JPS6017106B2 - Photographic elements for color diffusion transfer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to color diffusion transfer photographic elements, and more particularly to color diffusion transfer (DTR color) photographic elements having a neutralizing timing layer formed from a polymer latex.

Conventionally, in the color diffusion transfer method, a high pH state based on an aqueous alkaline developer is continued for a predetermined period of time to diffusely transfer color image-forming substances to a soot beam layer, and then the photosensitive material is exposed to light using an acid in a neutralization layer. The pH of the layer, etc. is lowered to stop the formation of a color image.

In addition, color diffusion transfer photographic elements are provided with a timing layer as a neutralization system in conjunction with the neutralization layer to adjust the high pH duration depending on the actual processing temperature. (W.T. Hinson, Jr. Chopsticks, “Pho
to crab aphicSci. &Eng. ” magazine second lid 15
Page 5, 197 Mother King). For example, Japanese Patent Application Laid-open No. 481/1986, U.S. Pat. No. 3,929-7600, U.S. Pat.
, No. 144, No. 3,932, No. 1, which is initially non-diffusible, but becomes diffusible through redox reaction or coupling reaction with the oxidation product of the developer. In the color diffusion transfer method using a type of dye image-providing material that releases The density loss is compensated for by increasing the high pH duration, extending the time available for development and dye release and transfer. It is desirable to provide a timing layer with zero "temperature compensation" functionality. Examples of this type of timing layer include the timing layer made of polyvinyl alcohol described in U.S. Pat.
Examples include those described on page 86 of Disclosure magazine (i.e., a timing layer formed from a latex of methyl acrylate-vinylidene chloride-itaconic acid copolymer or acrylonitrile-vinylidene chloride-acrylic acid copolymer). . However, in the timing layer described in Tokoseki Sho 49-22935, the degree of decrease in horse mackerel permeability on the low temperature side is low, and the development error cannot be sufficiently compensated for.

Also, the above “Research Disclosure”
The timing layer described in the magazine requires the use of vinylidene chloride, which is a chemical that is harmful to the human body, has a low boiling point, and requires special equipment to produce polymer latex, which has the disadvantage of increasing production costs. . Furthermore, through a heat sealing process suitable for high-speed mass production, a cover sheet with a neutralization system and a photosensitive sheet consisting of an image receiving element and a photosensitive element sequentially coated on a support are laminated into an integrated film unit. If the film unit is handled roughly, especially at low temperatures, the heat-sealed portion of the film unit may break and the processing liquid spread between the photosensitive element and the cover sheet may leak out of the unit. It's easy to get up.

In many cases, this peeling of the heat-sealed portion is often caused by poor adhesion between the timing layer and the adjacent layer. As a result of intensive research, the present inventors have found that by incorporating a transition metal compound and using a redox polymerization initiator during the synthesis of the polymer latex of the present invention, a surprising temperature compensation function and adhesion with adjacent layers are improved. I found it.

The first object of the present invention is to provide a cover sheet with a large temperature compensation function. Second, it provides a timing layer that has good adhesion with adjacent layers even at low temperatures, and as a result, provides a film unit for color diffusion transfer method that does not cause peeling of the film unit at heat-sealed areas. It's about doing. The above objects can be effectively achieved by a photographic element having a timing layer made of the polymer latex described below.

Neutralization system for lowering the axis of aqueous alkaline developer [This neutralization system includes a neutralization layer and a timing layer,
The timing layer is placed directly or indirectly overlapping the neutralization layer in such a positional relationship that the developer reaches the neutralization layer via the timing layer. ] in which the timing layer is copolymerizable with at least one polymerizable ethylenically unsaturated monomer having at least one free carboxylic acid or phosphoric acid group or a salt thereof; It is formed from at least one type of polymer latex obtained by emulsion polymerizing at least one other polymerizable ethylenically unsaturated monomer using a redox polymerization initiator in the presence of a transition metal compound. A color diffusion transfer photographic element characterized by: The above polymer latex is obtained by emulsion polymerizing at least one monomer selected from the following groups A, B, and C together using a redox polymerization initiator in the presence of a transition metal compound. Preferably.

Group A: Monomers represented by the following general formula (1) (approximately 0.
5 to 4% by weight is appropriate) General formula (1) J: represents a hydrogen atom, a methyl group, or.

K: represents a chlorine atom, a cyano group, or J.

Was. GI, 〇, G3 representing or: May be the same or different, and each represents also.

A: hydrogen atom, methyl group, 10-0, or 1NH-Y
represents.

or represents.

R: represents an aliphatic divalent group having 2 to 6 carbon atoms.

R2: represents a hydrogen atom or an alkyl group or acyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms). R3
, R4, R5, R6, R7: represents a hydrogen atom or -CH20, excluding combinations in which all of R3 to R7 are hydrogen atoms at the same time.

R8a, R8b: may be the same or different, and each represents an alkyl group, formyl group, or acyl group having 1 to 6 carbon atoms (preferably 1 to .4 carbon atoms), and R8a and R8
b may be connected to form a ring.

×: Represents a halogen atom (e.g. chlorine, bromine atom) n
,: Represents an integer of 0 or 1.

Mountain: represents an integer from 1 to 10.

m: represents an integer from 2 to 8.

Examples of the acyl groups for R2, R8aHa, and R8b include aliphatic groups (acetyl groups, etc.).

The ring formed by the connection of R8a and R8b is
For example, it is a 5- to 6-membered saturated heterocycle (hetero atoms may include oxygen atoms in addition to nitrogen atoms). Group B): polymerizable ethylenically unsaturated monomers having at least one free carboxylic acid group or phosphoric acid group or a salt thereof.

(approximately 1 to 1% by weight) Group C): Ethylene monomers other than Group A and Group B that can be copolymerized with Group A and Group B. (
Approximately 48 to 99% by weight) In more detail,
Component A) A reactive monomer group represented by the general formula (1), which includes glycidyl compounds and their precursors (e.g. glycidyl acrylate, glycidyl methacrylate,
Glycidyl p-vinylbenzoate, glycidyl crotonate, diglycidyl itaconate, diglycidyl maleate, diglycidyl methylene malonate, glycidyl vinyl ether, allyl glycidyl ether, glycidyl-Q-chloroacrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-chloropropyl methacrylate, etc.), hydroxymethylacrylamide, hydroxymethylmethacrylamide, alkoxymethylacrylamide (e.g. 0 methoxymethylacrylamide, ethoxymethylacrylamide, butoxymethylacrylamide, hexyloxymethylacrylamide, etc.), alkoxymethylmethacrylamide , (e.g. methoxymethylacrylamide, poxymethacrylamide, etc.), acyloxymethylacrylamide (e.g. acetoxymethylacrylamide, propionyloxymethylacrylamide, etc.)
, acyloxymethylmethacrylamide (for example, acetoxymethylmethacrylamide 0, etc.), dialkylaminomethylacrylamide (for example, dimethylaminomethylacrylamide, diethylaminomethylacrylamide, dibutylaminomethylacrylamide, N-methyl-N-ethylaminomethylacrylamide, etc.). dialkylaminomethylmethacrylamide (e.g. dimethylaminomethylmethacrylamide, dipropylaminomethylmethacrylamide, N-methyl-N-hydroxyethylaminomethylmethacrylamide, etc.), morpholinomethylacrylamide, N-(acrylamidomethyl)- Prolactam, N-(acrylamidomethyl)-pyrrolidone, acrolein, methyl vinyl ketone, aziridinoalkyl acrylate (e.g. aziridinoethyl acrylate, etc.), aziridinoalkyl methacrylate, etc.) Hydroxymethylated diacetone acrylamide , hydroxymethylated diacetone methacrylamide, etc.

Others “Makromo-lec’s are Chemie
Examples include derivatives of acrylamide or methacrylamide described in ``Wang,'' Vol. 57, pp. 27-51 (1962). When it is a single-pronged formula (1), it represents a methylolated product of diacetone acrylamide or diacetone methacrylamide.

R3, R4, R5, R6 and R7 each represent -CH20 or a hydrogen atom, excluding combinations in which all are hydrogen atoms at the same time. Generally, the methylolated product includes mono-
, di-, tri-, tetra-, and pentamethylolated forms. Generally, the main component is a substituted product with a degree of substitution of 3, which is different from the trimethylolated product, and a mixture containing partially methylolated products with a degree of substitution of 1, 2, 4, and 5. A derivative having a degree of methylolation of approximately 3 is meant. Among copolymer component B), preferred monomers include unsaturated acids represented by the following general formula (0) or salts thereof.

