Color photographic paper and method of making same

Abstract

The application belongs to the technical field of imaging, and provides a color paper and a preparation method thereof. The structure of the color paper comprises a support, a blue-sensitive emulsion layer, a first gelatin separation layer, a green-sensitive emulsion layer, a second gelatin separation layer, a red-sensitive emulsion layer, an ultraviolet absorption layer and a protective layer arranged in sequence, wherein the protective layer comprises gelatin, oxidized polyethylene wax, silica sol and a surfactant. The color paper has high anti-blocking performance and high glossiness.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of imaging technology, and particularly relates to a color paper and a preparation method thereof. BACKGROUND

[0002] The color paper is generally a photographic emulsion and a spacer solution which are melted and supplemented, and then are coated on a moving support by a coating method such as slope flow extrusion, and are dried to be a photosensitive material for viewing by reflected light. The structure of the color paper generally comprises a support, a photosensitive layer, a spacer layer and a protective layer, and the photosensitive layer and the spacer layer can comprise a blue-sensitive emulsion layer, a gelatin spacer layer, a green-sensitive emulsion layer, a gelatin spacer layer, a red-sensitive emulsion layer and an ultraviolet absorption layer which are sequentially arranged on the surface of the support, and the protective layer is arranged on the ultraviolet absorption layer. The protective layer (i.e. the outermost layer of the color paper) plays an important role in protecting the emulsion layer, and particularly provides the color paper with anti-static performance, scratch resistance, anti-blocking performance and glossiness. The main carrier of each coating layer is gelatin, and in a high humidity environment, the hygroscopicity of the gelatin can cause the color paper to be damaged or blocked during the process of being processed into an album or during storage, and chemical substances are often used for "film coating" in the market, which increases the process of album production and increases the production cost, and the chemical reagents affect the health of the human body and destroy the environment.

[0003] At present, the silica sol can be used in the protective layer to improve the anti-blocking performance of the color paper, the silica sol forms a three-dimensional network structure and has hydrophobicity, and cross-linking reaction occurs between the silica sol and active groups such as amino groups of the gelatin, so that the water absorption of the gelatin is reduced, and the color paper has high anti-blocking performance. However, in actual production, the silica sol has a small particle size, and the viscosity of the coating liquid changes quickly, for example, the viscosity of the coating liquid becomes large during storage, and the coating liquid is difficult to filter, which leads to low production efficiency of the color paper. In addition, the amount of the silica sol directly affects the anti-blocking performance and glossiness of the color paper, and a large amount of the silica sol can improve the anti-blocking performance but also leads to a decrease in the glossiness, so that the color image is dark and has no gloss.

[0004] Therefore, it is still necessary to further study the color paper. SUMMARY

[0005] The present application aims to at least partly solve one of the problems in the related art.

[0006] In one aspect of the present application, the present application provides a color paper, and the structure of the color paper comprises a support, a blue-sensitive emulsion layer, a first gelatin spacer layer, a green-sensitive emulsion layer, a second gelatin spacer layer, a red-sensitive emulsion layer, an ultraviolet absorption layer and a protective layer which are sequentially arranged, the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer are referred to as a photosensitive layer, and the first gelatin spacer layer and the second gelatin spacer layer are referred to as a spacer layer, wherein the protective layer comprises gelatin, oxidized polyethylene wax, silica sol and a surfactant. Thus, the color paper with high anti-blocking performance and high glossiness can be obtained.

[0007] According to an embodiment of the present application, the ratio of the coating amounts of the gelatin, the oxidized polyethylene wax, the silica sol, and the surfactant in the protective layer is 1:(0.7-5.25):(0.1-0.35):(0.3-2.65). Thus, the viscosity stability of the protective layer coating solution can be improved.

[0008] According to an embodiment of the present application, the coating amount of the gelatin is 0.35 g / m 2 -0.45 g / m 2 .

[0009] According to an embodiment of the present application, the average particle diameter of the oxidized polyethylene wax is 50 nm-110 nm.

[0010] According to an embodiment of the present application, the coating amount of the oxidized polyethylene wax is 0.3 g / m 2 -2.0 g / m 2 .

[0011] According to an embodiment of the present application, the gelatin includes at least one of acid gelatin, alkali gelatin, and gelatin derivatives, and is preferably acid gelatin. Thus, the stability of the coating solution can be improved.

[0012] According to an embodiment of the present application, the silica sol includes at least one of spherical silica sol, string-shaped silica sol, and branched silica sol. Preferably, the silica sol is at least one of the string-shaped silica sol and the branched silica sol. Thus, the film-forming property can be further improved.

[0013] According to an embodiment of the present application, the average particle diameter of the silica sol is 11 nm-15 nm. Thus, the silica sol has a low surface free energy, is stable in storage, and makes the viscosity of the coating solution more stable.

[0014] According to an embodiment of the present application, the coating amount of the silica sol is 0.05 g / m 2 -0.11 g / m 2 .

[0015] According to an embodiment of the present application, the surfactant is an acetylenic alcohol multifunctional surfactant. Thus, the compatibility with other components in the protective layer can be further improved, and the uniformity of the distribution of the components can be improved.

[0016] According to an embodiment of the present application, the coating amount of the surfactant is 0.13 g / m 2 -1 g / m 2 .

[0017] According to an embodiment of the present application, the first gelatin barrier layer and / or the second gelatin barrier layer each independently comprises gelatin and a film hardener, and the film hardener comprises an alkene sulfone compound. Thus, the film hardener can react with the amino group or carboxyl group in the gelatin molecule to form a network structure, thereby reducing the water absorption of the gelatin and improving the anti-sticking property of the photographic paper.

