JPS59166940A - Photosensitive material containing polymer latex - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material having improved photographic performance by using aqueous polymer latex ultrafiltered with a membrane as polymer latex to be contained in a constituent layer. CONSTITUTION:Aqueous polymer latex having about 1-80wt% concn. of solid matter, e.g., latex of a polymer of about 0.01-1mum particle size represented by the formula is ultrafiltered with a membrane having about 500-50,000 fractional mol.wt. under about 1-15kg/cm<2> pressure at about 0.1-10m<3>/m<2> day average rate of water permeation for about 6-8hr. The resulting aqueous polymer latex is used in a constituent layer of a photosensitive material such as the underlayer, the intermediate layer or the antihalation layer. The degree of ultrafiltration is judged from the electric conductivity of the ultrafiltered latex, and it is regulated according to the application. For example, when the latex is used as a mordant, the preferred electric conductivity is <= about 400muOMEGA/cm in case of 1wt% concn. of latex.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photographic material containing a polymer latex (excluding a silver halide dispersion; the same applies hereinafter) treated with an ultrafiltration membrane.

Polymer latex is used in various layers of photographic materials, such as undercoat layer, intermediate layer 1, etc.
A dye image donor containing layer, a scavenger layer, a holding layer, an auxiliary layer, a backing layer, an image receiving layer, a reiming layer, a barrier layer, a release layer and an antistatic layer.

This is a layer for preventing halayon, etc.

In terms of its functions, polymer latex is used as a mordant, antistatic agent, coloring agent, ultraviolet absorber, adhesion improver, film quality improver, etc. .

Antioxidants, brighteners, development inhibitors, development accelerators.

It has also been proposed to use it as a dispersion medium for filling or adsorbing photographic additives such as dye image donors. For information on how to use these latexes, specific latex examples, 2 documents, etc., please refer to Re5earch Disclosure (
Research Disclosure) Magazine 1trx19srt
(/9♂O).

What does "polymer latex" refer to in this specification?

It is used in the sense of fine particle dispersion.

Generally, when polymer latex is incorporated into a photographic material, it is added to a coating solution to produce a photographic material or film unit, but certain components mixed into the polymer latex may have an adverse effect on photographic performance. It is known that it may have an adverse effect. For example, in synthesizing a polymer latex containing a ψ class ammonium salt, US Pat. Monomers having halogenated alkyl groups, as described in Tata G, Tata No.

A method is known in which a monomer having at least one ethylenically unsaturated group and a monomer having an α,β-ethylenically unsaturated group are emulsion polymerized and then reacted with a primary secondary amine. However, according to this method, unreacted tertiary
It is described in JP-A-51-2337 that residual amines are undesirable in the case of @fabric because they cause a "repellent" phenomenon and have an adverse effect on photographic performance.

For this reason, great efforts have been made to examine synthesis conditions and search for new monomers to reduce the amount of components that adversely affect photographic performance. It also causes problems and increases manufacturing costs.

The present inventors have repeatedly investigated synthesis conditions and synthesis methods, including the search for new monomers, but it has become clear that there are limits to the synthetic approach alone in order to dramatically improve photographic performance. Understood. Therefore, the inventors of the present invention have set their sights on the new task of exploring approaches other than one synthesis method in order to dramatically improve photographic performance.

Therefore, one object of the present invention is to achieve the same photographic performance.

An object of the present invention is to provide a photographic material containing polymer latex.

The present inventors have attempted to purify the aqueous polymer latex, for example, by simple dialysis, ion exchange, or membrane filtration using a microfilter or microfiber, or by blowing steam or ozone into the remaining monomer. Attempts were made to use catalysts, but none of them succeeded in achieving the intended purpose. In the end, it was discovered that the above purpose could be effectively achieved by using a polymer aqueous suspension (excluding silver halide dispersion) treated with an ultraviolet filtration film in a photographic light-sensitive material. Ta.

By the way, ultrafiltration method (111trafiltrati)
on) itself is generally well known from the Chemistry Dictionary (Kyoritsu Shuppansha), the Iwanami Physical and Chemical Dictionary, and "Chemical Real Family Manipulation Method" by Akira Ogata (Nankodo) Volume 2/3ri~/ll-3 Sada.

