JPS5931946A - Photographic coating solution containing gelatin - Google Patents

Abstract

PURPOSE:To exhibit thickening effect, such as max. elevation of viscosity, with the min. amt. of thickening agent used, and to keep film hardness good, by adding a thickening agent to a coating soln., and controlling a content of calcium in gelatin used for protective colloid down to 2,000ppm of dry gelatin. CONSTITUTION:The present photographic coating soln. contg. gelatin is controlled in calcium content to <=2,000ppm of dry gelatin for use in protective colloid, and is made viscous with a compd. represented by the general formula P-(A)n. Its typical example is polymer sulfate compds. As said thickening agent, any known thickening agent compd. can be used besides said compd. shown by the general formula. As the gelatin used for the coating soln., lime-treated gelatin, acid-treated gelatin, geletin derivs., and every kind of gelatin can be used alone or in combination, and natural or synthetic polymers can be added to it.

Description

[Detailed description of the invention]

``Mizumotori'' is a gelatin-containing copy suitable for printing on a flexible support such as film. , and good quality Q71!Vt4' This relates to an O cloth liquid for photocopying that is suitable for high-speed thin layer coating that provides good physical properties and surface gloss characteristics. Gelatin is commonly used as a supplementary agent.Gelatin is a characteristic natural polymer substance whose aqueous solution can undergo a sensitive solki-gel conversion by changing the temperature of hot water. 1 for the photographic industry.
, '=x, gelatin has not yet been able to replace other synthetic molecular compounds. In addition to the above-mentioned properties, the advantages of gelatin are that it is easy to crosslink with a hard 1jζ1 agent, (2) that the water content is less than f, that it is easy to shrink M, and that it is oriented (1) The surface of the film is good in terms of its surface brittleness; (1) it is graphically inert or if it is active, (C) it is easy to handle. It is pollution-free, and has excellent transparency and no color addition, so today's photo! It has become an indispensable building block for stone production. 16. Including Zera-won R. ': The coating liquid for 4'S is usually applied using the tipping method, the scraping coating method using an air knife, the extrusion method using an extra run-on. Coating method: What method do you use to apply it to film, paper, etc.? Is it possible to apply it? -In addition, it is necessary that there be no defects called hankies (spot-like uncoated areas).Furthermore, the gloss of the surface of the paint film is suppressed, and the surface becomes cloudy or matte. These requirements are positive sums that determine the factory's 1°, 1° position, and therefore the physicochemical properties m of φ blood are the same as these requirements' fr, less than '', consideration is given to the sea urchin. What is important in addition to quality is the production (-'F), and the establishment of fabric conditions for i-+ ir at a commercial pace. One countermeasure for this Vl-like problem is coating. faster and thinner j5
It is in one coat. If the water content of the O cloth solution is reduced and a thin layer coating is performed, the dry film 4+11 will swell, making high-speed printing possible and increasing economical efficiency. Another countermeasure is to reduce variable costs such as raw materials.
It is to be. Photo 4゛) In addition to the kimono, which are essential in order to maintain Hakunoh, there is a coating film ri'? r) Applying the total amount of force necessary to make it appear advantageous is done carefully, and for example, surfactants as coating aids and thickening agents to give the necessary viscosity are effective as appropriate. used for. Minimizing the need for all these materials will lead to increased productivity, increased productivity, and improved commercial profits. One of the conditions for stably applying a gelatin-containing photographic fabric solution at the highest speed is i'B Ji's method. Group completion [
In order to maintain the performance, it is necessary to keep the 91 limit O cloth 1 copy thick even if it contains the z-+q Latin quantity, failure (Mi
Since this causes the streaks and unevenness mentioned above, the lower limit of the coating film thickness is limited, and it is very likely that the necessary viscosity cannot be obtained due to insufficient gelatin concentration. In recent years, the amount of gelatin has been reduced more and more in order to improve the suitability for rapid processing, reduce costs, and improve the sharpness of images by reducing the thickness of the film layer (dry film). Along with this, the viscosity of the Qi5 liquid for photo doors is also decreasing. One way to increase the viscosity of gelatin is to use gelatin with a high viscosity. It has a low opaque content and is not suitable for thickening purposes.