General Formula (0) Specific examples of the monomer of General Formula (B) include the following compounds.

Acrylic acid, methacrylic acid, itaconic acid, maleic acid
Crotonic acid, fumaric acid, methylene malonic acid, monoalkyl itaconate (e.g. monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.), monoalkyl maleate (e.g. monomethyl maleate, monoethyl maleate, monobutyl maleate, etc.) monobutyl, monooctyl maleate, etc.), sodium acrylate citraconate, ammonium acrylate, ammonium methacrylate, acryloyloxyalkyl phosphate (e.g. acryloyloxyethyl phosphate, 3M acryloyloxypropyl-2-phosphate, etc.), methacryloyloxyalkyl Phosphates (eg methacryloyloxyethyl phosphate (acid phosphooxyethyl methacrylate), 3-methacryloyloxypropyl-2-phosphate, etc.), 3-chloro 2-acid phosphooxypropyl methacrylate.

Copolymerization component C) can be freely selected from ethylene monomers known in the art, but monomers represented by the following general formula (m) are particularly effective.

General formula (town) represents an integer from 0 to 3.

The aliphatic groups RII to R13 include linear or branched alkyl groups (including cyclic ones) and substituted alkyl groups, and the number of carbon atoms in the alkyl group is preferably 1 to 12.

Substituents for substituted alkyl groups include alkoxy groups, aryl groups, aryloxy groups, arylalkyleneoxy groups, halogen atoms, cyano groups, acyl groups, alkylcarbonyloxy groups, arylcarbonyloxy groups, amino groups (also substituted amino groups). including an alkyl group as a substituent,
such as aryl groups.

The number of substituents is 1 to 2), hydroxy group, alkoxyalkyleneoxy group, heterocyclic residue (hetero atoms include, for example, oxygen atom, nitrogen atom, sulfur atom, etc. The number of ring members is 5 to 6), Preferably, the ring may be unsaturated or saturated.An aromatic ring may be further fused to the heterocycle. Also, RII~R13
Of course, the substituted phenyl group of the aryl group includes a naphthyl group, and examples of the substituent include an alkyl group in addition to the substituents listed above for the substituted alkyl group.

Examples of halogen atoms for R, o and Z include chlorine, bromine,
One can mention fluorine. The monomers of copolymerization component C) are not particularly limited as long as they have at least one vinyl group and are copolymerizable with group A and group B monomers, but examples include acrylic acid esters and methacrylic acid esters. esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, pinylesters, vinyl heterocyclic compounds, styrenes, maleic acid esters, fumaric acid esters, itaconic acid esters, olefins, crotonate esters, It can be selected from unsaturated nitriles etc. (However, monomers corresponding to Group A and Group B are excluded) Among these, acrylic esters, methacrylic esters, vinyl esters, styrenes and olefins are particularly preferred.

Examples of acrylic esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, nx butyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, inbutyl acrylate, and SeC-butyl acrylate. , amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, 2-phenoxyethyl acrylate, 2-chloroethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate
Cyclohexyl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,3-dihydroxypropyl acrylate, ethylene glycol diacrylate, triethylene glycol triacrylate, Methylolpropane triacrylate, 2
-methoxyethyl acrylate and 2-ethoxyethyl acrylate.

Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec.
-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate,
Penzyl methacrylate, acetoacetoxyethyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate (ethylene) Glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane monomethacrylate, bentaerythritol trimethacrylate, 2-methoxyethyl methacrylate t2-ethoxyethyl methacrylate can be mentioned.As vinyl esters, for example, vinyl acetate, vinyl propio Examples include vinyl ester, vinyl butyrate, vinyl chloroacetate, pinyl dichloroacetate, vinyl methoxy acetate, vinyl acetoacetate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, and the like.

Examples of styrenes include tostyrene, methylstyrene, chloromethylstyrene, trifluoromethylstyrene, acetoxymethylstyrene, methoxystyrene,
Chlorstyrene, dichlorostyrene, trichlorstyrene, divinylbenzene.

Examples include mustyrene. Examples of olefins include ethylene, butadiene, isobrene, chloroprene, propylene, vinyl chloride, pinyl bromide, vinylidene chloride, vinylidene bromide, vinylideso fluoride, and the like.

Examples of acrylamides include acrylamide
Examples of allyl compounds include allyl acetate and allyl benzoate; examples of pinylethers include methyl vinyl ether and chloroethyl pinylether. .

It is preferable that at least one of the group C monomers constituting the polymer latex of the present invention is water-insoluble.

When there are two Group C monomers constituting the polymer latex, it is preferable that the monomer that is larger in quantity is water-insoluble. Here, water-insoluble means that the solubility in water (25° C.) is 3% by weight or less. The transition metal compounds used in the present invention include Sc with atomic number 21 to Zn with atomic number 30, Y with atomic number 39 to Cd with atomic number 48,
It consists of elements from 7 La to 80 Hg, and 89 Ac or more.

Preferred examples include compounds of metals such as manganese, cobalt, nickel, iron, chromium, molybdenum, copper, tungsten, zinc, cadmium, tin, cerium, and titanium. Among these compounds, water-soluble salts are particularly preferred. Specific examples include acobentamine cobalt (m) chloride, zinc chloride, cadmium chloride, chromium chloride (b), cobalt chloride (D), tin chloride (n), titanium chloride (m) , (W), Iron chloride (B), (
m) and its hydrates, steel chloride (b) and its hydrates, nickel chloride (D) and its hydrates, manganese chloride (D) and its hydrates, cobalt perchlorate (b)
, nickel (0) perchlorate pentahydrate, dichlorotetraacochrome (m) chloride, dihydrate, cadmium bromide and its hydrate, cobalt (0) bromide and its hydrate,
Cerium bromide, cerium bromide (machi) pentahydrate, iron bromide (
0), (m)) and its hydrates, steel bromide (0), nickel bromide (0), manganese bromide (b) and its hydrates, cadmium nitrate and its hydrates, chromium nitrate ( m)
Nonahydrate, cobalt nitrate (0) hexahydrate, cerium nitrate (m), (W) ammonium and its hydrates, iron nitrate (0), (m) hydrate, steel nitrate (0) water nickel (0) nitrate hexahydrate, manganese (n) nitrate hexahydrate, potassium tungstate, ammonium hexachlorostannate (N), potassium molybdate, zinc sulfate and its hydrate, cadmium sulfate and its hydrate, chromium (0), (m) sulfate, hydrate, cobalt (0) sulfate and its hydrate, tin sulfate (W) dihydrate, cerium sulfate (m)
), iron sulfate (0), (m) hydrate, steel sulfate (0) and its hydrate, nickel sulfate (0) and its hydrate, manganese sulfate, and the like. Among these, iron, copper,
Particularly preferred are compounds of nickel and cerium. The amount of the transition metal compound added during latex synthesis is preferably 10-9 mol/g to 10-4 mol/g based on the polymer solid content; if it is too large, not only will the effects of the present invention not be achieved, It can adversely affect the photographic imaging process and reduce the quality of the final photographic image. A particularly preferable amount of the transition metal compound added is 1% based on the solid content of the polymer.
0-8 mole grams to 10-6 mole grams. The copolymer composition of the latex that can be used in the present invention has a desirable copolymer composition from the following viewpoints: the latex is cheap and easy to manufacture, and the latex has long-term storage stability. The timing layer formed from the latex should have appropriate alkali aqueous solution permeability and the permeability should have the desired temperature dependence, and the adjacent layer to which the latex timing layer is applied (if (a relatively hydrophobic layer formed by applying an organic solvent solution of polymer) and good adhesion strength over a wide temperature range.

The present inventors have found the following preferred copolymer components and their compositions: As component (A), glycidyl acrylate, glycidyl methacrylate, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, or Particularly preferably, about 0.5% to 4% by weight of N-alkoxymethylacrylamide, N-alkoxymethylmethacrylamide: about 1% to 4% by weight of acrylic acid, methacrylic acid or itaconic acid as component (B) % by weight, particularly preferably about 1 to 8% by weight; as component (C) at least 1% by weight of the general formula (m)
About 48 to 9% by weight of the ethylene-based monomers, particularly preferably about 77% by weight.