[0018] According to an embodiment of the present application, the alkene sulfone compound comprises bis(ethylene sulfone) methane. In this way, the reaction speed of the film hardener can be further improved, and the anti-sticking property of the photographic paper can be further improved.

[0019] According to an embodiment of the present application, in the first gelatin barrier layer, the coating amount of the gelatin is 0.4 g / m 2 ~ 0.8 g / m 2 , and the coating amount of the bis(ethylene sulfone) methane is 0.08 g / m 2 ~ 0.15 g / m 2 . In this way, the anti-sticking property of the photographic paper can be further improved.

[0020] In another aspect of the present application, a method for preparing the above-mentioned color photographic paper is provided, which comprises forming a photosensitive layer, a barrier layer, and an ultraviolet absorption layer on a support, and coating a coating liquid comprising the gelatin, the oxidized polyethylene wax, the silica sol, and the surfactant on the ultraviolet absorption layer to form a protective layer. In the method of the present application, the viscosity of the coating liquid is stable, which is conducive to stable coating and improves the preparation efficiency of the color photographic paper. In addition, the color photographic paper prepared by the method has high anti-sticking property and high gloss.

[0021] According to an embodiment of the present application, the pH of the coating liquid is greater than 6; and / or the viscosity of the coating liquid at 40°C ~ 45°C is 18 mPa·s ~ 22 mPa·s. Thus, the coating liquid has higher storage stability. BRIEF DESCRIPTION OF DRAWINGS

[0022] The above and / or additional aspects and advantages of the present application will become apparent and more readily appreciated from the following description of embodiments, taken in conjunction with the accompanying drawings in which:

[0023] Figure 1 A schematic view of the structure of the color photographic paper according to some embodiments of the present application.

[0024] REFERENCE NUMERALS

[0025] 1: support; 2: blue-sensitive emulsion layer; 3: first gelatin barrier layer; 4: green-sensitive emulsion layer; 5: second gelatin barrier layer; 6: red-sensitive emulsion layer; 7: ultraviolet absorption layer; 8: protective layer. DETAILED DESCRIPTION

[0026] Embodiments of the present application are described in detail below. The embodiments described below are exemplary only and are not intended to be limiting of the present application. Unless otherwise indicated, technical or scientific terms used in the embodiments have the same meaning as commonly understood by one of ordinary skill in the art to which the present application pertains. Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application pertains. The materials, methods, and examples provided herein are illustrative only and are not intended to be limiting.

[0027] The inventors of the present application found that, in the protective layer of color paper, although silica sol makes the color paper have anti-sticking property, most of the silica sol is deposited in the inside of the coating layer during coating process, which leads to the decrease of gloss of the color paper; and the coating liquid containing silica sol has the problem of large viscosity during storage process and difficult filtration, which leads to low production efficiency of color paper. Accordingly, the present application is provided.

[0028] According to one aspect of the present application, the present application provides a color paper, which comprises a support, a blue-sensitive emulsion layer, a first gelatin spacer layer, a green-sensitive emulsion layer, a second gelatin spacer layer, a red-sensitive emulsion layer, an ultraviolet absorption layer and a protective layer arranged in sequence, wherein the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer are referred to as photosensitive layers, and the first gelatin spacer layer and the second gelatin spacer layer are referred to as spacer layers; and the protective layer comprises gelatin, oxidized polyethylene wax, silica sol and a surfactant. In the color paper of the present application, the oxidized polyethylene wax is introduced into the protective layer, and a film is formed on the surface of the color paper, so that the protective layer has flatness, smoothness and hydrophobicity; and under the dispersion effect of the surfactant, the oxidized polyethylene wax is used in combination with the gelatin and the silica sol to ensure the anti-sticking property and improve the gloss of the color paper.

[0029] In some embodiments, the coating amount ratio of the gelatin, the oxidized polyethylene wax, the silica sol and the surfactant in the protective layer is 1:(0.7-5.25):(0.1-0.35):(0.3-2.65), for example, 1:5:0.125:0.325. In this way, when the coating liquid for forming the protective layer is prepared, the components can be stably dispersed in the solvent, agglomeration is avoided, and the stability of the coating liquid is improved; and the components in the formed protective layer can effectively play their respective roles, and the comprehensive performance of the protective layer is improved.

[0030] In some embodiments, the coating amount of the gelatin in the protective layer is 0.35 g / m 2 ~0.45 g / m 2 , for example, 0.35 g / m 2 , 0.4 g / m 2 , 0.45 g / m 2 , etc.

[0031] In the present application, in order to further improve the flatness and smoothness of the film, in some embodiments, the average particle size of the oxidized polyethylene wax is 50 nm to 110 nm, such as 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm and 110 nm, etc. In this case, during the drying process of forming the protective layer, the particles of the oxidized polyethylene wax can further float to the surface and fuse into a film.

[0032] Further, the average particle size of the oxidized polyethylene wax is 50 nm to 100 nm.

[0033] According to embodiments of the present application, the coating amount of the oxidized polyethylene wax is 0.3 g / m 2 to 2.0 g / m 2 , such as 0.3 g / m 2 , 0.5 g / m 2 , 0.8 g / m 2 , 1.0 g / m 2 , 1.3 g / m 2 , 1.5 g / m 2 , 1.8 g / m 2 and 2.0 g / m 2 , etc. Within this coating amount range, the transparency can be improved while ensuring the coating effect (smoothness).

[0034] In some embodiments, the gelatin includes at least one of acid gelatin (type A gelatin), alkali gelatin (type B gelatin) and gelatin derivatives. The acid gelatin refers to gelatin prepared by hydrolyzing bone collagen by immersion in acid, and has an isoelectric point at pH of about 6.0 to 7.0; the alkali gelatin refers to gelatin prepared by treating a collagen-containing raw material with lime milk, and has an isoelectric point at pH of about 4.7 to 5.2; the gelatin derivative refers to a product obtained by modifying gelatin by chemical reaction of a functional group in the gelatin with isocyanate or anhydride. In order to further improve the stability of the protective layer coating solution, the gelatin is preferably acid gelatin.