There are problems such as crystallization of the gelatin and the tendency to form poorly soluble gelatin lumps. A much more advantageous way to increase the viscosity is to add a thickening agent, which allows large thickening rates to be obtained with the addition of small amounts. Particularly suitable for this purpose is a thickening agent for example! 1. J Kaisho 53-39118 Publication C1:
Like a shot, sulfur? These are esterified polymeric compounds, such as partial molecular jJj acid esters of polyvinyl alcohol and sulfuric acid esters of polysaccharides. These thickening agents can be expected to have a necessary and sufficient thickening effect on gelatin by adding a few scratches or less. ” JIJ @ a liquid k H; freight Z)
IIe, "" This is usually done by reducing a certain amount of thickening agent based on a certain prescription for each lot, but even if the consistency of the thickening agent is constant, this Sometimes, when the production lot of gelatin used changes, the viscosity changes, which is a serious problem. To remedy this, add a small amount of thickening agent to the prescribed amount and adjust the coating solution, then measure the viscosity. It requires an operation to return 1. Such work is extremely inefficient in routine work, and causes other problems as described below. f
′! Also, when the amount of the thickening agent added changes, the orientation of gelatin changes. As the amount added increases, the sol → gel specific optical rotation of the O-sheath liquid decreases, and the specific rotation of the coating film ->t-,
fXF- also does 1. For this reason, even if the viscosity and freezing point (set point) are the same, the surface smoothness of the actually obtained coating film will deteriorate, and the gloss will deteriorate b; In addition, for the hardening of gelatin films, inorganic hardening agents are usually used, but the viscosity;
As the hardening agent increases, the cross-linking reactivity due to the hardening agent decreases, and the hard material is @! ＃＜&ru. The present inventors conducted research on the causes of large changes in viscosity depending on gelatin manufacturing lots, and found that
Calcium ion (C,) contained in gelatin
It was determined that Nosuke was the main cause. Calcium ions inevitably remain in gelatin produced by the full, ill, or acid treatment method, and the +? The i1 degree always exists with some variation. The presence of this calcium ion inhibits the thickening caused by the reaction between gelatin and the thickening agent compound, and therefore, the variation in calcium ion content in gelatin is slightly different from that of gelatin. When a thickening agent is added, this causes a large variation in viscosity. From this, if the calcium ion density in gelatin is kept completely constant71-, the above-mentioned problem will not occur, but the lower the calcium ion content, the less the thickening agent used. This not only reduces manufacturing costs, but also improves the hardness and surface properties (gloss) of the O film after it is coated on the support. The object of the present invention is to form films, etc.;
Our goal is to provide a gelatin-containing fabric solution that is suitable for use with cloth, and uses the minimum amount of thickening agent to maximize the viscosity effect such as thickening. Membrane properties and Table 1+
(i) To provide a gelatin-containing coating liquid for printing 14 which can always maintain good original gloss properties. The purpose of coating is to coat on a flexible support;
In the gelatin-containing blood that should be formed,
Is the 5 coating liquid a thickening agent? Gelatin contains calcium ions (Ca) and is used as a protective colloid.
This is achieved by a coating solution for 11i 2% containing Zenboon, which has a content of 2.0 (10 ppm or less) based on dry gelatin. In the gelatin-containing coating solution for photographic photosensitive materials that is to be coated with a cloth to form a photosensitive layer, the content of calcium ions (Ca) in the gelatin used as a colloid is different from that of the dried gelatin. against 2,00
(1 ppm or more), and has the general formula [1] P(-A)
n (wherein, P represents the main chain or main chain including side chains of a natural or @I戊 polymer, and in most cases, it is a chain consisting of a carbon x 5-carbon bond, but carbon The outer D;; child may contain, for example, nine atoms, nitrogen, etc., and may also have a water group.Also, A I'1-0303M, -80
3M. Which acid group is represented by -COOM 7, M is hydrogen, alkali gold, or -Nr (II, n is an integer of 1 or more), or a compound represented by the general formula [11] JOQ (formula By using a gelatin-containing photographic coating liquid whose % characteristic is viscosity ζ with a compound represented by (where B represents an optionally substituted vinyl group, m is an integer). Gelatin, which is generally used for '1:j and 4°j, is manufactured by solubilizing collagen, the main component of animal skin and bones, in hot water. It is difficult for the collagen to be extracted during the process, so in an advanced manufacturing method, the raw material is soaked in milk of lime for 1 to 3 months, and a long-term pretreatment called R11 lime pickling is performed to extract collagen. Partially water-decomposed Katana II in advance. Beef bone ossein gelatin, which is commonly used, is also manufactured by the above method and is sold as a product in a state containing some calcium ion. The gelatin used in the present invention has a calcium ion content of 2,00 (l) compared to dry gelatin.