As component (C), two or more types of copolymerization components can be used in combination, if desired. For example, in order to obtain a latex having an appropriate minimum film forming temperature (described in detail later), a hard copolymer component and a softening copolymer component may be mixed in an appropriate ratio. In this case, the hard copolymerization component is preferably an ethylene monomer belonging to the general formula (machi) whose homopolymer has a glass transition temperature of 5000 or higher, and specifically includes, for example, styrene, acrylonitrile, ethyl methacrylate, isopropyl methacrylate, Mention may be made of ten-butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate or methyl methacrylate. Further, as the softening and copolymerization component, an ethylene monomer of the general formula (m) whose homobolymer has a glass transition temperature of 4000 or less is preferable, and specific examples include substituted or unsubstituted alkyl acrylates. (Substituents for alkyl groups include alkoxy groups, halogen atoms, etc.), ethylene, propylene, butadiene, isoprene, vinyl chloride, vinylidene chloride, and the like. Representative examples of preferred aqueous latex copolymers for use in coating the timing layer of the present invention are listed below.

1 Styrene-n-butyl acrylate acrylic acid-
N-Hydroxymethylacrylamide copolymer (weight ratio 51.7:42.3:2:4)<FeS04.7 days 20
, 4.3×10-7>2 Styrene-n-butyl acrylate acrylic acid-N-hydroxymethyl acrylamide copolymer (weight ratio 61:27:4:8)<FeS04
．． 7 days 20,1×10-6>3 Methyl methacrylate-n-butyl acrylate acrylic acid-N-hydroxymethyl acrylamide copolymer (weight ratio 32:58:
4:6)
Weight ratio 63:28:3:6)<CuS0418L○,3
×10-7>5 Methyl methacrylate-acrylic acid-
N-Hydroxymethylacrylamide copolymer (weight ratio 93:3:4)<FeS04.7 days 20,5xlo-7
>6 Butyl methacrylate-acrylic acid-N-hydride 0
oxymethylacrylamide copolymer (weight ratio 90:4:
6) <CuS04.9 day 20,7xlo-7>7 se
c-butyl methacrylate-acrylic acid-N-butoxymethyl acrylamide copolymer (weight ratio 77:3:20
)<Cu(N03)2. crime 20, lxlo-6>8 ethyl methacrylate-itaconic acid-hydroxymethylated diacetone acrylamide (degree of hydroxymethylation 2.
5) English polymer (weight ratio 95:2.5:2.5) <CuS
04.9 days 20,2xlo-6>9 2-acetoxyethyl methacrylate-acrylic acid-N-ethoxymethylacrylamide copolymer (weight ratio 873:10) <F
e(N03)2. Thin 20,2x7xlo-7>10 Ethyl acrylate methacrylic acid-N-butoxymethylacrylamide copolymer (weight ratio 88:6:6) <(
N ratio) 2Ce (N03) 6,5×10-7>11 Propyl methacrylate-maleic acid-N-methoxymethylacrylamide copolymer (weight ratio 90:2:8)
(N03)2. Fine 20,6.5xlo-7>12 Styrene-n-butyl acrylate-2-methacryloyloxyethyl phosphate-N-butoxymethylacrylamide copolymer (weight ratio 50:40:2:8)<FeC
13.8 days 20,4.2xlo-7>13 Styrene-ethoxyethyl acrylate acrylic acid-N-hydroxymethyl acrylamide copolymer (weight ratio 43:43
:4:10) <CJC12.2nd 20.3xlo-7>
14 Styrene-n-propyl acrylate and taconic acid-N-methoxymethyl methacrylamide copolymer (weight ratio 40:8:14)<FeS04.7 days 20,8.
6×10-7>15 Styrene-n-butyl acrylate acrylic acid-hydroxymethylated diacetone acrylamide (degree of hydroxymethylation 2.5) copolymer (weight ratio 51.7; 41:8:2:4.5)< Cu (N03)
2, Pan 20, 7.2XIO-7>16 Methyl methacrylate-butylacrylate acrylic acid-N-hydroxymethylacrylamide copolymer (weight ratio 36.1:
53.9:2:8)<Ni(N03)2・Navy 20.4×
10-7>17 n-butyl methacrylate-acrylonitrile-acrylic acid-N-ethoxymethylacrylamide copolymer (weight ratio 78:6:4:12)<FeS0
4.7 days 20,9xlo-7>18 n-butyl methacrylate-acrylonitrile-itaconic acid-N-hydroxymethyl methacrylamide copolymer (weight ratio 79:5
:2:14) <FeC12,1×10-7>19 Styrene-n-butyl acrylate acrylic acid-N-acetoxymethyl acrylamide copolymer (weight ratio 50:4
0:3:7)<CuS04.9 days 20,6.7xlo-
7>20 Styrene-n-butyl acrylate acrylic acid-N-(morpholinomethyl)methacrylamide copolymer (weight ratio 48:40:4:8)<Ce2(S○4)3
, 8×10-7> 21 Vinylidene chloride-ethyl acrylate acrylic acid-N-methoxymethyl acrylamide copolymer (weight ratio 85:8:3:4) <FeC 12.4 days 20.8×1
0-8>22 n-butyl methacrylate-acrylic acid-glycidyl acrylate copolymer (weight ratio 87:3:
10)<Cu(N○3) 2.3 days 20,5.6×10-
7>23 Methyl methacrylate-n-butyl acrylate-itaconic acid-glycidylmethac, rylate copolymer (weight ratio 46:40::2:12)<FeC13-Mother's day 20,4-7×10-7 >24 sec-butyl methacrylate-2-methacryloyloxyethylphosphonate to glycidyl arylate copolymer ((weight ratio 80:
9:11) FeSO4.7 days 20,6×10-7>25
Styrene-n-butyl acrylate acrylic acid-glycidyl acrylate copolymer (weight ratio 47.9: mottled.
1:2:12)<CuS04.9 days 20,4×10-7
>26 Styrene-n-butyl acrylate-acrylic acid-glycidyl acrylate copolymer (weight ratio 46:8
:37.2:4:12) CuC〆2-2 days 20,3×1
0-7> 27 Styrene-ethoxyethyl acrylate acrylic acid-glycidyl acrylate copolymer (weight ratio 43
:43:4310) <FeC so2.4 days 20,7×10
-7>28 Styrene-n-butyl acrylate itaconic acid-glycidyl methacrylate copolymer (weight ratio 4
4:42:3:11)<Ni(N03)2. Group 20,6
xlo-7>29 Styrene-butyl acrylate methacrylate-glycidyl methacrylate copolymer (weight ratio 40:38:8:14)<FeS04.7 days 20.1×
10-6>30 Styrene-n-butyl acrylate acrylic acid-glycidyl methacrylate copolymer (weight ratio 44:2:34:8:6:15) FeC12.4 days 20,2.7×10-7> 31 Ethyl methacrylate-acrylic acid copolymer (weight ratio 97:3) <FeS04
:7 days 20,2×2×10-7>32 Butylmethac I
J-rate-acrylic acid copolymer (polymerization ratio 97.5:25
)<FeC12.4 days 20,4×10-7>33 Butyl methacrylate-itaconic acid copolymer (polymerization ratio 98:
2) <F(N03)2,5xlo-7> 34 Methyl methacrylate-butyl acrylate acrylic acid copolymer (polymerization ratio 50; 47:3) <CWC12
．． 2 days 20,1・2×10-6>35 Styrene-butyl acrylate to acrylic acid copolymer (polymerization ratio 53:4
3:4) <FeS04.7th 20,6×10-7>36
Styrene-ethyl acrylate maleic acid copolymer (polymerization ratio 54:44:2) <CuS04.9 days 20.8
．． 2xlo-7>37 Penzyl methacrylate-butyl acrylate-methacrylate acid copolymer (polymerization ratio 5
5:39:6)<FeS04.7 days 20,7.5×10
-7>38 Butyl methacrylate-N,N-diethylacrylamide-acrylic acid copolymer (polymerization ratio 80:1
7:3) FeC12.4 days 20,6.3xlo-7>3
9 Vinyltoluene-ethoxyethyl acrylate-acrylic acid copolymer (polymerization ratio 54:43:3) <FeS0
4.7 days 20,5.3xlo-7>40 Propyl methacrylate-ethyl acrylate methacrylic acid-acrylic acid copolymer (weight ratio 72:24:2:2)<FeS
04.7 days 20,7.4×10-7> Here, the description in <> is the type and amount of transition metal compound added during polymer latex synthesis (mol/g (polymer solid content))
represents.