[0035] In the present application, the silica sol can include at least one of spherical silica sol, string-bead-shaped silica sol and branched-chain-shaped silica sol, and preferably at least one of string-bead-shaped silica sol and branched-chain-shaped silica sol, which can further improve the film-forming property.

[0036] In some embodiments, the average particle size of the silica sol is 11 nm to 15 nm, such as 11 nm, 12 nm, 13 nm, 14 nm and 15 nm, etc. Thus, the silica sol has a low surface free energy, good storage stability, and makes the viscosity of the coating solution more stable.

[0037] In some embodiments, the coating amount of the silica sol is 0.05 g / m 2~0.11g / m 2 , such as 0.05g / m 2 , 0.08g / m 2 , 0.1g / m 2 , and 0.11g / m 2 , etc. The anti-blocking property of the photographic paper mainly depends on the surface property. During the drying process, the silica sol particles are adsorbed on the gelatin to form a film by itself or cross-link with the gelatin, thereby improving the anti-blocking property of the photographic paper.

[0038] In the present application, the surfactant can be selected from at least one of ionic surfactants, non-ionic surfactants, and amphoteric surfactants. The surfactant generally functions to reduce the surface tension, quickly wet, and emulsify. Alternatively, the surfactant is a non-ionic surfactant. Further, the surfactant is an acetylenic alcohol multifunctional surfactant, which can further improve the compatibility with other components in the protective layer and improve the uniformity of the distribution of the components in the protective layer.

[0039] In some embodiments, the coating amount of the surfactant is 0.13g / m 2 ~1g / m 2 , such as 0.13g / m 2 , 0.3g / m 2 , 0.5g / m 2 , 0.8g / m 2 , and 1g / m 2 . In this way, the coating liquid can be uniformly spread at a high speed, and the water absorption of the coating layer can be reduced.

[0040] According to an embodiment of the present application, referring to Figure 1 , the color photographic paper comprises a support 1, a photosensitive layer, a barrier layer, an ultraviolet absorption layer 7, and a protective layer 8, wherein the photosensitive layer comprises a blue-sensitive emulsion layer 2, a green-sensitive emulsion layer 4, and a red-sensitive emulsion layer 6; the barrier layer comprises a first gelatin barrier layer 3 and a second gelatin barrier layer 5; the blue-sensitive emulsion layer 2, the first gelatin barrier layer 3, the green-sensitive emulsion layer 4, the second gelatin barrier layer 5, the red-sensitive emulsion layer 6, and the ultraviolet absorption layer 7 are sequentially stacked on the surface of the support 1.

[0041] The blue-sensitive emulsion layer 2, the green-sensitive emulsion layer 4, and the red-sensitive emulsion layer 6 are not particularly limited in the present application, and the components thereof are well known in the art.

[0042] Generally, the blue-sensitive emulsion layer 2 can mainly comprise blue-sensitive silver halide and yellow color coupler. As an example, the blue-sensitive emulsion layer 2 comprises blue-sensitive emulsion silver, gelatin, yellow color coupler (e.g., CAS: 168689-49-4), image light stabilizer (e.g., CAS: 90498-90-1), and high-boiling-point solvent (e.g., tributyl citrate), and the coating amounts thereof can be 0.172g / m 2~ 0.192 g / m 2 , 0.957 g / m 2 ~ 0.977 g / m 2 , 0.422 g / m 2 ~ 0.442 g / m 2 , 0.074 g / m 2 ~ 0.094 g / m 2 , 0.217 g / m 2 ~ 0.237 g / m 2 .

[0043] The green-sensitive emulsion layer 4 can include green-sensitive silver halide and a color developing agent. As one example, the green-sensitive emulsion layer 4 includes green-sensitive emulsion silver, gelatin, a color developing agent (e.g., CAS: 124351-77-5), an image light stabilizer (e.g., 1,1-dioxo-4-(4-tridecyl- oxypenyl)-thiazolidine), and a high-boiling solvent (e.g., trimethylphosphine cresyl phosphate, oleyl alcohol, ethyl 2-(2-n-butoxyethoxy)acetate), at coating amounts of 0.069 g / m 2 ~ 0.089 g / m 2 , 1.133 g / m 2 ~ 1.153 g / m 2 , 0.208 g / m 2 ~ 0.228 g / m 2 , 0.077 g / m 2 ~ 0.097 g / m 2 , 0.154 g / m 2 ~ 0.174 g / m 2 , 0.154 g / m 2 ~ 0.174 g / m 2 , 0.099 g / m 2 ~ 0.119 g / m 2 .

[0044] The red-sensitive emulsion layer 6 can include red-sensitive silver halide and a cyan color developing agent. As one example, the red-sensitive emulsion layer 6 can include red-sensitive emulsion silver, gelatin, a cyan color developing agent (e.g., CAS: 93951-12-3), an ultraviolet absorber (e.g., UV-328, UV-326), and a high-boiling solvent (e.g., trimethylphosphine cresyl phosphate, dibutyl phthalate, ethyl 2-(2-n-butoxyethoxy)acetate), at coating amounts of 0.078 g / m 2 ~ 0.098 g / m 2 , 1.072 g / m 2 ~ 1.092 g / m 2 , 0.152 g / m 2 ~ 0.172 g / m 20.403 g / m 2 ~ 0.423 g / m 2 0.063 g / m 2 ~ 0.083 g / m 2 0.256 g / m 2 ~ 0.276 g / m 2 0.256 g / m 2 ~ 0.276 g / m 2 0.151 g / m 2 ~ 0.171 g / m 2 .