The method of converting pprn to 1- is arbitrary, but can be easily achieved, for example, by passing it through a cation exchange resin column. Also, recently, gelatin made from pig skin has been attracting a lot of attention, but this gelatin does not require lime treatment like bone ossein, but is extracted after soaking in an acid such as sulfuric acid for several days. Processed gelate/also the rash of the present invention i>Ji,, :)
Contains FC and is considered useful as a low-calcium ceratin. 1iiJ g+,'; general formula used in the present invention [
Typical examples of the compounds shown in 1) include compounds of polymeric sulfate esters (c), 11. The raw material is a synthetic or natural molecular substance having a hydroxyl group, such as hollyhinyl alcohol, cellulose, alginic acid, starch, etc., and it is added with sulfuric acid, chlorsulfone, etc. Specific examples include Japanese Patent Publication No. 36-21574 and U.S. Patent No. 3.3.
83.3 (+ No. 7-, 1I11 No. 3.51 (i,
No. 983, No. 3, 39], No. 061, No. 3. (1
II O179 (No. 1, (++l No. 3.624,069
No. 3.653.9 (16) Although it is stated in each specification CI, etc.,
2t+! ;O'、Jiha''
Examples include t=5 to 1,110 (l) exemplified attachment [B].Also, as a commercially available product, for example, it is supplied by Kelco Company of New Jersey, USA. There is KELCOSC8. In the compound represented by the general formula [■] used in the present invention, B is styrene, α-methylstyrene, vinyl acetate, acrylic acid, methacrylic acid, acrylic acid methyl ester, ethyl vinyl ether oyohiin. Examples include flobyl vinyl ether. Those in which B is a vinyl methyl group include vinyl methyl ether anhydride 71/
As an inic acid copolymer, the product name is GANTREZ AN,
GeneralAni 1ine & Film C
There is orp. The 111 general formula [T] used in the present invention is a viscous 1r agent shown by Mr. There is also a melting angle qshiq
x+ru. The aqueous solution and organic solvent solution are viscous, and the solution remains stable even if drunk or alcoholic acid is added. Rough contact property The following margin ゝr' The viscosity j:', j (Y, agent and 173 -jA=3/
1 glue; dY and B substances that are completely compatible in 11 go are:
pnozein, hydroxyethylcellulose] 1J
Acrylic 1 True J-Mi M, Acrylic Bumide Volume 1, Ra=Yaston 1), S:++ Vinyl Alcohol, Horibini A/H L3'J ton, Vinipanohyloridone-Vinyl Acetate JWl, = G book, Tenbun food is strong now. The viscous Y agent used in the present invention is Tl

[General formula [1]
Or the conversion shown in [1]
, approximately any of the known thickening agent compounds t1'x J'l
I can be 1, it's not limited to 1 type, it's 2 or more types k D)
)Tj may be done. As an emulsion that can be used for the gelatinized photographic 4゛r@a' of
r, : "tJ"A 1j's 14th 1st, - as silver halide sealed Ii', ter! I'm confused, -) 1 piece (
6) J41. However, even if silver chloride iodobromide or silver iodobromide exists, <, the crystal form and crystal habit of silver in halogen, ζ, etc. The present invention &:1 suitable 1) can be done without depending on the silver ion 6 degree, practical, yp!I (yearly yen of 5 to 7) etc. That Hao Ken (I'', in the silver emulsion there is gold of each E 1h)
4i-7 (43.1 [poor, rhodium, iridium 1
1, lead, lead, lead, etc.) or two or more types of lead, etc.) can be included in combination, and the Journal of Photographic 1 Lien 7. (The J
oural of photograbic 5c
iennece) Vol. 13 (1965) A
Crystal habit regulators and known fogging agents that appear to be j
It can also include all drugs such as anti-inflammatory drugs and anti-517 drugs. My father's silver halide emulsion is a well-known chemical compound X7 F'4.