The above weight ratios are for each monomer during polymer latex synthesis.
is the addition weight ratio of Polymer used in the present invention.

For synthesis of latex, Japanese Patent Publication Nos. 47-29195, 48-37,488, 48-76,593,
No. 48-92,022; No. 49-219134;
No. 49-120, 634, Hakama Gansho 51-14 & 58
9, British Patent No. 1,211,03y, British Patent No. 961,3
No. 95, U.S. Patent No. 2,795,564, U.S. Patent No. 2,9
No. 14,499, No. 3,033, No. 3, No. 3, 5
47,89 number, same number 3,227,672, same number 3,
No. 290,417, No. 3,262,919, No. 3
, 245 932, 2,6817897, Mukai No. 3,230,275, Canadian Patent No. 704,778
No., John, C., Bethlop. Sura chopsticks ``Official Digest''(John's Petropoulose)
Ne1: enemyfjejaIDigest)3〆? 19-7
36 (1961), “Introduction to Emulsion” (1) by Sadao Hayashi
970), “Chemistry of Polymer Latex” by Soichi Muroi (1)
970), “Vinyl Mulsion” by Takuhiko Motoyama (196)
5), Mike Shi-der, Journal of Science 'Polymer Chemistry Edition' by Mike Shi-der, Juan et al.
l;JomMI ○f PoIMmer Science
e, PolymerChemis○yEditio
It is convenient to carry out the method with reference to the method described in eg. It goes without saying that the concentration, polymerization temperature, reaction time, etc. can be varied widely and easily depending on the purpose. For example, polymerization is generally carried out at 20-180 oo, preferably 40-120 oo.

In the polymerization reaction, 0.0% of the total monomers to be polymerized are usually used.
05 to 5% by weight of a redox radical polymerization initiator and the transition metal compound of the present invention io-9 to 10-4 mol/g
and, if necessary, 0.1 to 10% by weight of an emulsifier. A redox polymerization initiator is achieved by combining an oxidizing agent and a transition agent. Examples of oxidizing agents used as redox polymerization initiators include potassium persulfate, ammonium persulfate, sodium perphosphate, sasa rt-butyl/di-octoate, benzoyl peroxide, isopropyl percarbonate, 2,4-dichlorobenzoyl peroxide, Methyl ethyl ketone peroxide, cumene hydro/gu oxide, dicumyl/
Examples include f-oxide. Examples of reducing agents used as redox polymerization initiators include bisulfites (e.g., sodium bisulfite, potassium bisulfite, etc.), primary salts of polyvalent metals (e.g., ferrous salts (e.g., ferrous chloride, etc.), , ferrous sulfate, etc.), cuprous salts (e.g., cuprous chloride, cuprous sulfate, etc.), amine compounds (e.g., ethanolamine, triethanolamine, polyethylene polyamine, N,N-dimethyl aniline, etc.), mercapto compounds (eg, mercaptobenzothiazole, 2,4,6-trichlorothiophenol, etc.), and the like.

Among these, a combination of persulfate and bisulfite is particularly preferred from the viewpoint of stability, safety, handling, economy, odorlessness, etc. The molar ratio of the above-mentioned oxidizing agent to the reducing agent is suitably 1'10 to 1, preferably 1.

As the reducing agent for the redox polymerization initiator, the first salt of a polyvalent metal L, especially when using the first salt of a transition metal, is a polyvalent metal that is different from the metal of the transition metal compound used during polymerization of the polymer latex. Primary salt should be used.

Examples of emulsifiers include anionic, cationic, amphoteric, and nonionic surfactants as well as water-soluble polymers.

For example, sodium laurate, sodium dodecyl sulfate,
Sodium 1-octoxycarbonylmethyl-1-octoxycarbonylmethanesulfonate, Sodium laurylnaphthalenesulfonate, Sodium laurylbenzenesulfonate Sodium traurylphosphate Tocetyltrimethylammonium chloride, Dodecyltrimethylammonium chloride, N-2-ethylhexylpyridinium Examples include chloride, polyoxyethylene nonyl ether, polyoxyethylene sorbitan lauryl ester, polyvinyl alcohol, an emulsifier described in Japanese Patent Publication No. 1983-619, and a water-lacquer polymer. Next, a specific synthesis example will be given and explained, but it is not limited to this.

Synthesis Example 1 (Synthesis of Exemplified Compound 5) 1. Place the three-tube flask on a water bath, and equip it with a Kashihiro apparatus, a nitrogen introduction tube, a thermometer, and a reflux condenser tube.

In addition, alkylphenyl is also used as sodium phenyl ether disulfonate (the number of carbon atoms in the alkyl is 12 as the main component).
Palisade t% aqueous solution 3. Pour the fins and 750 ml of distilled water and raise the temperature while replacing the air in the flask with nitrogen gas to 600 ml of distilled water.
Set to 0. 6g of N-methylolacrylamide, 4g of acrylic acid. Beard, methyl methacrylate 139. Add a rudder, fly and emulsify. Ferrous sulfate. 20 m' of an aqueous solution containing 9 of 21 heptahydrate, 20 m of an aqueous solution of 9 of 410 ljium persulfate, and 1 of sodium bisulfite.
10 m' of an aqueous solution in which 9 of 60 was dissolved was added one after another. Polymerization starts immediately and heat is generated to about 7,000 ℃. After 2 hours, 50 parts of an aqueous solution containing 410 parts of potassium persulfate and 160 parts of sodium bisulfite were added and the mixture was heated at 6,000 °C for another 2 hours, and then allowed to fall to room temperature to stop the reaction. The average particle diameter measured with a microscope was in the 0.0 range. Synthesis Example 2 (Synthesis of Exemplified Compound 1) In the same apparatus as in Synthesis Example 1, sodium alkyl phenyl phenyl ether disulfonate (alkyl carbon number Inject a 43wt% aqueous solution of 12) 3. acid and 750% of distilled water.

The air in the flask was replaced with nitrogen gas and the temperature was raised to 50:00.
Make it. N-hydroxymethylamide base, acrylic acid spots, styrene 77. Gunship and butyl acrylate63. In addition, Isobai ``emulsifies. Ferrous sulfate. Heptahydrate 1 x 9
Sequentially add 10 parts of an aqueous solution in which ammonium persulfate is dissolved. Polymerization reaction begins and heat is generated to about 50 parts. After 2 hours, 30 parts of ammonium persulfate and sodium bisulfite are added. Add 50 ml of an aqueous solution containing 140 chloride, stir for another 2 hours at 50 pm, and let the mixture reach room temperature to stop the reaction.

The average particle diameter measured using an electron microscope was 0.07 mm. Other polymer latexes of the present invention can also be synthesized in the same manner as these synthesis examples. The particle size of the polymer latex according to the invention is thus significantly finer than that of the prior art. For reference purposes, the following is a synthesis method for a secondary polymer latex (comparative synthesis example). Comparative Synthesis Example la Ferrous sulfate used in Synthesis Example 1. A latex of Exemplified Compound 6 and Compound 5 was synthesized in the same manner as in Synthesis Example 1 except that heptahydrate 21 and 9 were not used.

The average particle diameter measured with an electron microscope was 0.1 small.
Comparative Synthesis Example Ferrous sulfate used in Synthesis Example 2. A latex of exemplified compound 0 and 1 was synthesized in the same manner as in Synthesis Example 2 except that heptahydrate 18 was not used.

The average particle diameter measured with an electron microscope was this. Comparative Synthesis Example lb 9×2 of sodium bisulfite 160 used in Synthesis Example 1
Latex was synthesized in the same manner as in Synthesis Example 1 except that .

The average particle diameter measured with a cypress microscope was 0.1 Iso.
Comparative Synthesis Example Sodium bisulfite used in Synthesis Example 2 9×2
0 lattetus was synthesized in the same manner as in Synthesis Example 2 except that .

The average particle diameter measured using an electron microscope was 0.17 mm. The average particle size of the timing layer latex of the present invention is preferably between 0.02 and 0.02. It's Sha.

