Photographic paper

Abstract

A photographic paper comprising a base layer having an average surface roughness (Sa) of at least 0.7 pm and an outer-most layer comprising a hydrophilic colloid binder and colloidal silica, wherein: (i) the weight ratio of colloidal silica to hydrophilic colloid binder in the outer-most layer is 0.05:1 to 0.28:1; and (ii) the amount of colloidal silica present in the outer-most layer is in the range of 8 mg/m2 to 280 mg/m2. The photographic paper is useful for preparing non-noisy photobooks.

Claims

1. A photographic paper comprising a base layer having an average surface roughness (Sa) of at least 0.7 m and an outer-most layer comprising a hydrophilic colloid binder and colloidal silica and one or more light sensitive emulsion layers between the outer-most layer and the base layer, wherein: (i) the weight ratio of colloidal silica to hydrophilic colloid binder in the outer-most layer is 0.05:1 to 0.28:1; (ii) the amount of colloidal silica present in the outer-most layer is in the range of 8 mg/m.sup.2 to 225 mg/m.sup.2; and (iii) the colloidal silica has a mean particle size of 3 to 70 nm.

2. The photographic paper according to claim 1 wherein the base layer has a specular gloss of less than 50%, when measured at an angle of 60 degrees by the method of JIS Z8741.

3. The photographic paper according to claim 1 wherein the base layer is a laminated paper support.

4. The photographic paper according to claim 1 wherein the amount of colloidal silica present in the outer-most layer is in the range of 10 mg/m.sup.2 to 225 mg/m.sup.2.

5. The photographic paper according to claim 1 wherein the amount of colloidal silica present in the outer-most layer is in the range of 40 mg/m.sup.2 to 225 mg/m.sup.2.

6. The photographic paper according to claim 5 wherein the base layer comprises a paper substrate and a polymer wherein the polymer is bonded to the paper and provides a textured surface profile thereon.

7. The photographic paper according to claim 1 wherein the amount of colloidal silica present in the outer-most layer is in the range of 40 mg/m.sup.2 to 225 mg/m.sup.2.

8. A lustre or matte photographic paper according to claim 1.

9. A method for preparing a photographic paper comprising applying a composition to a base layer having an average surface roughness (Sa) of at least 0.7 m and one or more light-sensitive emulsion layers, wherein: the composition comprises a hydrophilic colloid binder and colloidal silica in a weight ratio of 0.05:1 to 0.28:1; the colloidal silica has a mean particle size of 3 to 70 nm; and the amount of colloidal silica provided by the composition is in the range of 8 mg/m.sup.2 to 225 mg/m.sup.2 of colloidal silica.

10. The method according to claim 9 wherein the composition further comprises a hardening agent and the hydrophilic colloid binder in the ratio (R) satisfying the following equation:
R=(Hmol/HCg) wherein: R is greater than 0.00013; Hmol is the number of moles of hardening agent in the compositions; and HCg is the weight in grams of hydrophilic colloid binder in the composition.

11. The method according to claim 9 wherein the composition is applied to the base layer at a coating speed higher than 200 m/min.

12. The method according to claim 9 wherein the composition is applied to the base layer using a slide coater or curtain coater.

13. The method according to claim 9 wherein the composition and at least one light-sensitive emulsion layer are applied to the support simultaneously.

14. An album-book comprising one or more photographs comprising photographic paper according to claim 1.

15. The album-book according to claim 14 comprising at least two of said photographs positioned such that the photographs are in face-to-face contact when the album book is closed.

16. The album-book according to claim 14 which is free from interleaf foils.

Description

EXAMPLES

(1) The four base layers described in Table 2 above (LR-Pyramid, LR-Lustre, LR-Matte and LR-Glossy, all from Schoeller) were each coated, in one step, with 7 emulsion layers using a slide coater operated at a speed 300 m/min. The first six emulsion layers were identical in each case and were as described below. However the outer-most (seventh) layer was varied as described below in Table 3 in order to compare the performance of photographic papers comprising an outer-most layer according to the present invention with comparative photographic papers falling outside of the claims.

(2) The silicas used in the Examples and Comparative Examples were colloidal silicas obtained from H. C. Starck under the trade name Levasil.

(3) The hardening agent used in the Examples and Comparative Examples is sodium 1-oxy-3,5-dichloro-s-triazine.