[0045] After exposure of each layer of silver halide, latent image centers composed of 3-4 silver atoms are generated, which can initiate development. During development, silver halide and the developer react to form a metallic silver image, developer oxide, and halide ions. Simultaneously with the formation of the silver image, the coupler reacts with the developer oxide to form a dye. After fixing, the unexposed silver halide and metallic silver are removed, and a color image is formed.

[0046] In some embodiments, the first gelatin barrier layer 3 and / or the second gelatin barrier layer 5 each independently comprises gelatin and a hardener. The hardener can cross-link with the amino or carboxyl groups in the gelatin molecules to form a network structure, thereby reducing the water absorption of the gelatin and improving the anti-sticking property of the photographic paper. The gelatin can be an alkali gelatin, which is advantageous for the stability of the coating solution.

[0047] In the present application, the hardener can comprise an inorganic hardener and / or an organic hardener. Examples of inorganic hardeners include chromium trichloride, aluminum trichloride, and chromium acetate. Examples of organic hardeners include epoxy compounds, ene-sulfone compounds, aldehyde compounds, and s-triazine hardeners. Preferably, the hardener comprises an ene-sulfone compound, which can increase the reaction speed of the hardener and improve the anti-sticking property of the photographic paper.

[0048] Preferably, the ene-sulfone compound comprises bis(ethylene sulfone) methane. During preparation, it is preferred that the first gelatin barrier layer 3 and / or the second gelatin barrier layer 5 comprises bis(ethylene sulfone) methane, which is advantageous for the reaction with the gelatin to form a network structure and further improve the anti-sticking property of the photographic paper.

[0049] In some specific embodiments, the first gelatin barrier layer 3 comprises gelatin (e.g., alkali gelatin), hardener (e.g., bis(ethylene sulfone) methane), antioxidant (e.g., 2,5-di-tert-octyl hydroquinone), and high-boiling-point solvent (e.g., diundecyl phthalate), with coating amounts of 0.39 g / m 2 ~ 0.41 g / m 2 0.07 g / m 2 ~ 0.16 g / m 2 0.061 g / m2 ~ 0.081 g / m 2 , 0.119 g / m 2 ~ 0.139 g / m 2 .

[0050] In some specific embodiments, the second gelatin barrier layer 5 comprises gelatin, an antioxidant (e.g., 2,5 di-tert-octyl hydroquinone) and a high-boiling solvent (e.g., di (undecyl) phthalate) with coating amounts of 0.597 g / m 2 ~ 0.617 g / m 2 , 0.061 g / m 2 ~ 0.081 g / m 2 , 0.119 g / m 2 ~ 0.139 g / m 2 .

[0051] In some embodiments, the coating amounts of gelatin in the first gelatin barrier layer 3 and the second gelatin barrier layer 5 are 0.4 g / m 2 ~ 0.8 g / m 2 , such as 0.4 g / m 2 , 0.5 g / m 2 , 0.6 g / m 2 , 0.7 g / m 2 and 0.8 g / m 2 , etc.; and the coating amount of bis (vinylsulfonyl) methane is 0.08 g / m 2 ~ 0.15 g / m 2 , such as 0.08 g / m 2 , 0.1 g / m 2 , 0.12 g / m 2 and 0.15 g / m 2 , etc.

[0052] In the present application, the ultraviolet absorbing layer 7 can comprise gelatin, an ultraviolet absorber (e.g., UV-328, UV-326), a high-boiling solvent (e.g., tributyl phosphate) with coating amounts of 0.603 g / m 2 ~ 0.623 g / m 2 , 0.071 g / m 2 ~ 0.091 g / m 2 , 0.004 g / m 2 ~ 0.024 g / m 2 , 0.022 g / m 2 ~ 0.042 g / m 2 .

[0053] In the present application, the coating amount is the amount of each component excluding its solvent. For example, if the gelatin is a gelatin solution, the coating amount of the gelatin refers to the coating amount excluding its solvent. For another example, if the silica sol is a silica sol solution, the coating amount refers to the coating amount excluding its solvent.

[0054] According to another aspect of the present application, the present application provides a method for preparing the color paper of the first aspect of the present application, the method comprising: forming a photosensitive layer, a barrier layer, an ultraviolet absorption layer on a support, and coating a coating liquid containing the gelatin, the oxidized polyethylene wax, the silica sol and the surfactant on the ultraviolet absorption layer to form a protective layer.

[0055] In the present application, the coating liquid for forming the protective layer can be prepared by uniformly mixing the components including the gelatin, the oxidized polyethylene wax, the silica sol, the surfactant and a solvent (such as deionized water) at high speed. In order to further improve the stability of the coating liquid, the method for preparing the coating liquid preferably comprises: first heating the gelatin to 40-45°C, then sequentially adding the silica sol, the oxidized polyethylene wax and the surfactant, and adjusting the pH to be weakly acidic or neutral.

[0056] In some embodiments, the coating liquid satisfies at least one of the following conditions: (1) the pH is greater than 6, such as 6, 6.5 and 7, etc.; (2) the viscosity at 40-45°C is 18-22 mPa·s, such as 18 mPa·s, 19 mPa·s, 20 mPa·s, 21 mPa·s and 22 mPa·s, etc. The coating liquid has high viscosity stability, and the viscosity of the coating liquid changes little during long-term storage.

[0057] In some embodiments, the method for preparing the color paper comprises:

[0058] In some embodiments, the method for preparing the color paper comprises:

[0059] It should be noted that the features and advantages described above for the color paper also apply to the method, and will not be repeated here.

[0060] The present application will be described below with reference to specific embodiments, and it should be noted that these embodiments are merely descriptive and do not limit the present application in any way.