(This average particle size is determined by measuring the particle diameter using an electron microscope in a conventional manner and taking the number average of these measurements.)
. The timing layer polymer latex of the present invention may be further modified.

That is, it can be improved by the method described below. 0 ■ Method of introducing hydrophilic groups into polymer latex.

In the above general formula (heavy), "R2 is a hydrogen atom or R3~
A hydrophilic group is introduced into a polymer latex obtained by using a monomer in which at least one of R7 corresponds to a -CH20 group. Specifically, this can be done by adding, for example, sodium bisulfite to the above polymer latex. Other specific examples include C. E. Schildk Fertilizer Department ``Pomer Pratio Polymer Process, Inte Daielence (1965 King) 3
This can be done according to the method described on page 40.

(2) Copolymerizing at least four types of monomers, including the monomers listed above and the sulfonic acid-containing monomers, among the monomers of Groups A) and B) and the monomers of Group C), How to make polymer latex.

Examples of the sulfonic acid-containing monomer include styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxylkylsulfonic acid (for example,
(acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, acryloyloxybutylsulfonic acid, etc.)
, Metacris. methyloxyalkyl sulfonic acids (e.g. methacryloyloxymethyl sulfonic acid, methacryloyl ethyl sulfonic acid, methacryloyloxypropylsulfonic acid, methacryloyloxybutyl sulfonic acid, etc.), acrylamide alkyl sulfonic acids (e.g. 2- Acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.), methacrylamide alkylsulfonic acid (for example, 2-methacrylamido-2-methylethanesulfonic acid) tansulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc.) Generally, hydrophilic groups such as sulfonic acid groups are added to polymer latex. The introduction rate of N-methylol groups and other crosslinking groups can be varied within the range of 0.1 to 80 mol% of the total crosslinking groups. can be applied directly or indirectly on the neutralization layer as it is or diluted with water as appropriate.Here, "indirectly" means other timing layers (e.g., cellulose acetate layer) or This means applying the timing layer of the present invention on the neutralizing layer via a layer such as an adhesion improving layer. Examples of adhesion improving layers include layers containing hydrophilic colloids such as gelatin and polypinyl alcohol.

Further, the reactive latex of the present invention may be added to about 0.1 to lr.
It can be used as an adhesion-improving layer by coating it to a thickness of 100 mL, and a known latex timing layer can also be coated.

Other timing layers mentioned above include U.S. Pat.
, 029 84y and 4,050 394, maleic anhydride copolymers such as styrene-maleic anhydride copolymers, methyl vinyl ether-maleic anhydride, vinyl acetate A timing layer coated by mixing a maleic anhydride copolymer or the like, or a homopolymer of hydroxyethyl acrylate or hydroxyethyl methacrylate as shown in Japanese Patent Publication No. 52-46496, or these and other vinyl monomers. It is preferable to use a timing layer made of an English polymer.

Photographic elements of the invention include a cover sheet for covering the "photosensitive element" provided that the neutralization system of the invention is incorporated therein.

), or a photosensitive sheet consisting of an "image-receiving element" and a "photosensitive element" sequentially coated on a support, a "cover sheet" having the neutralization system of the present invention, and the photosensitive element. To be spread between the cover sheets
A so-called laminate-integrated film in which "processing elements" are integrated (however, these elements may be removable as necessary). Although it may be a unit, such a film. Preferably a unit. The photographic element of the present invention also includes an image receiving element coated on a support, a neutralizing layer, a timing layer (the layers may be two or more, and includes a timing layer according to the present invention) on the support; A type of film that is so-called peelable and can be used as a negative, in which a developing solution is spread between the photosensitive elements and the members coated in sequence. It may be a unit.

Additionally, although in a less preferred embodiment, the neutralization system of the invention o may be located in the receiver element.

The latex for the timing layer of the present invention can be prepared by a known method, for example, by spiral coating. Rod (spiralrM) coater, extrusion. Courter, Deep. Kota,
Ea knife. It can be applied using a method such as a coater. Various additives known in the art can be mixed into this latex depending on the purpose.
dMtMensingIndex is written in Report 9232 of Port 9 (December 1971).

The additives include surfactants for improving wetting during coating, which are described on pages 107 to 108 of the above literature;
Solvents to facilitate manufacturing (e.g. methyl cellosolve, ethyl cellosolve, cyclohexanone, toluene, etc.), matting agents such as powdered silica and bead-shaped polymers used to prevent adhesive failure during manufacturing and use;
Fillers (e.g. colloidal silica, titanium dioxide, carbon black, diatomite, etc.) to improve the strength of the film; plasticizers (such as
For example, dibutyl phthalate (phthalate esters such as dihexyl phthalate, phosphate esters such as trialkyl phosphate, tricresyl phosphate),
It is desirable to use the following depending on the purpose.

The amount of the above additive used is selected depending on the purpose, but it is preferably 0.1 to 20% based on the solid content of the latex polymer.
(by weight), particularly preferably from 1 to 10% (by weight).
However, the preferred amount of the surfactant used to improve wetting is about 0.05 to 0.5%. When applying the polymer latex liquid of the present invention having a reactive group such as an N-hydroxymethyl group or its precursor alkoxymethyl group, a condensation catalyst for this reactive group may be used.

Generally, the lower the pH of the coating solution, the higher the activity of the above-mentioned reactive groups, but conversely, the storage stability of the coating solution decreases. Stability can be improved by converting this functional group into a precursor such as alkyl ether. The preferred pH of the coating solution is about 1 to
6.5, particularly preferably about 2-5. Excellent effects can be obtained by adding a strong organic or inorganic acid such as P-toluenesulfonic acid or hydrochloric acid as a condensation catalyst for reactive groups. In addition, the use of ammonium salts of these strong acids as condensation catalysts for reactive groups results in a latex with excellent shoulder-to-shoulder adhesion without lowering the pH of the coating solution. This is particularly preferred in that a timing layer can be obtained. Specific examples of ammonium salts of inorganic or organic strong acids include ammonium chloride, ammonium bromide, ammonium iodide, ammonium nitrate p-
Examples include toluenesulfonic acid ammonium salt.
The amount added is preferably about o
．． 1 to 100 mmol, particularly preferably about 1 to 1
It is 0 mmol. The thickness of the timing layer of the present invention is preferably 0.5 to 2 mm, particularly preferably 2 to 8 mm, but can be freely selected depending on the intended use of the timing layer and is not particularly limited.

latex. The timing layer was made with different copolymer compositions.
It may also be formed from a mixture of more than one type of latex.

One method for this is to blend latexes with different minimum film formation temperatures. In other words, the minimum film forming temperature is 35qo
The following polymer latex (group 1) and the minimum film formation temperature are 3
By applying a mixture of latexes (group 0) at temperatures exceeding 5°C, latexes with less blocking failures can be created. A timing layer can be applied. The minimum film forming temperature (MFT) mentioned here is a characteristic value well known to those familiar with technology in the industry, and is determined by the American Standard 0 Bureau's standard test method ATSM-02354-68 at a temperature of 25°C or lower. ``It can be easily measured for latex with T. For latex with M'T over 2500, please refer to the "Joumalof Appli"
ed PoIMmerScience”, Journal
According to the method described in Applied Polymer Science, Vol. W, No. 1, pp. 81-85 (1960),
By creating a temperature gradient up to the desired temperature, the M'
T can be measured. Examples of latexes with M'T exceeding 3500 include 65% by weight or more of styrene or 65% by weight of methyl methacrylate as component (C).
Examples include the polymer latex of the present invention containing 9% by weight or more as a copolymer component.

An example of a latex with an MFT of 3500 or less is n-
The polymer latex of the present invention contains 36% by weight or more of butyl acrylate as a copolymer component. Also, blocking failure refers to latex. After winding up a film in which the timing layer is coated as the outermost layer on a support, the timing layer may adhere to the back side of the film, or D
This means that the latex timing layer preferably adheres to the surface of the photosensitive element after formation of the TR color photographic film unit.

The mixing ratio of the polymer latex of leather and nryogun sheep is 1:2:95:5 to 20:80 in terms of solid content ratio, and particularly preferably 30:70 to 70:30.