(4) The following dyes (coating amounts in brackets) were included in the layers where indicated.

(5) ##STR00001##
Layer Constitution

(6) The composition of each layer is shown below. The numbers show coating amounts (g/m.sup.2). In the case of the silver halide emulsion, the coating amount is in terms of silver.

(7) TABLE-US-00004 First layer (Blue sensitive emulsion layer) Examples and Comparative Examples Component Amount All Silver chlorobromoiodide Emulsion 0.24 A.sup.# (containing gold-sulfur sensitized cubic grains and being a 3:7 (by mole on a silver basis) mixture of large-sized Emulsion A-1 and a small-sized Emulsion A-2) Gelatin 1.25 Yellow coupler (Ex Y 1) 0.34 Colour image stabilizer (Cpd-1) 0.07 Colour image stabilizer (Cpd-2) 0.04 Colour image stabilizer (Cpd-3) 0.07 Colour image stabilizer (Cpd-8) 0.02 Solvent (Solv-1) 0.21 .sup.#= Preparation Emulsion A is disclosed on columns 94/95/96 in U.S. Pat. No. 6,921,631.

(8) TABLE-US-00005 Second layer (Colour Mixing Inhibiting layer) Examples and Comparative Examples Component Amount All Gelatin 1.15 Colour mixing inhibitor (Cpd-4) 0.10 Colour mixing image stabilizer(Cpd-5) 0.018 Colour image stabilizer(Cpd-6) 0.13 Colour image stabilizer (Cpd-7) 0.07 Dye-1 0.001 Dye-2 0.001 Dye-3 0.0015 Dye-4 0.0035 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.12 Solvent (Solv-5) 0.11 All Hardening agent 0.038

(9) TABLE-US-00006 Third layer (Green sensitive emulsion layer) Examples and Comparative Examples Component Amount All Silver chlorobromoiodide Emulsion 0.14 C* 0.14 (containing gold-sulfur sensitized cubic grains and being a 1:3 (by mole on a silver basis) mixture of large-sized Emulsion C-1 and a small-sized Emulsion C-2) Gelatin 0.46 Magenta coupler (Ex M) 0.15 Ultraviolet absorber (UV-A) 0.14 Colour image stabilizer (Cpd-2) 0.003 Colour image stabilizer (Cpd-5) 0.002 Colour image stabilizer (Cpd-6) 0.09 Colour image stabilizer (Cpd-8) 0.02 Colour image stabilizer (Cpd-9) 0.01 Colour image stabilizer (Cpd-10) 0.01 Colour image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.09 Solvent (Solv-4) 0.18 Solvent (Solv-5) 0.27 *= Preparation Emulsion C is disclosed in columns 96/97 in U.S. Pat. No. 6,921,631.

(10) TABLE-US-00007 Fourth layer (Colour Mixing Inhibiting layer) Examples and Comparative Examples Component Amount All Gelatin 0.68 Colour mixing inhibitor (Cpd-4) 0.06 Colour image stabilizer (Cpd-5) 0.011 Colour image stabilizer (Cpd-6) 0.08 Colour image stabilizer (Cpd-7) 0.04 Dye-1 0.001 Dye-2 0.001 Dye-3 0.0015 Dye-4 0.0035 Solvent (Solv-1) 0.02 Solvent (Solv-2) 0.07 Solvent (Solv-5) 0.065 All Hardening agent 0.068

(11) TABLE-US-00008 Fifth layer (Red sensitive emulsion layer) Examples and Comparative Examples Component Amount All Silver chlorobromoiodide Emulsion E.sup.$ 0.10 (containing gold-sulfur sensitized cubic grains and being a 5:5 (by mole on a silver basis) mixture of large-sized Emulsion E-1 and a small-sized Emulsion E-2) Gelatin 1.11 Cyan coupler (ExC-1) 0.02 Cyan coupler (ExC-3) 0.01 Cyan coupler (ExC-4) 0.11 Cyan coupler (ExC-5) 0.01 Colour image stabilizer (Cpd-1) 0.01 Colour image stabilizer (Cpd-6) 0.06 Colour image stabilizer (Cpd-7) 0.02 Colour image stabilizer (Cpd-9) 0.04 Colour image stabilizer (Cpd-10) 0.01 Colour image stabilizer (Cpd-14) 0.01 Colour image stabilizer (Cpd-15) 0.12 Colour image stabilizer (Cpd-16) 0.01 Colour image stabilizer (Cpd-17) 0.01 Colour image stabilizer (Cpd-18) 0.07 Colour image stabilizer (Cpd-20) 0.01 Ultraviolet absorber (UV-7) 0.01 Solvent (Solv-5) 0.15 .sup.$= Preparation Emulsion E is disclosed in columns 97/98 in U.S. Pat. No. 6,921,631.