[0061] In the following examples and comparative examples, the gelatin of the protective layer is acid gelatin, which is photographic gelatin purchased from Sichuan Ruibao Biotechnology Co., Ltd.

[0062] The branched silica sol and the string bead silica sol are purchased from Shandong Baiter New Material Co., Ltd.

[0063] The acetylenic alcohol surfactant is purchased from Tianjin Hupuful New Material Co., Ltd., and the model is FS-204.

[0064] The oxidized polyethylene (100 nm) is purchased from Nanjing Tianshi New Material Technology Co., Ltd., and the model is OE6102.

[0065] The oxidized polyethylene (50 nm) is purchased from Wacker, and the model is CT1389.

[0066] The support (material: paper base, size: 3 m x 0.24 m) is coated with a blue-sensitive emulsion layer, a first gelatin separation layer, a green-sensitive emulsion layer, a second gelatin separation layer, a red-sensitive emulsion layer, and an ultraviolet absorption layer in sequence by using a multi-layer extrusion coating method. The preparation method of the coating liquid for the protective layer is as follows: the gelatin is heated to 42°C, and then the silica sol, the oxidized polyethylene wax, and the acetylenic alcohol multifunctional surfactant are sequentially added to prepare a coating liquid with a pH of 6.5. The coating liquid is coated on the ultraviolet absorption layer, and after drying, the image is formed by exposure, development, and fixing. The blue-sensitive emulsion layer, the green-sensitive emulsion layer, the second gelatin separation layer, the red-sensitive emulsion layer, and the ultraviolet absorption layer are the same in Examples 1-18 and Comparative Examples 1-5, and the main components are shown in Table 1.

[0067] Table 1

[0068]

[0069]

[0070] In addition, in the following examples and comparative examples, the solvent used in the protective layer is deionized water; the high-boiling solvent used in the first gelatin separation layer is diundecyl phthalate, the gelatin in the first gelatin separation layer is alkali gelatin, and the antioxidant is 2,5-di-t-octyl hydroquinone.

[0071] Example 1

[0072] In the protective layer, the coating amount of the acid gelatin is 0.35 g / m 2 , the average particle size of the branched silica sol is 11 nm, and the coating amount is 0.05 g / m 2 , the average particle size of the oxidized polyethylene wax is 50 nm, and the coating amount is 2.0 g / m 2 , and the coating amount of the acetylenic alcohol multifunctional surfactant is 0.13 g / m 2 ; in the first gelatin separation layer, the coating amount of the bis(ethylene sulfone) methane film former is 0.08 g / m2 0.4 g / m 2 0.071 g / m 2 0.129 g / m 2 .

[0073] Example 2

[0074] In the protective layer, the acid gelatin was coated at 0.4 g / m 2 The average particle size of the branched silica sol was 11 nm and the coating amount was 0.05 g / m 2 The average particle size of the oxidized polyethylene wax was 110 nm and the coating amount was 2.0 g / m 2 The acetylenic alcohol multifunctional surfactant was coated at 0.13 g / m 2 In the first gelatin spacer layer, the bis(ethylene sulfone group) methane film hardener was coated at 0.08 g / m 2 The gelatin was coated at 0.8 g / m 2 The antioxidant was coated at 0.071 g / m 2 The high-boiling solvent was coated at 0.129 g / m 2 .

[0075] Example 3

[0076] In the protective layer, the acid gelatin was coated at 0.45 g / m 2 The average particle size of the string-shaped silica sol was 11 nm and the coating amount was 0.05 g / m 2 The average particle size of the oxidized polyethylene wax was 110 nm and the coating amount was 1.1 g / m 2 The acetylenic alcohol multifunctional surfactant was coated at 1 g / m 2 In the first gelatin spacer layer, the bis(ethylene sulfone group) methane film hardener was coated at 0.15 g / m 2 The gelatin was coated at 0.65 g / m 2 The antioxidant was coated at 0.071 g / m 2 The high-boiling solvent was coated at 0.129 g / m 2 .

[0077] Example 4

[0078] In the protective layer, the acid gelatin was coated at 0.4 g / m 2 The average particle size of the string-shaped silica sol was 11 nm and the coating amount was 0.05 g / m 2 The average particle size of the oxidized polyethylene wax was 50 nm and the coating amount was 1.1 g / m 2 The acetylenic alcohol multifunctional surfactant was coated at 1 g / m 2; the first gelatin barrier layer was coated with 0.15 g / m 2 of bis(ethylene sulfone) methane film hardener, 0.65 g / m 2 of gelatin, 0.071 g / m 2 of antioxidant, and 0.129 g / m 2 of high boiling point solvent.

[0079] Example 5

[0080] The protective layer was coated with 0.4 g / m 2 of acid method gelatin, 0.11 g / m 2 of branched silicon sol having an average particle size of 11 nm, 0.3 g / m 2 of oxidized polyethylene wax having an average particle size of 110 nm, and 1 g / m 2 of acetylenic alcohol multifunctional surfactant; the first gelatin barrier layer was coated with 0.08 g / m 2 of bis(ethylene sulfone) methane film hardener, 0.4 g / m 2 of gelatin, 0.071 g / m 2 of antioxidant, and 0.129 g / m 2 of high boiling point solvent.

[0081] Example 6

[0082] The protective layer was coated with 0.4 g / m 2 of acid method gelatin, 0.11 g / m 2 of beaded silicon sol having an average particle size of 11 nm, 0.3 g / m 2 of oxidized polyethylene wax having an average particle size of 50 nm, and 0.13 g / m 2 of acetylenic alcohol multifunctional surfactant; the first gelatin barrier layer was coated with 0.08 g / m 2 of bis(ethylene sulfone) methane film hardener, 0.8 g / m 2 of gelatin, 0.071 g / m 2 of antioxidant, and 0.129 g / m 2 of high boiling point solvent.