Furthermore, a polymer latex (group m) obtained by mutually emulsion polymerizing at least one monomer selected from the group A and group C monomers of the present invention, and a monomer selected from the group B and group C monomers of the present invention. They may also be blended with a polymer latex (W group) obtained by emulsion polymerization of at least one type of monomer.

In this case, based on the total solid content after blending, the A group monomer is 0.5 to 40% by weight, the B group monomer is 1%,
It is preferable to synthesize and blend the m group and W group polymer latexes by selecting the composition ratio so that the composition ratio is 10% by weight. The mixing ratio of the m-group and N-group polymer latexes was m:W=5:95 in terms of solid content ratio;
The ratio is preferably 0:40, particularly preferably 10:90 or 40:60. Preferred drying methods for applying the timing layer of the present invention include a method using infrared rays or ultrashort waves, a contact heat transfer method such as a method using a heat drum, and a method using hot air. In any case, it is preferable to make a transparent film from latex and heat it if necessary to dissipate the existing moisture and other luminescent components.

The timing layer used in the present invention can control the rate of alkali absorption by the neutralization layer, and can also halogenate substances in the layer on the opposite side of the silver halide emulsion layer with respect to the timing layer used in the present invention. Diffusion movement toward the silver emulsion side can be controlled.

The layer on the opposite side is, for example, a neutralization layer, or a neutralization layer and latex. Cell painted between timing layers.
-suacetate. One example is the timing layer. Additives that have unfavorable chemical effects if they reach the silver halide layer in the early stage of development (e.g. development inhibitors and their precursors (development inhibitor-releasing couplers, hydroquinone, etc.), as described in French Patent No. 2282124) It is preferable that a compound (such as a compound that releases a development inhibitor upon hydrolysis) or a reducing agent for preventing photobleaching (such as a compound that releases a development inhibitor upon hydrolysis) be mixed in advance into the neutralization layer or the cellulose acetate timing layer. By coating the timing layer of the present invention, such additives are isolated and incorporated into the cover sheet so that they do not reach the silver halide emulsion layer at the early stage of development, and are made to act only after development has sufficiently progressed. It can be done. Of course, the action of these additives can be made to have a desired temperature dependence. For example, if a development inhibitor or its precursor is mixed into the neutralization layer or the above-mentioned cellulose acetate timing layer to suppress excessive development, development can be performed without any inhibition at the start of development at any temperature. Only when proper progress can be made can development be suppressed and finally stopped. This can prevent staining and increase in image density due to excessive development. Particularly when the development temperature is high, the development speed is very fast and staining is likely to occur due to overdevelopment. Latex. The use of a timing layer is suitable for preventing the above-mentioned disadvantages. Development inhibitor releasing coupler (DIR coupler)
For example, U.S. Pat. No. 3,227,554, U.S. Pat. No. 3,617,291, U.S. Pat.
, 790,384, 3,632,345, West German Patent Application (OLS) 2,414,006, 2,454
, No. 301, No. 2,454,32y, British Patent No. 953
, No. 454 and Tokusekki No. 52-69624 can be used.

Other compounds that release development inhibitors during development include, for example, U.S. Pat. No. 3,297,445;
, 379752 needle number, West German patent application (OLS) 2,41
Those described in No. 7,914 can be used. Latex of the present invention. With a timing layer, high p on the cold side
The H sustaining effect is particularly remarkable, and the reduction in transferred image density that tends to occur in the past can be almost completely corrected. In addition, since the water permeability of the timing layer of the present invention increases significantly as the temperature rises, when the measurement temperature range is changed from room temperature to the high temperature side, the water permeation rate increases by approximately 2 for every 1000 degree rise in temperature.
．． Soundproof or 6. This has the effect of increasing the beeping sound. When the timing layer of the present invention is used, this effect makes it easier for the processing solution to pass through the timing layer used in the present invention and reach the neutralization layer at high temperatures, so the pH of the processing solution decreases quickly and excessive development is prevented. This has the advantage of being suppressed, that is, it is possible to prevent excessive transferred image density from being obtained. Therefore, by using the timing layer of the present invention, a "temperature compensation effect" can be obtained in which a constant transferred image density can be obtained regardless of changes in processing temperature.

In addition, the timing layer used in the present invention has greatly improved film strength and adhesion with adjacent layers, so even when a heat-sealed product is subjected to mechanical action from the outside, the timing layer will not only adhere to the inside of the layer but also with adjacent layers. The film will not be cut near the interface. Therefore, the film does not peel off during the manufacturing process or when the processing solution is developed after photography. units are obtained. Furthermore, even if the timing layer of the present invention is heat-sealed using a hot-melt adhesive, the adhesive strength after heat-sealing is high not only at room temperature but also at low temperatures around 0°C. ．．
The timing layer of the present invention is particularly useful in high speed mass production of units.

Any commonly known hot melt adhesive may be used as the hot melt adhesive. In this case, a support coated with a hot melt adhesive and the timing layer side of the photographic element of the present invention are brought together and sandwiched between heated metal blocks for heat sealing. Hot-melt adhesives include polyethylene-pinyl acetate adhesives, as well as "Research Discl.
osure” Research Desk No. 15, published in June 1977. It is particularly advantageous to use adhesives such as those described in No. 1583y applied to polyethylene terephthalate films, polycarbonate films or triacetylcellulose films.

Peel strength after heat sealing can be easily measured using a normal tensile tester. Further, in producing the latex used in the present invention, it can be produced using inexpensive raw materials and simple equipment, so that the production cost is low.

The usefulness of the timing layer of the present invention, whose water permeability increases significantly as the temperature rises, can be evaluated by comparing the temperature change in photographic development with the temperature change in water permeability.

In practical terms, it is best to discuss the water permeability of the timing layer based on the time required for an alkaline processing solution to permeate through the timing layer and for its pH to decrease as alkali is absorbed into the neutralization layer. Better,.

In this case, the fence is 10 (this fence is recognized in the industry as effectively stopping photographic development).

), and by comparing the rate of change due to temperature with the temperature change in the transferred image density, it was found that there was a very good correlation. PH is 10
It is preferable to measure the time required for mixing to reach the desired temperature using a spot indicator dye that does not decompose under alkaline conditions. In particular, pHIO as a pH indicator as described later in the Examples.
It is preferable to measure by a method using thymolphthalein, which is a pigment that changes color. By the method shown in the example of the present invention using thymol phthalein, the p of the alkaline treatment solution
When we measured the rate of temperature change during the time when H decreased to 10 for the timing layer used in the present invention and the timing layer according to other prior art techniques, and compared it with the temperature change in the transferred image density, a clear correlation was found. Ta.

The measurement temperature was set at two points: 260, which is suitable for humans to live in, and 15qo, which is slightly lower. , the time required to reach pHIO at 25° C.) to define the preferred range of the timing layer of the present invention. It is preferable that the value of T,5/Tru measured according to the method of Example 1 is 250 to 600%, particularly preferably 300 to 500%.

The silver halide emulsion used in the present invention is a hydrophilic colloidal dispersion of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide or a mixture thereof, The halogen composition is selected depending on the purpose of use of the photosensitive material and processing conditions, but it is recommended that the iodide content be 1 mol% to 10 mol% (the chloride content is 30 mol% or less) and the remainder be bromide. Silver iodobromide or silver chloroiodobromide emulsions are particularly preferred.

Emulsions that easily form latent images on the grain surfaces can also be used in the present invention; however, U.S. Pat.
76, 3,206,313 3,317,322, 3? 761,260 3,850,637, 3,
923, 513, 3,736, 14ri 3,761,
It is preferable to use an internal latent image type direct reversal emulsion such as that described in No. 267, No. 3,854,949. As the color image-providing substance for diffusion transfer method used in combination with the photographic emulsion used in the present invention, for example, US Pat.
No. 51, 3, Matsu 7, No. 5, 3,443, No. 93, 3
, No. 443,940, No. 3,658,524, No. 3,69
Pre-No. 897, 3,725 No. 062, 3,728,1
No. 13, No. 3,751.406, No. 3,929,76, No. 3,931,144, No. 3, Satoshi 2, No. 1, British Patent No. 840,731, No. 904,364, No. 1, 0 Ma ,33
No. 1, West German Patent Publication (OLS) No. 1,930,215,
2,214, Spot No. 1, 2,228,361, 2,24
No. 2,762, No. 2,317,134, No. 2,402,9
0pi No. 2,406,626, 2,400 653, Tokusei No. 49-114,424, 49-126332
No., 48-3 spot No. 26, 49-126 spot No. 1, 50-1
No. 15528, 51-113624, 51-1043
No. 43, No. 51-11493, No. 52 Iso No. 27, 53
-23628, Tokuiso Sho 52-Mada No. 318, 52-64
Waza group number, 52-64 ball number 3, 52-74601 number, 52
-131278, etc., but among these, colors that are initially non-diffusible but cleave to release a diffusible dye after a redox reaction with the oxidation product of the developing agent can be used. The use of image-donating substances (hereinafter abbreviated as DRR compounds) is preferred.