ζ (e.g. 'iI yellow sensitization, Vt metal sensitization, reduction sensitization, etc.)
? Optical sensitization (for example, tJ times!F Publication No. 43493t), No. 48429744, +% Iyd 1977-1, keeping in mind the sensitive wavelength range.
(No. 16322, 1”14 9 1] l
b 2 9%, ml No. 48-5 6 4 26, 1:q (Public IJ No. 46-549, 1rrl 5 (
No. 1-40662, Kan Hi1 1977-26126, Minister +48-28224 (J', li +48-24726, r*I48-33 s No. 17, No. 48-41733
No. t148-59828, U.S. Bamboo Permit No. 2.177,
4024, same No. 3.752゜670B1 special public service 1977-
No. 19o34, Den No. 150-37538, JP-A No. 1973-
The sensitizing dye described in No. 1630, etc.) may also be a syllable. Also, in history, purple line absorbers ((9i1 Ege German 11th Edition No. 1.182.066, JP-A-47-1026,
No. 50-87326, Rice II! 1 special fI No. 3.253
．． No. 921, No. 2739.888, No. 1111 No. 3,
No. 250,617 (compounds listed in Kil. 6LJ), color antifoggants (e.g., U.S. Pat.
9-Day, No. 2,991.177, UK %W [No. 89
No. 1,158, No. 861.138, JP-A-51-2
7333), desilvering accelerators (e.g. compounds described in JP-A-48-53725), sharpness-improving colored water (
For example, Amaranth-% (compounds described in 17421/1983) are preferably incorporated in equal proportions, and mainly in silver halide emulsions, conventional couplers (for example, the compound described in US Pat.
No. 2.376.679, No. 2.991,177,
No. &021,215, JP-A No. 48-3+) 933, No. 48-43938, No. 48-66836, No. 4
No. 9-42345, rl'fl No. 51-9449, No. 50-132926, Den 150-158329, %
Public Bd49-13576, rffl 51-1078
48, two-dimensional DIR couplers, etc. described in No. 3, etc.). Other thrust agents include hardeners, surfactants, etc.
+++ as appropriate. For example, Artehyde, para, ketone, carbo/acid, active no. 11, mono, 3; J
ζ4・shi system, aziridine, te 1'1°o1noa1n~
It is preferable to contain an inorganic or organic hardening agent such as amber, vinyl sulfur, chromium alum, potassium alum, etc., either alone or in combination. −
In addition, sandonin, argylben-(sodium insulfonate, sulfo-T1 (acid ester salt, hour 11iJ
J47-9303 = Bow, ql: Preferably, it contains a surfactant active agent known in the industry, such as a fluorine-based active PI agent. As the gelatin for the gelatin-containing coating powder according to the present invention, various types of gelatin, such as lime-treated gelatin, acid-treated gelatin, and gelatin conductors (for example, acylated gelatin), can be used alone or in combination. , which may further contain natural or synthetic polymers.
Sari. As a 31y body, various film combs such as Fi, cellulose acetate, polystyrene, polyethylene terephthalate, and monocaronate, polyolefin and 4-fat laminates are used.
I-j~izru. The gelatin of the present invention can be used in commercially available halogen silver photographic materials, such as color negative film, color photographic paper, monochrome photographic paper, and in addition to J.・, Hey) and X-ray films, special photosensitive materials using special light-sensitive materials such as photosensitive materials and Diveliner, etc., and the amount to be applied as the composition of all types of X-phase materials containing gelatin K. ]16, e.g. No Rodin 1
1. Silver emulsion layer, coupler 'dT? ↑Muno Rodinization (
[Ai Emulsion! Old packing 'It'? ,)・

[/-John defense + I = layer 1. It is useful for foils such as - pulling layer, intermediate layer, violet ray absorption filter layer, protection layer, and r'+ layer foil. In the embodiment of the present invention, the temperature of the thickening agent at 6°C is at least 1 ≦ 1.