In addition, when polymer latex is purified, its stability deteriorates, and on the contrary, it gives a bad photographic effect. Therefore, it was considered common technical knowledge to use it only during purification.

This is why there is no literature on the photographic use of purified polymer latexes. However, the polymer latex treated with ultraviolet filtration membrane was unexpectedly stable. in the end.

We were able to improve photographic performance using a stable polymer latex without any synthetic limitations.

By the way, the patent application for purifying halogenated emulsions and photographic gelatin by ultrafiltration, such as ultrafiltration during the growth process of silver halide, has been published! t-evening 0/
No. 774 and Re5earch Disclo
s ur e magazine &10102O/ri October 1972)
However, the ultrafiltration membrane treatment of polymer latex according to the present invention, its movement and effect are completely different. be.

The fact that the ultrafiltration membrane-treated polymer latex of the present invention has unexpectedly improved photographic performance is as follows.
It is presumed that this is due to the peculiarity of photographic materials in that even trace amounts of components can sometimes have a large effect on photographic performance.

In some cases, the minor components include the polymerization initiator used during latex synthesis and/or its decomposition products, in some cases residual monomers, and in other cases, the trace components used in large amounts may include emulsification and other components added after latex synthesis. When a reaction is caused and used, reaction reagents and/or reaction products may be used, such as halogenated emulsions, couplers, dyes, dye image donors, etc. during and/or after production and processing of photographic light-sensitive materials. It is presumed that there will be no adverse effects.

In particular, in the synthesis of certain mordants or antistatic latexes, monomers with active halogen atoms such as chloromethylstyrene, or monomers with heptameric 1μ class ammonium salts with tertiary amine groups, active polymers, etc.
When using amines as reaction reagents for active/logen, excess 7-logen atoms generated by hydrolysis of active/logen, residual monomers, amines, residual monomers having logen atoms, and tertiary amines. reacted 4
It is estimated that water-soluble or hydrophilic low molecular weight components such as ammonium salts have a particularly adverse effect.

However, if the polymer latex contains a water-miscible organic solvent that causes "repelling" when applied, this solvent can be removed by the ultrafiltration membrane treatment of the present invention. It also has some beneficial effects.

As a polymer latex treated with ultra-P film.

For example, the above Re5search Disclosure
These are various kinds of latexes such as those described in the magazine 79 Tata/(1910), which can be used in various layers of photographic light-sensitive materials, such as certain polymer latexes treated with ultrafiltration membranes. Can be mixed with photographic emulsion. A preferred polymer latex is a vinyl polymer latex.

More specifically, it is a cationic polymer latex such as a mordant polymer latex or an antistatic polymer latex.

Particularly preferred is a cross-linked microorganism represented by the following general formula (I) used as a mordant or an antistatic agent.
ammonium salt (or phosphonium salt) polymer latex.

N) 1 ■ ■ 4 The hole in the formula represents a copolymerizable monomer unit having at least two ethylenically unsaturated groups. B represents one ethylenically unsaturated monomer unit copolymerizable with component A and the like. R
1 represents a hydrogen atom or a lower alkyl group having from 1 to about 6 carbon atoms, and L&''il represents a divalent group having from 1 to about 1 carbon atoms. R2, R, a and R4 are each the same or different / represents an alkyl group having ~20 carbon atoms, or an aralkyl group having 7 to ~20 carbon atoms; 'R2, R3 and R4 may be interconnected to form a cyclic structure with Q; Good. Q is Nt or P and represents Xe ke anio/. X is about 0.2 to about 75
mole percent, y is θ to about 70 mole percent, and z is about j to about 7 mole percent. .

Regarding the preferred polymer latex of the present invention, the general formula (
J) Monomers having at least one ethylenically unsaturated group (preferably 2 to t) corresponding to one monomer unit of A in K include esters.

These include amides, olefins, and aryl compounds.