Specific examples of DRR compounds include those described in the above patent specifications, as well as magenta dye image forming substances such as 1
-Hydroxy-2-tetramethylenesulfayl-4-
[3-Methyl-4(2″-hydroxy-4″-methyl-5″-hexadecyloxyphenylsulfamoyl)
-phenylazo]-naphthalene, as a yellow dye image-forming substance 1-phenyl-3-cyano-413'f-hydroxy-4'-methyl-5'f2''',4''
Examples thereof include '-t-bentylphenoxyacetamino)-phenylsulfamoyl]phenylazo}-5-pyrazolone.

When using a DRR compound in the present invention, any silver halide developer can be used as long as it can cross-oxidize the DRR compound.

Such a developer may be included in the alkaline processing composition (processing element) or in an appropriate layer of the photosensitive element. Examples of developing agents that can be used in the present invention are as follows. Hydroquinone, aminophenols, such as N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-oxymethyl-3-pyrazolidone, N,N-diethyl-p- Phenyl diamine, 3-methyl-N,N-
Diethyl-P-phenylenediamine, 3-methoxy N
-Ethoxy-P-phenylenediamine, etc. Among those listed here, particularly preferred are black and white developers, which generally have the property of reducing stain formation in the image-receiving layer (unfavorable layer).

After exposure, the direct reversal photographic emulsion used in the present invention is developed in the presence of a fogging agent or as disclosed in US Pat.
953 (Knott and Stevens), a uniform exposure (high-light short exposure, i.e., shorter than 10-2 seconds) or low-light long exposure may be used during surface development. ) can be used to directly obtain a positive image.

It is preferable to use a fogging agent because the degree of fogging can be easily adjusted. The fogging agent may be contained in the photosensitive material or may be added to the developer, but it is preferable to include it in the photosensitive material. Fogging agents for this type of emulsion include U.S. Pat.
Hydrazines described in No. 785, No. 3, Secretion 7,55
No. 2' described hydrazide and hydrazone, British Patent No. 1,283,835, Japanese Patent Publication No. 164 of 1973, US Patent No. 3,7 I,738, No. 3,719,494, No. 3,615, A typical example is the quaternary salt compound described in No. 615. The amount of fogging agent used here is
It can vary widely depending on the desired result.
Generally, the concentration of this fogging agent when added to a photosensitive material varies depending on the fogging agent used, but is generally 0.
1 c to 1500 c/1 mol Ag preferably 0.5
It is used in the range of female to 700 female/1 mol Ag. When a fogging agent is added to the processing solution, it is generally about 0.05% fogging agent per 1 developer solution, and phosphoric acid (preferably 0.1 to 1g
). When a fogging agent is included in any layer of a light-sensitive material, it is effective to make the fogging agent diffusion resistant. As a means of imparting diffusion resistance, it is effective to bond a ballast group commonly used in couplers to a fogging agent. Additionally, U.S. Patent No. 3,227,551, 3
, 227,554, 3,364,022' or by a reversal emulsion method using dissolution physical development as described in British Patent No. 904,364. A transfer positive image can be obtained. U.S. Patent Nos. 3,227,550 and 3,
No. 227,552, British Patent No. 1,330,524, and others describe a series of processes for obtaining color diffusion transfer images. In the present invention, the diffusible dye-releasing coupler→(D
As a color developing agent when using a DR coupler), U.S. Pat.
Typical examples include the derivatives of phenylenediamine described in No. 1 and No. 3,813,244.

Furthermore, P-aminophenol derivatives such as those described in Tokukan Sho 48-26134 can also be advantageously used. The receiving element may be a poly(4-vinylpyridine) latex (particularly in polyvinyl alcohol) as described in U.S. Pat. No. 3,148,061, a polyvinylpyrrolidone as described in U.S. Pat.
No. 3,547,649, No. 3,709 69, No. 3,9 Moth 995, No. 3,770,439, No. 3,898,088, West German Patent Application (OLS) 2, 2
It is essential to have a soot beam layer consisting of a soot beam agent such as a polymer containing quaternary ammonium salts or phosphonium salts, such as those described in US Pat. No. 64,073.

As a soot dye, U.S. Patent Nos. 2,882,156 and 3
, 625 694, 3,709, 69, etc. are also effective. Other US patents 2,
No. 484,430, No. 3,958,995, No. 3,2
No. 71,147, No. 3,184,309, No. 3,27
The mordants described in No. 1,147 and the like are also effective. The DTR color photographic elements of this invention have supports that do not undergo significant dimensional changes during processing.

Examples of such supports include cellulose acetate film, polystyrene film, polyethylene terephthalate film, polycarbonate film, etc. which are used in common photographic materials. ．． Other useful supports include, for example, paper and paper whose surface is impermeable to water, such as polyethylene, and which is laminated with a polymer. Preferred acidic substances constituting the neutralizing layer used in the present invention include U.S. Pat.
No. 6, No. 2,584,030, No. 3,362,819
No. 3,765, Madara No. 5, No. 3,819 371,
A typical example is that described in French Patent No. 2,290,69y. Specifically, polymethacrylic acid, copolymers of acrylic acid and methacrylic acid in various copolymerization ratios, acrylic acid or methacrylic acid and other vinyl monomers (for example, acrylic acid esters, methacrylic acid esters, vinyl ethers) Examples include copolymers with various copolymerization ratios (preferably acrylic acid or methacrylic acid content of 50 to 90 mol%) with polyacrylic acid, acrylamides, methacrylamides, etc., among which polyacrylic acid, acrylic acid - The use of butyl acrylate copolymers is recommended. In addition to these acidic substances, the neutralizing layer can contain polymers such as cellulose, nitrate, and polyvinyl acetate, as described in U.S. Pat. No. 3,557,237.
Plasticizers can also be included as described in No. Acidic substances can be incorporated into the film unit in microencapsulation, as disclosed in German Patent Application No. 2,03&2. The processing composition used in the present invention is a liquid composition containing processing components necessary for developing a silver halide emulsion and forming a diffusion transfer dye, and the solvent is mainly water, and methanol, methanol, It may also contain hydrophilic solvents such as methyl cellosolp.

The processing composition maintains the pH necessary to cause development of the emulsion layer and removes acids generated during the development and dye image formation processes (e.g., hydrohalic acids such as hydrobromic acid, carboxylic acids such as acetic acid). Contains enough military alkali to neutralize acids (acids, etc.). Examples of alkalis include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide dispersion, tetramethylammonium hydroxide, sodium carbonate, phosphoric acid 3
Alkali metal or alkali metal salts, such as sodium, diethylamine, or amines are used, preferably with a pH of about 1 or more at room temperature, especially at pH 4.
It is desirable to contain caustic alkali at a concentration that will give a finishing touch. More preferably, the treatment composition comprises high molecular weight polyvinyl alcohol, hydroxyethyl cellulose,
Contains a hydrophilic polymer such as sodium carboxymethyl cellulose. These polymers may be present in the treatment composition at room temperature at least 1 voice, preferably in the hundreds (500-60
It provides a viscosity of about 0) to 1,000 voices, and not only facilitates the uniform spread of the composition during processing, but also allows the aqueous solvent to migrate to the photosensitive element and image receiving element during processing, thereby concentrating the processing composition. Sometimes a non-flowing film is formed to help the film unit unite after processing. This polymer film can also be used to inhibit further migration of colored components to the image-receiving layer after the formation of the diffusion-transferred dye image is substantially completed, thereby preventing changes in the image. The processing composition may also contain light-absorbing substances such as Ti02, carbon black, and PH indicator dyes to prevent the halogenated emulsion from fogging due to external light during processing. It may be advantageous in some cases to contain desensitizers such as those mentioned.