[0083] Example 7

[0084] The protective layer was coated with 0.4 g / m 2 of acid method gelatin, 0.11 g / m 2 of branched silicon sol having an average particle size of 11 nm, 2.0 g / m 2 of oxidized polyethylene wax having an average particle size of 110 nm, and 1 g / m of acetylenic alcohol multifunctional surfactant.2 ; the coating amount of bis(ethylene sulfone) methane film former in the first gelatin spacer layer was 0.1 g / m 2 ; the coating amount of gelatin was 0.4 g / m 2 ; the coating amount of antioxidant was 0.071 g / m 2 ; the coating amount of high boiling point solvent was 0.129 g / m 2 .

[0085] Example 8

[0086] ; the coating amount of acid method gelatin in the protective layer was 0.4 g / m 2 ; the average particle size of beaded silica sol was 11 nm, and the coating amount was 0.11 g / m 2 ; the average particle size of oxidized polyethylene wax was 50 nm, and the coating amount was 2.0 g / m 2 ; the coating amount of acetylenic alcohol multifunctional surfactant was 1 g / m 2 ; the coating amount of bis(ethylene sulfone) methane film former in the first gelatin spacer layer was 0.1 g / m 2 ; the coating amount of gelatin was 0.8 g / m 2 ; the coating amount of antioxidant was 0.071 g / m 2 ; the coating amount of high boiling point solvent was 0.129 g / m 2 .

[0087] Example 9

[0088] ; the coating amount of acid method gelatin in the protective layer was 0.4 g / m 2 ; the average particle size of beaded silica sol was 13 nm, and the coating amount was 0.08 g / m 2 ; the average particle size of oxidized polyethylene wax was 50 nm, and the coating amount was 0.3 g / m 2 ; the coating amount of acetylenic alcohol multifunctional surfactant was 0.13 g / m 2 ; the coating amount of bis(ethylene sulfone) methane film former in the first gelatin spacer layer was 0.15 g / m 2 ; the coating amount of gelatin was 0.4 g / m 2 ; the coating amount of antioxidant was 0.071 g / m 2 ; the coating amount of high boiling point solvent was 0.129 g / m 2 .

[0089] Example 10

[0090] ; the coating amount of acid method gelatin in the protective layer was 0.35 g / m 2 ; the average particle size of beaded silica sol was 15 nm, and the coating amount was 0.11 g / m 2 ; the average particle size of oxidized polyethylene wax was 50 nm, and the coating amount was 2 g / m 2, the acetylenic alcohol multifunctional surfactant was applied at a rate of 0.53 g / m 2 ; in the first gelatin barrier layer, the bis(ethylene sulfone group) methane film hardener was applied at a rate of 0.15 g / m 2 , the gelatin was applied at a rate of 0.4 g / m 2 , the antioxidant was applied at a rate of 0.071 g / m 2 , and the high-boiling solvent was applied at a rate of 0.129 g / m 2 .

[0091] Example 11

[0092] In the protective layer, the acid method gelatin was applied at a rate of 0.4 g / m 2 , the branched silicon sol had an average particle size of 15 nm and was applied at a rate of 0.08 g / m 2 , the oxidized polyethylene wax had an average particle size of 110 nm and was applied at a rate of 2.0 g / m 2 , the acetylenic alcohol multifunctional surfactant was applied at a rate of 0.53 g / m 2 ; in the first gelatin barrier layer, the bis(ethylene sulfone group) methane film hardener was applied at a rate of 0.08 g / m 2 , the gelatin was applied at a rate of 0.8 g / m 2 , the antioxidant was applied at a rate of 0.071 g / m 2 , and the high-boiling solvent was applied at a rate of 0.129 g / m 2 .

[0093] Example 12

[0094] In the protective layer, the acid method gelatin was applied at a rate of 0.45 g / m 2 , the string-shaped silicon sol had an average particle size of 15 nm and was applied at a rate of 0.11 g / m 2 , the oxidized polyethylene wax had an average particle size of 50 nm and was applied at a rate of 1.1 g / m 2 , the acetylenic alcohol multifunctional surfactant was applied at a rate of 0.13 g / m 2 ; in the first gelatin barrier layer, the bis(ethylene sulfone group) methane film hardener was applied at a rate of 0.08 g / m 2 , the gelatin was applied at a rate of 0.8 g / m 2 , the antioxidant was applied at a rate of 0.071 g / m 2 , and the high-boiling solvent was applied at a rate of 0.129 g / m 2 .

[0095] Example 13

[0096] In the protective layer, the acid method gelatin was applied at a rate of 0.4 g / m 2 , the branched silicon sol had an average particle size of 15 nm and was applied at a rate of 0.05 g / m 2 , the oxidized polyethylene wax had an average particle size of 80 nm and was applied at a rate of 2.0 g / m2 , the acetylenic alcohol multifunctional surfactant was applied at 1 g / m 2 ; in the first gelatin barrier layer, the bis(vinylsulfonyl)methane film strength agent was applied at 0.15 g / m 2 , the gelatin was applied at 0.8 g / m 2 , the antioxidant was applied at 0.071 g / m 2 , the high-boiling solvent was applied at 0.129 g / m 2 .

[0097] Example 14

[0098] In the protective layer, the acid gelatin was applied at 0.4 g / m 2 , the branched silicon sol had an average particle size of 15 nm and was applied at 0.11 g / m 2 , the oxidized polyethylene wax had an average particle size of 110 nm and was applied at 0.3 g / m 2 , the acetylenic alcohol multifunctional surfactant was applied at 1 g / m 2 ; in the first gelatin barrier layer, the bis(vinylsulfonyl)methane film strength agent was applied at 0.08 g / m 2 , the gelatin was applied at 0.4 g / m 2 , the antioxidant was applied at 0.071 g / m 2 , the high-boiling solvent was applied at 0.129 g / m 2 .

