KR100681894B1 - Color Inkjet Printing Paper and Process Thereof - Google Patents

Abstract

(1) 4 to 6 weights of cation-modified polyvinyl alcohol and cation-modified polyvinylpyrrolidone with a mixing ratio of 1: 0.3 to 0.7 so that color ink can be absorbed well by a computer digital inkjet printer. % Alumina having a primary particle size of 10-25 nm, zeta potential 40-44 ㎷, BET 103-171 m 2 / g and porosity 0.6-0.9 dl / g in 200-320 ml of aqueous solution Alumina sol dispersion step prepared by dispersing; (2) adding 0.6 to 1.5% by weight of dodecyltrimethylammoniummethylchloride cationic surfactant to the hydrophilic butadiene-styrene copolymer emulsion to obtain a cationic hydrophilic polymer; (3) an alumina polymer sol manufacturing step of preparing an alumina polymer sol having a viscosity of 15 to 40 cps and a zeta potential of 43 to 50.12 kPa by mixing 40 to 65% by weight of alumina sol with a remainder; (4) an application step of applying an alumina polymer sol in a range of 10 to 60 mu m by applying a thin film of 1 to 4 layers with a srod die coater on a photo paper at 30 to 36 DEG C; (5) It provides a method for producing a color inkjet printer photo paper comprising a drying step of drying the photo paper coated with the alumina polymer sol in the coating step.

Zeta potential, cationic polymer, alumina polymer sol, color printer, particle space, porosity

Description

Color inkjet printer photo paper and manufacturing method thereof {Color Inkjet Printing Paper and Process Thereof}

1 is a graph showing the zeta potential of the alumina polymer sol in the method of manufacturing a color inkjet printer photo paper according to the present invention.

2 is a photograph of the primary particle size of alumina in the method of manufacturing a color inkjet printer photo paper according to the present invention.

3 is a photograph of a secondary particle size of alumina in a method of manufacturing a color inkjet printer photo paper according to the present invention, in which alumina polymer sol is applied to a photo paper base and dried.

4 is a schematic diagram for explaining a state in which an alumina polymer sol is applied to a photo paper base paper in the method for manufacturing a color inkjet printer photo paper according to the present invention.

Fig. 5 is a schematic diagram for explaining the behavior of printing in a state where the alumina polymer sol is applied to a photo paper base and dried in the method for producing a color inkjet printer photo paper according to the present invention.

6 is a 200-fold enlarged side optical photograph of a state in which a layer of alumina polymer sol is applied in the method of manufacturing a color inkjet printer photo paper according to the present invention.

FIG. 7 is a 200-fold enlarged side optical photograph of a state in which two layers of alumina polymer sol are applied in a method of manufacturing color inkjet printer photo paper according to the present invention.

8 is a 200-fold enlarged side optical photograph of a state in which three layers of alumina polymer sol are applied in the method of manufacturing a color inkjet printer photo paper according to the present invention.

9 is a 200-fold enlarged side optical photograph photographing a state in which four layers of alumina polymer sol are applied in the method of manufacturing color inkjet printer photo paper according to the present invention.

FIG. 10 is a 200-fold enlarged side optical photo of a method of manufacturing a color inkjet printer photo paper according to the present invention, in which a line having a thickness of 0.1 μm is printed on a photo paper coated with one layer of alumina polymer sol.

FIG. 11 is a 200-fold enlarged side optical photograph of a method of manufacturing a color inkjet printer photo paper according to the present invention, in which a 0.1 μm-thick line is printed on a photo paper coated with two layers of alumina polymer sol.

FIG. 12 is a 200-fold enlarged side optical photo of a method of manufacturing a color inkjet printer photo paper according to the present invention, in which a line having a thickness of 0.1 μm is printed on a photo paper coated with three layers of alumina polymer sol.

FIG. 13 is a 200-fold enlarged side optical photograph of a method of manufacturing a color inkjet printer photo paper according to the present invention, in which a line having a thickness of 0.1 μm is printed on photo paper coated with four layers of alumina polymer sol.

The present invention relates to a color inkjet printer photo paper and a method of manufacturing the same, and more particularly, a water-soluble polymer and a neutral latex polymer are used as a cationic surfactant. Color printer image produced by forming a color ink absorption receiving layer with alumina polymer sol mixed with a cationic hydrophilic polymer and an oxidizing stabilizer is used to print a color image of a computer screen using a digital inkjet printer in yellow, magenta and cyan colors. And / or physicochemical properties such as ink penetrability, ink drying, water resistance, glossiness, weather resistance, alcohol resistance, versatility, rubbing resistance, whiteness, smoothness and light resistance in printing black color ink. An excellent color inkjet printer photo paper and a method of manufacturing the same.