1 not only allows for stable coating and coating of sticky ribs, but also enables uniformity at sieving speed.
Examples of the gelatin-containing photoresist of the present invention are shown below, which exhibits an excellent effect of being able to maintain the hard and brittle properties, surface -yc, and smoothness of the coating film with good Q-fK. The present invention is not limited to these examples. 5% water-soluble f! , so that the viscosity at 35°C is equal to 25 c, p, the above-mentioned exemplified compound [A] as a thickening agent (however, ! #4 (l)
Carve the Ijj of,! I put a lot of pressure on it and gave it a thrust. The sol-to-gel specific rotation of 791 was added to 6111 using a 10-machi quartz cell at Na DI #589 nm using a 'F'-4 type polarimeter manufactured by Nikko Bunko. This solution was mixed with 2 qb/dry gelatin of a hardening agent, and then applied to a copying support with polyethylene T lamination on both sides to a thickness of 60 μm, and dried under certain conditions. Using two meters for optical rotation, set the sample four times using IJ7 f4't for all color papers: * Soak in ζ for 3 minutes at 33°C.
l (1 (1%, Tsutsumi hitorift', !1,1 mid-dry?
,) This surface -) Y quality visual perception ('(Evaluation based on (0 =
, 11θr, ×-poor and △-slightly good, three prongs 11
By h method. ) to ;'ζ′). Table 1 shows the total CR of each viratin, the specific rotation of the sol → gel at 25°C, and the rotation of the rv membrane after application. , the swelling rate of the film at 25°C, and the gloss f) of the skin V surface. If the content of Ca in the gelatin is within the scope of the present invention)
It can be seen that 2) has excellent gelatin molecule orientation and good physical properties such as film hardness and surface gloss due to less viscosity rule 11. No. 31v1 is the /It light of the applied and peeling film, surrounding - [α]
d and the content of the thickening agent. 6/11 mixture of thickening agents used in the above examples [A]
()~Ig/17P-' ζ and 5 cycles of gelatin solution was added to the film support and then 40μ thick. After drying the gel in the freezing point range (set zone) of 2 to 3 degrees Celsius, it was dried for 2 minutes at 25 degrees Celsius and then for another 2 minutes with B air at 40 degrees Celsius. It was used as a sample. Depending on the type of gelatin rJ+, the ca content V differs; Therefore, in the case of Ge1-8 shown in Figure 3, where the amount of thickening agent added is small, the orientation of the gelatin molecules is higher than the viscosity ratio Ao1. ], it can be seen that it is possible to maintain a high optical rotation and create a bright surface gloss when formed into a film. Takarazuka Gelatin TM-3 (l old 1) 13: As shown in Table 2, by ion V exchange treatment, six types of gelatin molecules 5) to (Hl) containing (7a, 'L:'k) were changed. The viscosity [k] of the added mouth Jt at 35°C was
= 16ill - The result is 2nd 1st and not shown in 1st. 2-1 shows the relationship between the thickening agent [Ca] it and ca g'ii which give a constant viscosity of 25 cp at 35°C. 1st v, l, 97(,; 2 (y, · to viscous (r
, the viscosity that changes with the addition of agent [Ca depends on Ca 182 K in gelatin, especially Ca ++ tJ
DL% end six items “M Todoroki Heron is big, 2 (1101ppm
It can be seen that the thickening is inhibited when the temperature exceeds this. Example 3 5 lime-treated gelatin dissolved in water "g'1." (gelatin used was Takarazuka Gelatin TM-3000) was subjected to ion exchange treatment to obtain na Jl+', k K (l', =;
, ゛Three Gods No Sera 7'n Na (] I) ~(
13) Gold ¥4. '+ Adjustment, R1,4! , monifying agent [D]
The viscosity at 35°C when a constant frost was applied was measured J1. The results are shown in Table 883. Margin below Table 3 Table 3 Iwa Puff Rarizuki Raka fryo (lko, Y old (1) Addition of detergent [D] causes 1% viscosity in 1 gelatin, a+ -1-C! Death depends on degree, sometimes C
a The lower the opening is below 2000 ppm, the more the viscosity increases.