Examples of copolymerizable monomers having at least λ ethylenically unsaturated groups include, for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, neo-andyl glycol dimethacrylate, tetramethylene glycol dimethacrylate, hantaerythritol tetramethacrylate, and trimethacrylate. Methylolpropane trimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, neoantyl glycol diacrylate, tetramethylene glycol diacrylate, trimethylolpronocentriacrylate, allyl methacrylate, allyl acrylate, diallyl phthalate, methylene bisacrylamide, Methylenebismethacrylamide, trivinylcyclohexane, divinylbenzene, N,N-bis(vinylbenzyl)-N
, N-dimethylammonium chloride, N,N-diethyl-N-(methacryloyloxyethyl)-N-(
vinylbenzyl) ammonium chloride, N.

N,N',N'-tetraethyl-N,N'-bis(vinylbenzyl)-p-xylylene diammonium dichloride, N,N'-bis(vinylbenzyl)-)
Liethylene diammonium dichloride.

N, N, N', N'-tetraethyl N,
Examples include N'-bis(vinylbenzyl)-ethylenediammonium dichloride. Among these, divinylbenzene and trivinylcyclohexane are particularly preferred from the viewpoint of water resistance and alkali resistance.

A may contain two or more of the above monomers.

Examples of the ethylenically unsaturated monomer B include olefin 7jl! (For example, ethylene, zolopyrene, l-duthene, vinyl chloride, vinylidene thickening.

inobutene, vinyl bromide, etc.), dienes (e.g. butadiene, isoprene, chlorobrene, etc.).

Ethylenically unsaturated esters of fatty acids or aromatic carboxylic acids (e.g. vinyl acetate, allyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc.), esters of ethylenically dissonant acids (e.g. methyl methacrylate, butyl methacrylate) , tert-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, octyl methacrylate, amyl acrylate, no-ethylhexyl acrylate, benzyl acrylate, maleic acid cyphthyl ester, 7-malic acid diethyl ester, ethyl crotonate, methylene malonic acid dibutyl ester Such)
, styrenes (e.g. styrene, α-methylstyrene, vinyltoluene.

Examples include chloromethylstyrene, chlorstyrene, dichlorostyrene, bromustyrene, sodium trichloride (eg, acrylonitrile, methacrylonitrile, allyl cyanide, crotonitrile, etc.). Among these, styrenes and methacrylic acid esters are particularly preferred from the viewpoint of emulsion polymerizability, hydrophobicity, and the like. B may contain two or more of the above monomers.

R1 is preferably a hydrogen atom or a methyl group from the viewpoint of monopolymerization reactivity.

6 ■ 0 -C-N-7R5- from the viewpoint of resistance to alkali and alkali resistance.

1. In the above formula, R5 represents alkylene (for example, methylene, ethylene, trimethylene, tetramethylene, etc.), arylene, aralkylene (for example, alkylene having a child), and R6 represents the hydrogen atom size or R2. n
is/or an integer of λ.

Q is preferably N in view of the toxicity of the raw material.

Examples of Xe include... rogane ions (for example, chlorine ions, bromide ions, iodine ions, etc.).

Alkyl nitrate ions (e.g. methyl sulfate ions).

ethyl sulfate ions), alkyl or aryl sulfonic acid ions (such as methanesulfonic acid).

Examples include ethanesulfonic acid, benzenesulfonic acid (%p-)luenesulfonic acid, etc.), acetate ion, and sulfate ion. Among these, chloride ions, alkyl sulfate ions, and arylsulfonate ions are particularly preferred.

The alkyl groups and aralkyl groups of R2, R3 and R4 include substituted alkyl groups and substituted aralkyl groups.

Examples of the alkyl group include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, hexyl group, cyclohexyl group, -2-ethylhexyl group, and dodecyl Mfx.

Substituted alkyl groups, such as alkoxyalkyl groups (e.g., methoxymethyl, methoxybutyl, ethoxyethyl, butoxy/ethyl, vinyloxyethyl, etc.), cyanoalkyl groups (e.g., cocyanoethyl,
3-cyanopropyl group), halogenated alkyl group (
For example, there are 2-fluoroethyl groups (h2-chloroethyl groups, perfluoropropyl groups), alkoxycarbonylalkyl groups (e.g., ethoxycarbonylmethyl groups), allyl groups, 2-butenyl groups, propargyl groups, etc., and aralkyl groups. is an unsubstituted aralkyl group.