Recently, the supply of color inkjet printers is becoming more common as the supply of digital cameras and digital mobile phones is rapidly increasing, and high quality of images printed by color inkjet printers is required. Various studies are being done to obtain.

For example, a polymer sol which forms an ink absorbing water-receiving layer prepared from a polyvinyl alcohol (hereinafter referred to as PVA), a polyvinypyrrolidone (hereinafter referred to as PVP) as a water-soluble polymer, and a sol using a polyurethane as a composite agent. (J, image sci, Tech vol 45, No 1, 2000).

And a study for obtaining excellent properties using compounds such as water-soluble polymer cellulose, gelatin, starch and the like, polyurethane, polyacrylate, acryl-styrene, polyimide copolymer, acrylonitrile-butadiene-styrene copolymer, etc. Is actively underway.

For example, European Patent Nos. 934,905 and US Pat. No. 5,856,023 disclose the use of alumina sol and PVA as binders, and European Patent No. 937,825 discloses alumina sol; a gelling agent cyclotextrin compound and optionally a binder. An inkjet recording sheet having at least one adhesive layer on its surface is disclosed, and EP 887,201 discloses an inkjet recording sheet having an image receiving layer by mixing PVA, PVP and styrene-butadiene with a binder.

In addition, US Patent No. 5,856,023, US Patent No. 5,662,997, European Patent No. 1,219,457, and Japanese Patent No. 172,850 disclose an inkjet recording sheet having an ink receiving layer including modified PVA and unmodified PVA.

As described above, even when a photo paper having an inkjet printer receiving layer is prepared by adding a softener, a curing agent, an oxidative stabilizer, an antistatic agent, a defoamer, an ultraviolet absorber, and a fluorescent brightener to the ink absorbing water-soluble polymer sol thus prepared, Due to the low formation, the absorption ability of the ink solution having anions is lowered, and the ink penetration rate is lowered in the photographic images printed by the inkjet printer, so the drying speed is slow, the gloss is lowered, the alcohol resistance, the weather resistance, the water resistance is weak, the rubbing resistance, etc. There is a problem in that the color and chemical properties of the resin are poor, so that an excellent color image cannot be obtained from an image printed by an inkjet printer.

In addition, the alumina polymer sol, which has previously used polymers such as water-soluble polyacryl, polyacryl styrene, and polyacrylurea as a binder, when manufactured with inkjet photo paper, has a hardened surface, resulting in slow ink penetration, slow drying, and an ink absorbing layer. There are physical problems that separate from photo paper.

Accordingly, in the present invention, various researches have been conducted to solve the above problems. As a cationic surfactant, dodecyl trimethyl ammonium methyl chloride was added to the butadiene-styrene emulsion zone used as a hydrophilic binder, and thus, the ink penetration was rapidly increased. To develop a high zeta potential alumina polymer comprising a cationized butadiene-styrene emulsion and nanoparticle alumina, and furthermore, a hydrophilic oxidation stabilizer triethylene glycol-bis- [3 (3-tet-butyl-4 -Hydroxy-5-methylphenyl) propionic acid] (triethyleneglycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate]) Emulzon average particle size of 3.3 ~ 3.7㎛ By increasing the light resistance of the image and using it to form an ink receiving layer, the ink absorption speed of the anion is fast, permeability is good, and the drying speed is high. It was confirmed that the present invention can provide a color image excellent in weather resistance, water resistance, glossiness, alcohol resistance, rubbing resistance, resistance, whiteness and smoothness, and completed the present invention.

An object of the present invention is to print a computer screen with a printer photo paper manufactured with a color ink-receiving layer made of alumina polymer sol having a high zeta potential value obtained by mixing a porous alumina sol having a size of 10-25 nm with a cationic water-soluble polymer and a cationic hydrophilic polymer with a cationic surfactant. Color, yellow, magenta, cyan and / or black color inks by printing a color image of a digital inkjet printer to increase ink dryness, water resistance, glossiness and alcohol resistance. The present invention provides a color inkjet printer photo paper which maintains excellent physical and chemical properties such as resistance to weathering, weather resistance, general purpose, rubbing resistance, curling resistance, whiteness, smoothness and light resistance, and a manufacturing method thereof.