[0099] Example 15

[0100] In the protective layer, the acid gelatin was applied at 0.4 g / m 2 , the string-shaped silicon sol had an average particle size of 15 nm and was applied at 0.11 g / m 2 , the oxidized polyethylene wax had an average particle size of 100 nm and was applied at 2.0 g / m 2 , the acetylenic alcohol multifunctional surfactant was applied at 1 g / m 2 ; in the first gelatin barrier layer, the bis(vinylsulfonyl)methane film strength agent was applied at 0.15 g / m 2 , the gelatin was applied at 0.8 g / m 2 , the antioxidant was applied at 0.071 g / m 2 , the high-boiling solvent was applied at 0.129 g / m 2 .

[0101] Example 16

[0102] In the protective layer, the acid gelatin was applied at 0.4 g / m 2 , the string-shaped silicon sol had an average particle size of 11 nm and was applied at 0.11 g / m 2, the average particle size of the oxidized polyethylene wax was 50 nm, and the coating amount was 0.3 g / m 2 , the coating amount of the acetylenic alcohol multifunctional surfactant was 0.13 g / m 2 ; in the first gelatin barrier layer, the coating amount of the bis(ethylene sulfone group) methane film hardener was 0.08 g / m 2 , the coating amount of the gelatin was 0.4 g / m 2 , the coating amount of the antioxidant was 0.071 g / m 2 , the coating amount of the high-boiling-point solvent was 0.129 g / m 2 .

[0103] Example 17

[0104] In the protective layer, the coating amount of the acid gelatin was 0.45 g / m 2 , the average particle size of the spherical silica sol was 11 nm, and the coating amount was 0.05 g / m 2 , the average particle size of the oxidized polyethylene wax was 50 nm, and the coating amount was 2.0 g / m 2 , the coating amount of the acetylenic alcohol multifunctional surfactant was 0.13 g / m 2 ; in the first gelatin barrier layer, the coating amount of the bis(ethylene sulfone group) methane film hardener was 0.08 g / m 2 , the coating amount of the gelatin was 0.4 g / m 2 , the coating amount of the antioxidant was 0.071 g / m 2 , the coating amount of the high-boiling-point solvent was 0.129 g / m 2 .

[0105] Example 18

[0106] In the protective layer, the coating amount of the acid gelatin was 0.45 g / m 2 , the average particle size of the branched silica sol was 11 nm, and the coating amount was 0.11 g / m 2 , the average particle size of the oxidized polyethylene wax was 110 nm, and the coating amount was 2.0 g / m 2 , the coating amount of the acetylenic alcohol multifunctional surfactant was 1 g / m 2 , the solvent was deionized water; in the first gelatin barrier layer, the coating amount of the bis(ethylene sulfone group) methane film hardener was 0.15 g / m 2 , the coating amount of the gelatin was 0.8 g / m 2 , the coating amount of the antioxidant was 0.071 g / m 2 , the coating amount of the high-boiling-point solvent was 0.129 g / m 2 .

[0107] Comparative Example 1

[0108] In the protective layer, the coating amount of the acid gelatin was 0.4 g / m 2 , the coating amount of the acetylenic alcohol multifunctional surfactant was 1 g / m2 , the solvent was deionized water; in the first gelatin barrier layer, the coating amount of bis(ethylene sulfone) methane film former was 0.08 g / m 2 , the coating amount of gelatin was 0.4 g / m 2 , the coating amount of antioxidant was 0.071 g / m 2 , the coating amount of high boiling point solvent was 0.129 g / m 2 .

[0109] Comparative Example 2

[0110] In the protective layer, the coating amount of acid method gelatin was 0.4 g / m 2 , the average particle size of spherical silica sol was 6 nm, and the coating amount was 0.5 g / m 2 , the coating amount of acetylenic alcohol multifunctional surfactant was 1 g / m 2 , the solvent was deionized water; in the first gelatin barrier layer, the coating amount of bis(ethylene sulfone) methane film former was 0.08 g / m 2 , the coating amount of gelatin was 0.4 g / m 2 , the coating amount of antioxidant was 0.071 g / m 2 , the coating amount of high boiling point solvent was 0.129 g / m 2 .

[0111] Comparative Example 3

[0112] In the protective layer, the coating amount of acid method gelatin was 0.4 g / m 2 , the average particle size of spherical silica sol was 10 nm, and the coating amount was 1 g / m 2 , the coating amount of acetylenic alcohol multifunctional surfactant was 0.13 g / m 2 , the solvent was deionized water; in the first gelatin barrier layer, the coating amount of bis(ethylene sulfone) methane film former was 0.15 g / m 2 , the coating amount of gelatin was 0.4 g / m 2 , the coating amount of antioxidant was 0.071 g / m 2 , the coating amount of high boiling point solvent was 0.129 g / m 2 .

[0113] Comparative Example 4

[0114] In the protective layer, the coating amount of acid method gelatin was 0.4 g / m 2 , the average particle size of spherical silica sol was 11 nm, and the coating amount was 0.04 g / m 2 , the coating amount of acetylenic alcohol multifunctional surfactant was 0.13 g / m 2 , the solvent was deionized water; in the first gelatin barrier layer, the coating amount of bis(ethylene sulfone) methane film former was 0.15 g / m 2 , the coating amount of gelatin was 0.4 g / m 2, antioxidant coating amount 0.071 g / m 2 , high boiling point solvent coating amount 0.129 g / m 2 .