I'm sorry that it's a little ugly. 4 5% lime-treated gelatin aqueous solution (the gelatin used is Takarazuka Gelatin NT-3ooo) was adjusted to υ 1 by ion exchange. The above-mentioned thickening agent [B] and thickening agent [D] buttons were added in varying amounts to make 6 kinds of samples [Nαα(A) to (L9), and then heated to 35℃ ( ■1 measurement was carried out.The results are shown in Table 4. Below is Table 14 (with thickening agent [R] and withering ^11 [D] and (/l) for tJI!/, j5, It turns out that this M is slightly thicker and more sticky than the one used in Germany.
2 @mo(', a fff town is 2(ntl tl
It is recognized that the thickening effect is small when it exceeds 11 rn. 4, FIi'+ Jl'I of 1st page, Ming W1 figure ji
17F, -44'L containing gelatin of the invention? It is a graph showing the relationship between Cs concentration and viscosity in a coating liquid for Fj. jjt12MHr+σ gelatin-containing copy 1
Application fPi V(l constant f+'jl!!: (
35℃, 25cp) i5 viscous i11 agent [A]!
7+119. and Ca4! ! 1 Bl and ■ 1 part (there is. -'t, 'I, -(i, th: tsu[tsuIυ,
1 The relationship between the present invention and the content of copper in the thickening agent [A] is shown in the graph 4'. :) ゐ, To consult with the Imperial Revision l''・Representative of Nishiroku Photo Industry Co., Ltd. zu1' Buriji Saka Hi IB Akira (and 1 other person) IP, 1000 Figure 2 C-1 body xlo'ppm) @3FXJ 0 0.5 10 E b4 Lotus table 'l [A] @ I Mi (g/E) -
``-Itouri Neichi 1■ Mi -Written (spontaneous) September 12, 1980 Commissioner of the Patent Office Kazuo Wakasugi Tono 1 Small 1 Indication 1981 Special Fraud Order No. 141039!; 2 Name of the invention Gelatin Contains photographic coating liquid 3 Supplement 11: Person doing the above/Relationship with h matter Applicant name (127) Roku Konishi Photography Co., Ltd. 4 Agent 〒105 6 Number of inventions multiplied by 1 due to amendment 7 Subject of amendment Specification (Claims and Detailed Description of the Invention II)
8 Details of the amendment (Jl)
Complement 1 [- for t as follows. 1 Patent: Supplement the range of Ilj search as written in 1 [:,. In the gelatin-containing Magawa lacquer 7a solution which is to form the true layer, the coating solution contains a thickening agent and a calcined ion of seratin (which is used as a protective colloid). C
The content of t- in a4+) is 2.000P compared to dry gelatin.
A photographic coating liquid containing gelatin, characterized in that it is less than Pffl. 2 On page 1, lines 12-13, it says, “Phil 1, natono...
Delete the phrase "suitable for use." 3 On page 2, line 18, replace “Flexible support 1-” with “
"A flexible support or a non-flexible support such as glass," is the supplement 1. 4 On page 7, line 11, the phrase "flexible support" is amended to read "support." 5 Delete the words “coated on a flexible support” from page 7, line 18 and page 8, lines 5-6. 66 No. 17
On page M column [As a support, cellulose acetate-1.
``The support may be any conventional photographic support, such as cellulose acetate.'' 7. On page 18, line 3, “Laminated paper, etc. is used.”
The statement has been corrected to read, ``A flexible support such as laminated paper or a non-flexible support such as crow is used.'' Below 1

Claims (1)

[Claims] In the gelatin-containing photographic solution which should be coated onto a flexible support to form a photographic PWi, the cold cloth contains a thickening agent and is used with a retention colloid. The content of calcium ions (ma) in the gelatin -bi added to the dried gelatin jL2. [1 (1 ppmJ', below I!1'z) Photographic coating solution containing ceratin.