In the method for producing a color inkjet printer photo paper proposed by the present invention, (1) a cation-modified polyvinyl alcohol and a cation-modified polyvinylpyrrolidone having a pH ratio of 3.0 to 4.5 and a cation-modified polyvinylpyrrolidone having a mixing ratio (weight ratio) of 1: 0.3 to 0.7 ratio are 4 to 4. 200-320 ml of aqueous solution containing 6% by weight of pH 3.0-4.5, primary particle size 10-25 nm, zeta potential 40-44 mA, BET 103-171 m 2 / g and porosity 0.6-0.9 m 2 / an alumina sol dispersing step prepared by dispersing 90 to 130 g of alumina having HP g (HP 10 to 40 (trade name; manufactured by Sasol); (2) adding a dodecyltrimethylammoniummethylchloride cationic surfactant to the hydrophilic butadiene-styrene copolymer emulsion in a proportion of 0.6 to 1.5% by weight to obtain a cationic hydrophilic polymer; (3) 40 to 65% by weight of the alumina sol obtained in the alumina sol dispersion step of (1) and the polymer obtained in the cationic hydrophilic polymer preparation step of (2) as a balance, the viscosity of 15 to 40cps, zeta potential 43 An alumina polymer sol manufacturing step of preparing an alumina polymer sol having ˜50.12 Hz; (4) an application step of applying the alumina polymer sol obtained in the alumina polymer sol manufacturing step by applying a thin film of 1 to 4 layers with a srod die coater on a sheet of photo paper at 30 to 36 ° C. to apply a coating thickness in a range of 10 to 60 μm; (5) comprises a drying step of drying the photo paper coated with the alumina polymer sol in the coating step.

Triethyleneglycol-bis- [3 (3-tet-butyl-4-hydroxy-5-methylphenyl) propionic acid] (Triethyleneglycol-bis [3- (3-) as an oxidation stabilizer in the alumina polymer sol preparation step of (3). tert-butyl-4-hydroxy-5-methylphenyl) propionate]) It is also possible to prepare an alumina polymer sol having a viscosity of 15 to 40 cps by further adding the emulsion zone to the alumina polymer sol at a ratio of 0.2 to 0.8% by weight.

When the oxidative stabilizer is added as described above, the preservation of color is improved and durability is improved.

As the photo paper base paper, art paper, casp coated paper (CCP) paper, synthetic paper, polyethylene coated paper paper, etc. can be used.

By adjusting the mixing time in the alumina polymer sol preparation step of (3), it is also possible to produce a secondary alumina particle size of 30 to 60 nm with fast ink absorption.

It is also possible to further add 10 to 30 ml of the content of 10% propyl alcohol in the alumina polymer sol preparation step of (3).

In the step of preparing the alumina polymer sol of (3), it is also possible to add 3 to 10 ml of content of 3% sodium sulfite or sodium thiosulfate as a film-forming agent.

The alumina polymer sol may further include at least one or two or more additives selected from the group consisting of a fluorescent brightener, a defoamer, a surfactant, a lubricant, a UV absorber, a brightener, an anti-curling agent, and the like. For example, tinuvin 205 as a UV absorber, triethylene glycol as a curling inhibitor, and dodecyl benzene sulfonide as a surfactant can be used.

In the case of applying the thin alumina polymer sol of the above (3) with a multi-layered rod die coater, one layer has 3 to 35 µm, two layers have 5 to 8 µm, three layers have 3 to 5 µm, and four layers have 3 to 3 It is apply | coated in the range of 5 micrometers.

The multilayer coating can be set in combination with the thickness of each layer so that the total thickness applied from one layer to four layers is within the range of 10 to 60 µm.

Multi-layer coating in the above can also be configured to apply two or more layers at the same time in sequence using a rod die coater is provided with a plurality of nozzles. That is, one layer is applied as the slide die coater moves once, and then two, three, and four layers are sequentially applied simultaneously.

When the coating thickness is less than 10 μm, the ink and the ink solvent are mixed to reduce the quality of the printed image. When the coating thickness exceeds 60 μm, the water resistance tends to be inferior.