(12) TABLE-US-00009 Sixth layer (Ultraviolet Absorbing layer) Examples and Comparative Examples Component Amount All Gelatin 0.46 Ultraviolet absorber (UV-B) 0.35 Compound (S1-4) 0.0015 Solvent (Solv-7) 0.18 All Hardening agent 0.046
Seventh Layer (Outer-Most Layer)

(13) Fifty six compositions were prepared by mixing the ingredients indicated in Table 3 below (i.e. the 8 compositions A to H, each independently containing one of the 7 colloidal silicas indicated in the final row, making 87 compositions in total=56). These 56 compositions were then applied to the sixth layer mentioned above on each of the base layers such that the resultant, outer-most layer, after drying, comprised the amounts of hydrophilic colloid binder and colloidal silica indicated in Table 4 below (in g/m.sup.2). Thus the outer-most layers each comprised colloidal silica having a mean particle size of 3, 9, 12, 17, 34, 70 or 100 nm. The compositions had a pH of 9.5 at 40 C.

(14) TABLE-US-00010 TABLE 3 All units in g/m.sup.2 Composition Components A B C D E F G H Gelatin (Acid 0.86 0.86 0.86 0.86 0.86 0.86 0.86 0.86 processed) (a hydrophilic colloid binder) Acryl-modified 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 copolymer of polyvinyl alcohol (modification degree: 17%) (a hydrophilic colloid binder) Polymethyl 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 methacrylate mean particle size 4um Surface active 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 agents (Cmp-13) Liquid paraffin 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Coloidal silicas: 0.004 0.008 0.04 0.08 0.175 0.225 0.3 0.5 A1-H1 = 100 nm A2-H2 = 70 nm A3-H3 = 34 nm A4-H4 = 17 nm A5-H5 = 12 nm A6-H6 = 9 nm A7-H7 = 3 nm
Results

(15) The extent to which various photographic papers comprising an outer-most layer derived from the 56 compositions described in Table 3 made a noise when turned, bent and/or moved in a photobook was evaluated in the test described above as the Noise Test. The results on are shown in Tables 4 to 9 below in which 1 indicates not noisy and 0 indicates noisy:

(16) TABLE-US-00011 TABLE 4 Noise Results on LR-Lustre Base Layer (Sa of 1.9 m) Composition Amount of Average diameter of colloidal used to form colloidal silica in silica particles (nm) the outer- outer-most layer 100 70 34 17 12 9 3 most layer (mg/m.sup.2) Result of noise test A 4 0 1 1 1 1 1 1 B 8 0 1 1 1 1 1 1 C 40 0 1 1 1 1 1 1 D 80 0 1 1 1 1 1 1 E 175 0 1 1 1 1 1 1 F 225 0 1 1 1 1 1 1 G 300 0 0 0 0 0 0 0 H 500 0 0 0 0 0 0 0

(17) TABLE-US-00012 TABLE 5 Noise Results on LR-Matte Base Layer (Sa of 0.99 m) Amount of Composition colloidal Mean particle size of colloidal used to form silica in silica (nm) the outer-most outer-most layer 100 70 34 17 12 9 3 layer (mg/m.sup.2) Result of noise test A 4 0 1 1 1 1 1 1 B 8 0 1 1 1 1 1 1 C 40 0 1 1 1 1 1 1 D 80 0 1 1 1 1 1 1 E 175 0 1 1 1 1 1 1 F 225 0 1 1 1 1 1 1 G 300 0 0 0 0 0 0 0 H 500 0 0 0 0 0 0 0