For example, substituted aralkyl groups such as benzyl group, phenethyl group, diphenylmethyl group, naphthylmethyl group,
For example, an alkylaralkyl group (e.g., goomethylbenzyl group, 2.j-dimethylbenzyl group, quinpropylbenzyl group, kuoctylbenzyl group, etc.), an alkylaralkyl group (e.g., 14m methoxybenzyl group, 1 μm is a benzyl group, 4
1-x toxybenzyl group, etc.), cyanoaralkyl group (
For example, ≠-cyanobenzyl group b'' (≠-cyanophenyl) (methyl group, etc.), halogenated aralkyl group (
For example, a 1 μm chlorobenzyl group.

3-chlorobenzyl group %gubromobenzyl group.

There is a g-(g-chlorophenyl)benzyl group.

The number of carbon atoms in the alkyl group is preferably 1 to 72.

The number of carbon atoms in the aralkyl group is preferably 7 to 1 g.

Examples of R2, R3 and R4 interconnecting to form a cyclic structure with Q include the following.

An example of an aliphatic heterocycle (representing an atomic group necessary to form a bare ring) is, for example, R4. n is an integer from λ to lλ).

R□. represent a hydrogen atom and a lower alkyl group having 1 to 2 carbon atoms, respectively. ).

(represents the atomic group required to form a ring).

几2 Strive 几9　R1(.

and R2. When there are two R2s, they may be the same or different. ) etc.

Among these ring structures.

In the above example, R2, R41R6+ Q and X○ have the same meanings as in general formula (I).

Not only two components but also a mixture of two or more components may be used.

X is preferably 7.0 to 10 mol, y is preferably 20 to tO mol, and 2 is preferably 1% to 20 to 10 mol, 30 to 70 mol. .

The aqueous polymer latex of general formula (I) generally comprises a monomer having at least λ of the above ethylenically unsaturated groups, an ethylenically unsaturated monomer (this may be omitted) and general formula (11). It can be obtained by emulsion polymerizing a monomer represented by *2 and then reacting with a compound represented by Ra 4 to quaternize it.

(II) T(,1 C)12=C-L-X In the formula, L, X, and R are the same as those shown in general formula (I).

The compound (I(+
2゜4 R3, R4 and Q have the same meanings as in general formula (I).

) Examples include N-methylaziridine, N-methylacetidine, N-methylpyrrolidine%N-ethylpyrrolidine, N-MeF-ruviroline, N-benzylpyrrolidineSN-methylpiperidine, N-ethylpiperidine, N- Penzylpibe') Schiff, N-p-chlorobenzylbibe IJ Syn, N-p-isopropylbenzilbi is lysine, N-p-pentafluoropropenyloxybenzilbi is lysine, N-methylhexamethyleneimine, N-benzyl Hexamethyleneimine, N-methyldodecamethyleneimine, N-benzyldodecamethyleneimine, trimethylamine, triethylamine, tributylamine, dimethylzolobylamine, dimethylbenzylamine, tributylphosphine.

1-'J hexylamine, dimethyl-p-chlorobenzylamine, diazabicyclooctane% N-methylimidazole, N-methyl-2-methylimitazole, N
-Methylpyrazole, pyridine, 3. ! -lutidine, methylpyridine, /, and -diazabicyclo [! ,≠＋'
] Undesen/7 etc.

When the aqueous polymer latex represented by the general formula (I) of the present invention is synthesized by this method.

1 ■ (-CH2-C+ (L, X and R1 are general formula (1)
and X R1 ) and ÷c)+2-c+ typically contain from 0 to about 17 repeating H units.

In addition, the aqueous polymer latex represented by the general formula (1) includes a monomer having at least two ethylenically unsaturated groups, an ethylenically uncompatible monomer (this may be omitted), and a polymer latex represented by the general formula (11). After emulsion polymerization with an unsaturated monomer represented by

It can also be obtained by quaternization by reaction with an alkylating agent, alkenylating agent or aralkylating agent represented by R4-X.