Photo paper coated in the drying step (5) above 15 to 20 seconds in the first drying zone 5-8 ℃, 10 to 25 seconds in the second drying zone 20 ~ 28 ℃, 15 to 15 to the third drying zone 50 ~ 65 ℃ It is preferable to dry in order of 30 to 40 second at -20 second and the 4th drying area 80-110 degreeC.

The drying is preferably carried out by setting the secondary alumina particles in the form of a rank moor in the surface, the coated side in the form of a non-type, and setting the drying conditions in which the particle space can be maintained at 2 to 6 nm.

The primary particles of the alumina used in the alumina sol in the above is made of boenmite and / or needle-like.

The cation modified polyvinyl alcohol and cation modified polyvinyl pyrrolidone function as a binder.

The alumina sol is preferably added in a range of 40 to 70% by weight based on the total amount of the alumina polymer sol.

When the amount of the alumina sol added is less than 40% by weight, the size of the secondary alumina particles cannot be grown to 40 to 60 nm, so that the ink absorption is slowed to dry, and when the amount exceeds 70% by weight, matte and cracks are formed. There is concern.

The modified polyvinyl alcohol and modified polyvinyl pyrrolidone used as the binder are preferably used in a range of 15 to 30% by weight based on the total amount of the alumina polymer sol.

If the binder is less than 15% by weight, there is a high possibility that cracks are formed, and if the binder is more than 30% by weight, ink absorption tends to be inferior.

The hydrophilic butadiene-styrene copolymer emulsion zone used for increasing the adhesion is preferably set in the range of 0.6 to 1.5% by weight based on the total amount of the alumina polymer sol.

When the hydrophilic copolymer emulsion zone is used in less than 0.6% by weight, the adhesive strength is lowered. When the hydrophilic copolymer emulsion zone is used in excess of 1.5% by weight, ink absorption tends to be hindered.

And the manufacturing method of the color inkjet printer photo paper of the present invention is the primary adjusted to pH 3.0-4.5 while stirring the cation-modified polyvinyl alcohol and the cation-modified polyvinyl pyrrolidone aqueous solution as a binder at a high speed of 1500rpm at a temperature of 38 ~ 45 ℃ Particle size 10-25 nm alumina was dispersed and mixed therein, and then hydrophilic cationic butadiene-styrene copolymer emulsion was mixed therein, and triethylene glycol-bis- [3 (3-tet-butyl- 4-hydroxy-5-methylphenyl) propionic acid] (Triethyleneglycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate]).

Through the above process, it is possible to provide a color ink receiving layer alumina polymer sol having excellent absorption of inkjet ink, good light resistance, good water resistance, increased glossiness, and increased adhesion.

When the alumina polymer sol provided as described above is applied to the photo paper base and dried, the zeta potential of the alumina polymer ink receiving layer becomes 11.83 to 12.60 Pa, and the zeta potential of the portion absorbing yellow, magenta, cyan and black inks is increased. It will increase from 23.01 to 28.64 ms.

And the color inkjet printer photo paper of the present invention is 4 to 6% by weight of the photo paper and the cation-modified polyvinyl alcohol and cation-modified polyvinyl pyrrolidone at pH 3.0 to 4.5 at a ratio of 1: 0.3 to 0.7. A polymer prepared by mixing and dispersing alumina sol prepared by dispersing 90 to 130 g of alumina having a pH of 3.0 to 4.5 and primary particle size of 10 to 25 nm in 200 to 320 ml of an aqueous solution included in a hydrophilic cationic butadiene-styrene copolymer emulsion. And an ink receiving layer formed by applying a sol to the photo paper base material in a coating thickness of 10 to 60 mu m and drying it.

The alumina dispersed in the alumina sol maintains a zeta potential of 40 to 44 kV, BET 103 to 171 m 2 / g, and a porosity of 0.6 to 0.9 mW / g. Examples of the alumina include HP10, HP14, HP18, HP20, HP22 (above trade name; manufactured by Sasol).

The ink receiving layer is formed by applying one or more layers of polymer sol.

The ink receiving layer is formed by mixing alumina sol with a water-soluble and cationic hydrophilic binder resin to have a zeta potential of 43 to 50.12 ㎷, a porous alumina secondary particle size of 30 to 60 nm, and a particle space of 2 to 6 nm.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited thereto. Hereinafter, preferred embodiments and comparative examples of the present invention will be described.

The following examples are intended to illustrate the invention and should not be understood as limiting the scope of the invention.