(18) TABLE-US-00013 TABLE 6 Noise Results on LR-Glossy Base Layer (Sa of 0.6 m) Composition Amount of Mean particle size of colloidal used to form colloidal silica in silica (nm) the outer-most outer-most layer 100 70 34 17 12 9 3 layer (mg/m.sup.2) Result of noise test A 4 1 1 1 1 1 1 1 B 8 1 1 1 1 1 1 1 C 40 1 1 1 1 1 1 1 D 80 1 1 1 1 1 1 1 E 175 1 1 1 1 1 1 1 F 225 1 1 1 1 1 1 1 G 300 1 1 1 1 1 1 1 H 500 1 1 1 1 1 1 1
Note: the results in Table 6 show that glossy base layers do not suffer from noise problems.
Blocking Test Results

(19) The results in the blocking test were scored 1 to 5 as described above in which 1 is the best result (photographic papers were not damaged) and 5 is the worst result:

(20) TABLE-US-00014 TABLE 7 Blocking Results on LR-Lustre Base Layer (Sa of 1.9 m) Composition Amount of Mean particle size of colloidal used to form colloidal silica in silica (nm) the outer-most outer-most layer 70 34 17 12 9 3 layer (mg/m.sup.2) Result of blocking test A 4 3 3 2 2 2 2 B 8 2 2 2 2 2 2 C 40 1 1 1 1 1 1 D 80 1 1 1 1 1 1 E 175 1 1 1 1 1 1 F 225 1 1 1 1 1 1 G 300 1 1 1 1 1 1 H 500 1 1 1 1 1 1

(21) TABLE-US-00015 TABLE 8 Blocking Results on LR-Matte Base Layer (Sa of 0.99 m) Composition Amount of Mean particle size of colloidal used to form colloidal silica in silica (nm) the outer-most outer-most layer 70 34 17 12 9 3 layer (mg/m.sup.2) Result of blocking test A 4 3 3 2 2 2 2 B 8 2 2 2 2 2 2 C 40 1 1 1 1 1 1 D 80 1 1 1 1 1 1 E 175 1 1 1 1 1 1 F 225 1 1 1 1 1 1 G 300 1 1 1 1 1 1 H 500 1 1 1 1 1 1

(22) TABLE-US-00016 TABLE 9 Blocking Results on LR-Glossy Base Layer (Sa of 0.6 m) Composition Amount of Mean particle size of colloidal used to form colloidal silica in silica (nm) the outer-most outer-most layer 70 34 17 12 9 3 layer (mg/m.sup.2) Result of blocking test A 4 5 5 5 5 5 4 B 8 5 5 5 4 4 4 C 40 5 5 4 4 4 4 D 80 5 4 4 4 3 2 E 175 5 3 3 2 2 2 F 225 5 3 3 1 1 1 G 300 5 3 3 1 1 1 H 500 5 4 3 1 1 1

(23) The structural formulae of the compounds used herein are provided below:

(24) (ExY-1): Yellow coupler

(25) ##STR00002##
(ExM) Magenta Coupler 40:40:20 (by mole) mixture of (1), (2) and (3):

(26) TABLE-US-00017 (1) (2) (3) (ExC-1) Cyan coupler (Cpd-1) (ExC-3) Cyan coupler (ExC-4) Cyan coupler 0 (ExC-5) Cyan coupler (Cpd-1) Colour image stabiliser (Cpd-3) n = 7-8 (on average) Colour image stabilizer (Cpd-4) Colour mixing stabilizer (Cpd-5) Colour image stabilizer (Cpd-8) Colour image stabilizer (Cpd-9) Colour image stabilizer (Cpd-10) Colour image stabilizer 7:3 (by mole) mixture of (Cmp-13) (Cpd-14) 0 (Cpd-15) (Cpd-16) (Cpd-17) (Cpd-18) (Cpd-20) (Solv-1) (Solv-2) (Solv-3) (Solv-4) (Solv-5) 0 (Solv-7) (S1-4) (UV-1) Ultraviolet Absorbent (UV-2) Ultraviolet Absorbent (UV-3) Ultraviolet Absorbent (UV-5) Ultraviolet Absorbent (UV-6) Ultraviolet Absorbent (UV-7) Ultraviolet Absorbent UV-A: 7:2:2 (by weight) mixture of UV-1, UV-2 and UV-3 UV-B: 13:3:3:5:3 (by weight) mixture of UV-1, UV-2, UV-3, UV-5 and UV-6