Furthermore, a development inhibitor such as penzotriazole can be added to the processing liquid composition. The above treatment compositions are described in U.S. Pat.
No. 6, No. 2,653,732, No. 2,723,051
It is preferable to use it in a rupturable container as described in Japanese Patent Application No. 3,056,491, Japanese Patent No. 3,066,492, Japanese Patent No. 3,152,515, etc.

The photographic element of the present invention comprises a photographic film unit "i.e.
In the case of a film unit which is adapted to be processed by passing the film unit between a pair of juxtaposed pressing members, it has the following elements: a. at least one light-sensitive silver halide emulsion layer (light-sensitive element) in combination;
b. an image-receiving layer (image-receiving element); c. an alkaline processing composition, preferably a composition contained in a breakable container within the film unit and containing a silver halide developer; d. said alkaline processing composition. Preferably, it consists of a neutralizing layer for neutralizing substances and a latex according to the invention in combination with a timing layer (neutralizing system).

Example 1 A neutralization layer was applied on a polyethylene terephthalate film with a thickness of 10 mm using the recipe shown in (1) below, and a timing layer containing cellulose acetate was applied on top of it using the recipe shown in (0) below. did.

Furthermore, a polymer latex was applied thereon as shown in Table A, dried at 70 qo for 3 minutes, and then at 120° C. for 5 minutes to form a timing layer used in the present invention. (1)
Application of the neutralization layer 20% solution of acrylic acid-butyl acrylate (mole ratio 8:2) polymer having an average molecular weight of 50,000 (solvent: acetone-water 3:1 (volume ratio)) (2-thia/ethylthio)-1-phenyltetrazole 3.
Dissolve 8 ta.

This solution was coated at 110 ta per square meter using an extrusion coater, with a wind speed of ah per second and a temperature of 12 pi.
It was dried for 5 minutes using dry air with a dew point of 5°C to obtain a film about 2 mosquitoes thick. (0) Cell.

-Acetate timing layer coating degree of acetylation: 52.1% (
Cellulose acetate (LM-70 manufactured by Daicel Corporation) with an average molecular weight of 100
00 styrene-maleic anhydride (mole ratio 1:1) copolymer was dissolved in an acetone-cyclohexanone 3:1 (volume ratio) mixed solvent.

This solution was applied to the neutralization layer coated by the method shown in (1) using an extrusion coater to coat the solution at a rate of 5% per square meter.
It was coated with 0.0 tatre and dried with dry air at a wind speed of 4 m/s, an indoor temperature of 80°C, and a fog point of 5°C, to a thickness of about 2. Obtained turtle membrane. Table A List of photographic elements for testing This cover sheet No. 1 and 2 below (m
), the alkaline viscous liquid obtained by the preparation method shown in (N) below was spread out to a liquid thickness of 8.

Next, the concentration is measured from the side of the p elbow indicator coated film, and the desired time required for the reflection density of the high pH color (blue) of thymol phthalein to be reduced by neutralization and halved (this time is
10) was measured for 25qo and lyo. The test results are shown in Table B. (melon) PH
Preparation of indicator coated film A 7% gelatin solution containing 28.5 parts of thymol phthalene per 1 day of gelatin (the solvent is water-methanol volume ratio 4)
:1 mixed solvent) was applied at a rate of 100 tons per square meter to create a dry thickness of approximately 6.5 mm.

A titanium dioxide dispersion (solid content concentration 10%) mixed at a ratio of 9 parts of titanium dioxide to 1 part of gelatin is applied thereon at a rate of 300 tons per square meter to form a colored film with a dry thickness of about 9 degrees. Furthermore, the same thymol phthalein-containing gelatin solution as above was applied thereon in the same manner and dried to complete the process. (W) Preparation of alkaline viscous steel liquid Hydroxyethylcellulose (Nat manufactured by Hercules)
Rosol 1250-HR) was dissolved in water for 30 minutes and sodium hydroxide was dissolved in water for 940 minutes, and the mixture was defoamed before use.

As is clear from the comparison of the values in Table B, when the timing layer of the present invention is used, the temperature dependence of the alkali permeability is greater than that for comparison.

Table B Example 2 Photographic elements (cover sheets) produced in Example 1 (
rudder. The processing temperature latitude of 1 to 2) was examined using the following photosensitive sheets (in which an image-receiving element and a photosensitive element are integrally coated on a support) and a processing liquid (processing element).

Preparation of Photosensitive Sheet The following layers were provided in order on a transparent polyethylene terephthalate support having a thickness of 18 capes: 1. The following mordants (3.
Layer 2 containing titanium dioxide (20 m/m) and gelatin (3.0 m/m) and gelatin (2.0 m/m)
Layer 3 containing carbon black (2.5 m/m) and gelatin (2.5 m/m) Layer 4 containing the following cyan image-donor (0.50 m/m), diethyl laurylamide (0.25 evening/day) and gelatin (1.14 evening/day)
Layer 5 containing red-sensitive internal latent image type direct reversal silver iodobromide emulsion (halogen composition in silver halide: iodine 2 mol%, silver amount 1.9 m/m, gelatin 1) .4 tano)
, a fogging agent represented by the following formula (0.028 Tanomakura) and sodium becitadicyl hydroquinone sulfonate (
Layer 6 containing gelatin (2.6 g/g) and 2.5-dioctylhydroquinone (1.0 g/g); Layer 7 containing the following magenta color image-donor (0 g/g); .45
evening/final), diethyl laurylamide 0.10 evening/force),
2,5-di-t-butylhydroquinone (0.0074
Layer 8 containing ray-sensitive internal latent image type direct reversal silver iodobromide emulsion (halogen composition of silver iodobromide: 2 mol% iodine, 2 mol% silver gelatin 1.0 m/l), the same fogging agent added to layer 5) (0.024 m/l) and sodium pentadecylhydroquinone sulfonate (0.0 m/l) in an amount of 1.4 m/l. 11th evening/
Layer 9 containing gelatin (2.6 layers) "2,5
Layer containing -dioctylhydroquinone (i.0 m/m) *10 The following yellow dye-providing substance (0.78 m/m), diethyl laurylamide (0.16 m/m), 2,
Layer 11 Containing 5-di-t-butylhydroquinone (0.012 T) and Gelatin (0.78 T) : Iodine is 2 mol%, silver is 2.2 mol %, gelatin is 1.2 mol %, the same fogging agent (0.02 M/l) added to the layer 5) and pentadecyl hydroquinone sulfone are added. Layer 12 Containing Sodium Acid (0.094/m) Layer Processing Solution Containing Gelatin (0.949/m) A processing solution having the above composition was filled into a container breakable by pressure in 0.8 m/m units.

Processing process: The above test cover sheet and the above photosensitive sheet were overlapped and the color test chart was exposed from the side of the cover sheet, and then the above processing liquid was spread between the two sheets to a thickness of 78 cm.

(Unfolding was done with the help of a pressure roller). The processing is
35o09 25oo and 15'0 were used respectively.
After the treatment, the blue density, green density, and red density generated in the image-receiving layer were measured using a Macbeth reflection densitometer through the transparent support of the photosensitive sheet. (The density was measured after a sufficient period of time had elapsed for the image density to reach equilibrium.) Table C lists the maximum transfer density values when a certain optical density was reached. As is clear from Table C, cover sheet 1 has a higher transfer density at 15oo than cover sheet 2. Further, even when practical photography was carried out using a person as a model, cover sheet 1 used in the present invention had a better processing temperature latitude than cover sheet 2.

(Temperature 15-35oo) Table 0

Claims (1)

[Claims] 1. A neutralization system for lowering the pH of an aqueous alkaline developer [This neutralization system includes a neutralization layer and a timing layer, in which the developer passes through the timing layer. The neutralizing layer is directly or indirectly superimposed on the neutralizing layer in a positional relationship such that the neutralizing layer is reached by the neutralizing layer. ], wherein the timing layer is copolymerizable with at least one polymerizable ethylenically unsaturated monomer having at least one free carboxylic acid group or phosphoric acid group or a salt thereof. It is characterized by being formed from at least one type of polymer latex obtained by emulsion polymerizing at least one other ethylene monomer using a redox polymerization initiator in the presence of a transition metal compound. Photographic elements for color diffusion transfer methods.