Example 1

1000 ml of a 10 wt% polyvinyl alcohol aqueous solution of a water-soluble polymer was adjusted to pH 3.3 in a round flask, and 30 ml of 0.8 wt% dodecyltrimethylammonium methyl chloride was injected at 65 ° C. for 25 minutes, followed by stirring for 2 hours, and the temperature was 30 Cool to C to prepare Cationized Polymer 1.

Example 2

1000 ml of a 5% by weight polyvinyl pyrrolidone aqueous solution of a water-soluble polymer was adjusted to pH 3.3 in a round flask, 25 ml of 0.4% by weight dodecyltrimethylmethylammonium methyl chloride was injected at 65 ° C. for 25 minutes, followed by stirring for 2 hours. The temperature was cooled to 30 ° C. to prepare cationized polymer 2.

Example 3

Hydrophilic polymer 3% by weight Butadiene-styrene copolymer Emulsion 500ml 45 ℃, 1500rpm while stirring with 0.01N sodium bicarbonate titration adjusted to pH 3.4, when the emulsion is entangled 300 ℃ 300ml 0.3ml % Dodecyltrimethylammonium methyl chloride was added thereto, followed by stirring for 2 hours to prepare a cationized polymer 3.

In Table 1 below, zeta potentials before and after adding a cationic surfactant (dodecyltrimethylammoniummethyl chloride) to 1,000 ml of butadiene-styrene copolymer emulsion are measured. The zeta potential was measured using an ELS 8000 (product of Otsuka Electronics Co., Ltd. Japan).

Added amount of cationic surfactant pH Zeta potential Before addition After addition 10 ml 3.4 36 40 25 ml 3.4 36 42 30 ml 3.4 36 43 40 ml 3.4 36 43

As can be seen from Table 1, the zeta potential was increased compared to the case where the cationic surfactant was not added.

Example 4

Alumina sol having a pH of 3.3 and a particle size of 20 to 25 nm (HP18 (H18) while maintaining 200 ml of 6 wt% cation modified polyvinyl alcohol of Polymer 1 and 2 wt% cation modified polyvinyl pyrrolidone of Polymer 2 at 43 ° C. 250 ml of 22 weight% and 300 ml of 3 weight% of butadiene-styrene copolymers are added, and it stirs at 1500 rpm and mixes. At this time, while mixing, add a few drops of 0.2% by weight of a defoamer (Sen 384 (trade name; Sannopus Co.)). Next, 15 ml of 4% by weight propyl alcohol was added to the mixture, and 3 ml of 4% by weight butyl alcohol and 30 ml of polymer 3 were added and mixed with 10 ml of 0.5% by weight of an antioxidant stabilizer (product of Korea Songwon Industry). 15 ml of 1% by weight dodecylbenzelselperate, 10 ml of 1% by weight polyethylene glycol, and 20 ml of 0.3% by weight sodium thiosulfate were added thereto to prepare an alumina polymer sol 1 having a viscosity in the range of 15 to 40 cps.

The result of measuring the zeta potential of the alumina polymer sol prepared as described above is shown graphically in FIG. 1.

Then, the alumina polymer sol 1 prepared as described above was applied to a paper sheet with a thickness of 33 μm using a srod die coater, dried, and then measured in various properties of the color inkjet printer photo paper. .

The step of applying and drying the alumina polymer sol is 15 to 20 seconds in the first drying zone 5 to 8 ℃, 10 to 25 seconds in the second drying zone 20 to 28 ℃, 50 to 65 ℃ in the third drying zone 15 to 20 seconds, and the fourth drying region in the order of 30 to 40 seconds at 80 to 110 ℃.

As described above, the secondary alumina shape of the dried ink absorbing layer is arranged in a rank moor shape and a side surface in a bitty shape, and has a particle size of 40 to 60 nm and a space spacing between secondary particles of 2 to 6 nm. Set the drying conditions so that they can be dispersed.

2 shows an electron microscope picture of 100,000 times of alumina having a primary particle size of 10 to 25 nm, and FIG. 3 shows electrons photographing alumina having a secondary particle size of 30 to 60 nm coated with an alumina polymer sol. A microscope picture of 100,000 times is shown.

4 shows a surface in which alumina secondary particles are arranged in a rank moor shape, and in FIG. 5, side surfaces and particle spaces arranged in a non-typical shape.