[0115] Comparative Example 5

[0116] In the protective layer, acid gelatin coating amount 0.4 g / m 2 , oxidized polyethylene wax average particle size 90 nm, coating amount 2.0 g / m 2 , acetylenic alcohol multifunctional surfactant coating amount 1 g / m 2 , solvent deionized water; in the first gelatin barrier layer, bis(ethylene sulfone) methane firming agent coating amount 0.15 g / m 2 , gelatin coating amount 0.8 g / m 2 , antioxidant coating amount 0.071 g / m 2 , high boiling point solvent coating amount 0.129 g / m 2 .

[0117] Performance evaluation:

[0118] 1. Coating liquid viscosity test

[0119] Test method: the protective layer coating liquid (prepared and stored for 24 h) is kept at 42°C, and the viscosity is tested by SNB-2EL digital rotary viscometer.

[0120] 2. Anti-blocking performance test

[0121] Test method: 1 mL of water is added between the two color paper samples after washing and processing, and they are pasted together, and a 200 g weight is placed on them, and they are stored in an environment of 50°C and 90% relative humidity for 24 h, and the blocking condition is evaluated by peeling off the two color paper samples. It is divided into three grades, namely: I grade: no damage, II grade: slight damage, III grade: damage.

[0122] 3. Gloss test

[0123] Test method: the gloss of the color paper sample after washing and processing is measured at 60° by using XGP series portable mirror gloss meter.

[0124] Table 2: Physical performance test results of each example and comparative example

[0125]

[0126]

[0127] As can be seen from the test results of each example and comparative example in Table 2, compared with Comparative Examples 1-5, the protective layer coating liquid viscosity of Examples 1-18 is more stable, and the anti-blocking performance and gloss are better.

[0128] In addition, comparing Examples 1 to 18 with Comparative Example 1, Comparative Example 4 and Comparative Example 5, it is found that the addition of the silica sol and the oxidized polyethylene wax improves the anti-blocking property of the photographic paper.

[0129] Comparing Examples 1 to 18 with Comparative Example 2 and Comparative Example 3, it is found that the addition of the oxidized polyethylene wax not only improves the glossiness, but also improves the stability of the coating liquid.

[0130] In the description of the present specification, the description referring to the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. The illustrative expressions of the above terms in the present specification do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in the present specification and the features of the different embodiments or examples can be combined and combined by those skilled in the art without contradiction.

[0131] Although the embodiments of the present application have been shown and described above, it is understood that the above-described embodiments are exemplary and are not to be construed as limiting the present application, and those ordinarily skilled in the art can make changes, modifications, replacements and variations to the above-described embodiments within the scope of the present application.

Claims

1. A color paper, which comprises, in order, a support, a blue-sensitive emulsion layer, a first gelatin barrier layer, a green-sensitive emulsion layer, a second gelatin barrier layer, a red-sensitive emulsion layer, an ultraviolet absorbing layer, and a protective layer, the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer being referred to as photosensitive layers, and the first gelatin barrier layer and the second gelatin barrier layer being referred to as barrier layers, characterized in that, The protective layer comprises gelatin, oxidized polyethylene wax, silica sol, and a surfactant, ​ In the protective layer, the coating amounts of the gelatin, the oxidized polyethylene wax, the silica sol, and the surfactant are in a ratio of 1:(0.7-5.25):(0.1-0.35):(0.3-2.65). The average particle size of the oxidized polyethylene wax is 50-110 nm. The average particle size of the silica sol is 11-15 nm.

2. The color paper according to claim 1, wherein The coating amount of the gelatin is 0.35 g / m 2 0.45 g / m 2 .

3. The color paper according to claim 1 or 2, characterized in that, The coating amount of the oxidized polyethylene wax is 0.3 g / m 2 2.0 g / m 2 .

4. The color paper according to claim 1 or 2, characterized by The gelatin includes at least one of acid gelatin, alkali gelatin, and a gelatin derivative.

5. The color paper according to claim 4, wherein The gelatin is acid gelatin.

6. The color paper according to claim 1, wherein The silica sol includes at least one of spherical silica sol, string-bead-shaped silica sol, and branched-chain-shaped silica sol.

7. The color paper according to claim 6, wherein The silica sol is at least one of string-bead-shaped silica sol and branched-chain-shaped silica sol.

8. The color paper according to claim 1 or 6, wherein The coating amount of the silica sol is 0.05 g / m 2 0.11 g / m 2 .

9. The color paper according to claim 1, wherein The surfactant is an acetylenic alcohol multifunctional surfactant.

10. The color paper according to claim 9, wherein The coating amount of the surfactant is 0.13 g / m 2 1 g / m 2 .

11. The color paper according to claim 1, wherein The first gelatin spacer layer and / or the second gelatin spacer layer each independently comprises gelatin and a film hardener, and the film hardener includes an olefin sulfone compound.

12. The color paper according to claim 11, wherein The olefin sulfone compound includes bis(ethylene sulfone) methane.

13. The color paper according to claim 12, wherein In the first gelatin barrier, the coating amount of gelatin was 0.4 g / m 2 0.8 g / m 2 The coating amount of bis(ethylene sulfone) methane was 0.08 g / m 2 0.15 g / m 2 .

14. A method of producing the color paper according to any one of claims 1 to 13, characterized by, Comprising: forming a photosensitive layer, a spacer layer, and a UV absorbing layer on a support, coating a coating liquid comprising the gelatin, the oxidized polyethylene wax, the silica sol, and the surfactant on the UV absorbing layer to form a protective layer.

15. The method of claim 14, wherein, The coating liquid satisfies at least one of the following conditions: (1) pH is greater than 6; (2) viscosity at 40-45°C is 18-22 mPa·s.

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