent phase paper coating composition the most according to claim 1, it is characterised in that: described self-crosslinking propylene
Acid esters emulsion contains ammonia, volatile amine compounds, and described ammonia, volatile amine compounds are several mixture.
Delustring Weak solvent phase paper coating composition the most according to claim 1, it is characterised in that: described self-crosslinking propylene
Acid esters emulsion contains adipic dihydrazide.
Delustring Weak solvent phase paper coating composition the most according to claim 1, it is characterised in that: described self-crosslinking propylene
Acid esters emulsion solid content 30-60%.
Delustring Weak solvent phase paper coating composition the most according to claim 1, it is characterised in that: described ethyl vinyl acetate second
Alkene copolymer emulsion solid content 40-70%.
Delustring Weak solvent phase paper coating composition the most according to claim 1, it is characterised in that: described silicon dioxide is heavy
Shallow lake method silicon dioxide.
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| CN108466422B (en) * | 2015-04-17 | 2020-06-19 | 珠海天威飞马打印耗材有限公司 | Working method of three-dimensional printer |
| CN105131747B (en) * | 2015-08-06 | 2018-08-21 | 乐凯胶片股份有限公司 | A kind of environmentally-frieweak weak solvent type inkjet medium and preparation method thereof |
| CN106221468A (en) * | 2016-08-19 | 2016-12-14 | 上海谷奇数码科技有限公司 | Multi-functional Weak solvent prints coating and preparation method thereof |
| CN109263335B (en) * | 2018-08-22 | 2021-02-26 | 安徽文峰特种纸业有限公司 | Anti-aging film-covering-free ink-jet printing photo paper |
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| CN101879820A (en) * | 2010-06-24 | 2010-11-10 | 中国乐凯胶片集团公司 | Ink-jet recording material used for full-face spray light box film |
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