FIG. 6 shows a 200-fold side optical photograph showing a state in which the ink is absorbed (received) to a thickness (depth) of 20 µm when printing is carried out using magenta ink in Example 4, and FIG. 10 Shows a 200 times optical photograph showing a state in which a line having a thickness of 0.1 mu m is printed.

As can be seen from FIG. 10, since the line having a thickness of 0.1 μm is clearly distinguished, it can be confirmed that the resolution is excellent.

Example 5

Distilled water was added to the alumina polymer sol 1 of Example 4 to prepare an alumina polymer sol 2 having a viscosity of 10 to 30 cps.

Then, on the photo paper, one layer was coated with alumina polymer sol 1 at a coating thickness of 26 μm, and the second layer was coated with alumina polymer sol 2 at a coating thickness of 8 μm, dried under the same drying conditions as in Example 4, and then colored. The result of having measured the various characteristic of the inkjet printer photo paper is shown in following Table 2.

The alumina polymer sol is applied to the alumina polymer sol 1 using the sroded die coater provided with a plurality of nozzles, and the alumina polymer sol 2 is sequentially applied onto the alumina polymer sol 1.

FIG. 7 shows a 200-fold side optical photograph showing a state in which the ink is absorbed (received) to a thickness (depth) of 25 μm when printing is performed using magenta ink in Example 5, and FIG. 11 Shows a 200 times optical photograph showing a state in which a line having a thickness of 0.1 mu m is printed.

As can be seen from FIG. 11, since the line having a thickness of 0.1 μm is clearly distinguished, it can be confirmed that the resolution is excellent.

Example 6

Distilled water was added to the alumina polymer sol 1 of Example 4 to prepare an alumina polymer sol 3 having a viscosity of 8 to 25 cps.

On the photo paper, one layer was coated with alumina polymer sol 1 at a coating thickness of 20 μm, the second layer was coated with alumina polymer sol 2 at a coating thickness of 8 μm, and the third layer was coated with alumina polymer sol 3 at a coating thickness of 6 μm. After drying under the same drying conditions as in Example 4, the results of measuring various characteristics of the color inkjet printer photo paper are shown in Table 2 below.

In the above application of alumina polymer sol, alumina polymer sol 1 is applied on the alumina polymer sol 1 and alumina polymer sol 2 is sequentially applied at the same time as the alumina polymer sol 1 is applied using a multi-layered rod rod coater provided with a plurality of nozzles. Polymer sol 3 is applied.

FIG. 8 shows a 200-fold side optical photograph showing a state in which the ink is absorbed (received) to a thickness (depth) of 30 µm when printing is carried out using magenta ink in Example 6, and FIG. Shows a 200 times optical photograph showing a state in which a line having a thickness of 0.1 mu m is printed.

As can be seen from FIG. 12, since the line having a thickness of 0.1 μm is clearly distinguished, it can be confirmed that the resolution is excellent.

Example 7

Distilled water was added to the alumina polymer sol 1 of Example 4 to prepare an alumina polymer sol 4 having a viscosity of 5 to 15 cps.

On the photo paper, one layer is coated with alumina polymer sol 1 at a coating thickness of 18 μm, the second layer is coated with alumina polymer sol 2 at a coating thickness of 6 μm, and the third layer is coated with an alumina polymer sol 3 at a coating thickness of 5 μm. The four layers were coated with alumina polymer sol 4 at a coating thickness of 4 μm, dried under the same drying conditions as in Example 4, and then measured for various properties of the color inkjet printer photo paper. .

In the above application of alumina polymer sol, alumina polymer sol 1 is applied on the alumina polymer sol 1 and alumina polymer sol 2 is sequentially applied at the same time as the alumina polymer sol 1 is applied using a multi-layered rod rod coater provided with a plurality of nozzles. Polymer sol 3 is applied, and alumina polymer sol 4 is applied on the alumina polymer sol 3.

FIG. 9 shows a 200-fold side optical photograph showing a state in which the ink is absorbed (received) to a thickness (depth) of 25 µm when printing is performed using magenta ink in Example 7. FIG. 13 Shows a 200 times optical photograph showing a state in which a line having a thickness of 0.1 mu m is printed.

As can be seen from FIG. 13, since the line having a thickness of 0.1 μm is clearly distinguished, it can be confirmed that the resolution is excellent.

division Example 4 Example 5 Example 6 Example 7 Glossiness 85 ° 60 ° 90.56 78.45 89.76 78.00 88.79 77.96 88.78 77.90 Light stability normal Yellow fuchsia turquoise black 0.82 1.44 1.12 1.61 0.8 1.42 1.10 1.60 0.8 1.41 1.09 1.59 0.8 1.4 1.09 1.58 10 hours later Yellow fuchsia turquoise black 0.8 1.42 1.09 1.62 0.79 1.39 1.06 1.60 0.78 1.30 1.04 1.59 0.76 1.21 1.04 1.59 Water Resistance Drying Time Decrease (%) seconds 1.5% 0.3 2.0 0.3 2.0 0.3 2.0 0.3 General Purpose Alcohol Resistance Weather Resistance Whiteness Smoothness Curling Very good Very good Very good 97.6 0.17 Very good Very good Very good Very good 9.60 0.17 Very good Very good Very good Very good 9.59 0.17 Very good Very good Very good Very good 9.55 0.17 Very good Adhesion Very good Very good Very good Very good

In Table 2, the image concentration and smoothness were measured using a spectrophotometer (manufactured by X-light), and the versatility of MJC 2500C (Samsung Electronics), Japan-Xerox 250, Canon BJC 8200, US-HP Deskjet 870K, etc. Measured by using a color printer of, the alcohol resistance is determined by immersing the printed image in ethanol for 3 hours at room temperature and confirming the deterioration of the image, and the water resistance after immersing the printed image in water for 3 hours at room temperature Determination of the quality of the image was determined by determining the degree of weathering. The weather resistance was measured after exposure to 50 ° C. and RH 90% for 48 hours, and the curling test was performed under the condition of 35 ° C. and RH 90%. The adhesiveness was measured by immersing the printed image in water at 30 ° C. for 10 minutes, and then measuring the state in which the ink receiving layer and the paper were bonded after rapid drying, and the rubbing resistance was applied to the surface of the printed image. It is determined by checking the bleeding state of the image when rubbed.

As can be seen from Table 2, Examples 4 to 7 according to the present invention can confirm that all of the various properties of the photo paper is excellent.

In Examples 4 to 7, the zeta potentials before and after color printing of the ink receiving layer were measured and shown in Table 3 below.

division Zeta potential Example 4 Example 5 Example 6 Example 7 Ink Receptive Layer Before Printing 12.60 11.90 11.83 11.67  Printed Ink Receptive Layer Black color 23.80 23.01 23.31 22.44 Turquoise 26.43 26.67 27.30 26.08 claret 28.64 28.23 19.06 18.22 yellow 26.66 25.60 26.19 26.58

As can be seen from Table 3, Examples 4 to 7 according to the present invention is increased since the zeta potential after printing than before printing, it can be confirmed that the ink is sufficiently absorbed in the ink receiving layer. That is, when the zeta potential having a positive potential increases, the absorbency of the ink having a negative potential is improved, so that the ink is well absorbed in the ink receiving layer.

In the photo paper manufactured by the method of manufacturing a color inkjet printer photo paper according to the present invention from Table 3, the ink receiving layer has a zeta potential of approximately 10 to 15 GPa and a zeta potential after printing of yellow, magenta, cyan and black. It can be seen that is improved to 15 ~ 30㎷.

Although the present invention has been described in detail only with respect to the embodiments, it will be apparent in the art that various modifications and variations are possible in the art, and such modifications are within the scope of the appended claims.

According to the color inkjet printer photo paper according to the present invention and the manufacturing method thereof according to the present invention, a nonionic water-soluble polymer and a hydrophilic polymer are prepared as a cationic polymer using a cationic surfactant, and then added to a polymer containing alumina sol of nanoparticles. It increases the zeta potential of the ink receiving layer and uniformly disperses the space gap between the alumina particles and the array having porous cations in the surface and side of the secondary alumina particle size in drying, so that the ink absorption and drying of the color inkjet printer photo paper is quick. It is made to, and excellent in alcohol resistance, weather resistance, glossiness, whiteness, smoothness, water resistance, curling resistance and adhesion.

In addition, according to the color inkjet printer photo paper according to the present invention and a method for manufacturing the same, it is possible to provide a high-definition color inkjet printer photo paper having a high resolution, in which a line having a thickness of 0.1 μm is clearly printed, so that natural colors can be reproduced. It is possible to obtain a color print image that can be.

In addition, according to the color inkjet printer photo paper and the manufacturing method thereof according to the present invention, since an oxidative stabilizer is used, it is possible to improve the preservation power and durability of the color.

Claims (9)

(1) pH 3.0- to 200-320 ml of aqueous solution containing 4-6 weight% of cation-modified polyvinyl alcohol and cation-modified polyvinylpyrrolidone of pH 3.0-4.5 which mix ratio (weight ratio) is 1: 0.3-0.7 ratio. Alumina sol prepared by dispersing 4.5, primary particle size 10-25 nm, zeta potential 40-44 mA, BET 103-171 m 2 / g, porous alumina 90-130 g having 0.6-0.9 mW / g Dispersion step; (2) adding a dodecyltrimethylammoniummethylchloride cationic surfactant to the hydrophilic butadiene-styrene copolymer emulsion in a proportion of 0.6 to 1.5% by weight to obtain a cationic hydrophilic polymer; (3) 40 to 65% by weight of the alumina sol obtained in the alumina sol dispersion step of (1) and the polymer obtained in the cationic hydrophilic polymer production step of (2) by mixing the remaining viscosity 15 ~ 40cps, secondary particles Preparing an alumina polymer sol having a size of 40 to 60 nm and a zeta potential of 43 to 50.12 제; (4) an application step of applying the alumina polymer sol obtained in the alumina polymer sol manufacturing step by applying a thin film of 1 to 4 layers with a srod die coater on a sheet of photo paper at 30 to 36 ° C. to apply a coating thickness in a range of 10 to 60 μm; (5) A method of manufacturing a color inkjet printer photo paper comprising a drying step of drying the photo paper coated with the alumina polymer sol in the coating step. The method according to claim 1, Triethylene glycol-bis- [3 (3-tet-butyl-4-hydroxy-5-methylphenyl) propionic acid as an oxidative stabilizer that maintains an average particle size of 3.32 to 3.74 µm in the alumina polymer sol preparation step of (3). ] (Triethyleneglycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate]) Emulsion was added to the alumina polymer sol at a ratio of 0.2 to 0.8 wt% to have a viscosity of 15 to 40 cps. A method for producing color inkjet printer photo paper for producing an alumina polymer sol. The method according to claim 1 or 2, A method of manufacturing a color inkjet printer photo paper further comprising adding at least one or two or more additives selected from the group consisting of a lubricant, a surfactant, a brightener, a UV absorber, a defoamer, an anti-curling agent, a fluorescent brightener, and a film-forming agent to the alumina polymer sol. The method according to claim 1 or 2, The drying step of (5) is 15 to 20 seconds in the first drying zone 5-8 ℃, 10 to 25 seconds in the second drying zone 20 to 28 ℃, 15 to 20 seconds in the third drying zone 50 to 65 ℃, A fourth method of manufacturing a color inkjet printer photo paper comprising 30 to 40 seconds in a drying area of 80 to 110 ° C. The method according to claim 4, As the photo paper base paper, one selected from art paper, CCP paper, synthetic paper, polyethylene coated photo paper, The ink-receiving layer zeta potential of the photo paper dried through the step (5) is 10 to 15 GPa, and the zeta potential after printing of yellow, magenta, cyan and black is 15 to 30 GPa. Photo paper stock selected from art paper, CCP paper, synthetic paper, polyethylene coated photo paper, PH 3.0-4.5 in 200-320 ml of aqueous solution containing 4-6 weight% of cation-modified polyvinyl alcohol and cation-modified polyvinyl pyrrolidone of pH 3.0-4.5 which mix ratio (weight ratio) is 1: 0.3-0.7 A polymer sol prepared by mixing and dispersing alumina sol prepared by dispersing 90 to 130 g of alumina having a primary particle size of 10 to 25 nm in a hydrophilic cationic butadiene-styrene copolymer emulsion was coated on a base paper of a thickness of 10 to 60 μm. A color inkjet printer photo paper comprising an ink receiving layer formed by applying and drying 1 to 4 layers so as to be in a range. The method according to claim 6, The alumina dispersed in the alumina sol is a color inkjet printer photo paper that maintains the zeta potential of 40 ~ 44㎷, BET 103 ~ 171m2 / g and porous 0.6 ~ 0.9㏄ / g range. The method according to claim 6 or 7, The ink receiving layer is a color inkjet printer photo paper formed by coating a polymer sol in a range of 3 to 35 µm, 2 layers of 5 to 8 µm, 3 layers of 3 to 5 µm, and 4 layers of 3 to 5 µm. delete

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