T(, t, L + Q + 几2, R3 is the general formula (I)
is synonymous with Examples of monomers represented by general formula (III) include: For example, N-vinylbenzylpyrrolidine, N-vinylbenzylpyrroline, N-vinylbenzylhibalicin, N-vinylbenzylhexamethyleneimine, N-vinylbenzyldodecamethyleneimine. N, N-
Dimethylaminopropyl methacrylate, N,N-diethylamine ethyl methacrylate, N,N-dimethylaminopropylmethacrylamidoaminomethylphenyl)acrylamide, N-(N'
, N'-dihexylaminomethyl) methacrylamide, and the like. Among these, N-bi-rubenzylhyhalicin, N-vinylbenzylsamethylenimine, N-(N
',N'-dimethylaminemethylphenyl)acrylamide is particularly preferred.

Examples of R4-X (L4, n-butyl bromide, ethyl chloroacetate, n-! -hexyl bromide,
benzyl chloride, p-chlorobenzyl chloride,
p-methylbenzyl chloride, p-isopropylbenzyl chloride.

p- includes antafluoroprobenyl oquine benzyl chloride, among these, benzyl chloride,
Preferred are p-chlorobenzyl chloride, methyl p-toluenesulfonate, dimethyl chain acid, and diethyl chain acid.

Furthermore, the aqueous polymer latex represented by the general formula (1) can be prepared by using the above monomer having at least two ethylenically unsaturated groups, ethylenically unsaturated groups. It can also be obtained by emulsion polymerization of a tt+ monomer (which may not be present) and an unsaturated monomer represented by general formula (IV).

1 ■I CH2=C-L-Q-:R. 4 Xe3 R,1, R2, R3, I(+4, L, Q., X
eIri has the same meaning as general formula (I).

Examples of monomers represented by formula (IV) include c. Tato, tfd'N-hensil-N-vinylbenzylvinyldinium chloride, N-benzyl-N-vinylbenzyl/g-hydroazebinium chloride, N-(4'-chlorobenzyl)-N-vinylbenzylnoξ- Hydroazepinium-p-)luenesulfonate, N-methyl-N-
Vinylbenzyldodecamethyleneiminium chloride, N
-pendino-h-vinylbenzylimidazolium chloride, /-hexyl-2-methyl-3-vinylbenzylimidazolium chloride, /-butyl-2-phenyl-3-vinylbenzylimidazolium chloride.

l-Octyl-2-isopropyl-3-vinylbenzylimidazolium chloride, N-vinylbenzyl-p-phenylbilidinylamuku01J)', N-vinylbenzyl-p-benzylpyridinium-p-toluenesulfonate, N- Vinylbenzyl-p-phenylpropylpyridinium chloride, N-benzyl-N'-vinylbenzylbenzimidazolium chloride N C N t
, N/-diethyl=-N'-(p-1 soprobylbenzyl)ammoniomethylphenyl)acrylamide chloride%N-methacryloyloxyethyl-N,N
-diethyl-N-p-chlorobenzylammonium chloride, N-methacrylamidopropyl-N,N-dimethyl-N-p-octylbenzylammonium chloride,
N-vinylbenzyl-N,N,N-trihexylammonium chloride l-', N-vinylbenzyl-N,N
, N-)butylammonium-p-toluenesulfonate, N-vinylbenzyl-N,N-diythyl-N-benzylammonium chloride, N-vinylbenzyl-N,N-diethyl-N-p-1 soprobil Examples include benzylammonium chloride.

For the synthesis of the aqueous polymer latex used in the present invention, 4tI
No. g, 4t 7A,! No. r93, the same μdota λ, 0
．． 2.2, Getter 2/, /34L.

Getter/20, t3≠ issue, JP-A-53-72.

1, 22, British Patent No. 1, 2//, 039, 9t/, 39. ! issue. U.S. Patent No. 2,7 Tata, jA≠ No. 2, R/G, μ? No. 2, same @ 3. o33, A13
No. 3, No. 3.3177, IFF No. 3, 227
, +72, No. 3, 2 O, μ No. 17, No. 3, 2t
2,? /ri No. 3, 2≠j.

23, No. 2, Same No. λ, +! Ir/, f? No. 7, same whistle 3.

, No. 230,276, Canadian Patent No. 70≠, No. 77, John C. Petropoulosula, "Official,
Digest J (John C.

Petropoulos etal:Officia
ll) igest ) no L, 7/ri~73t(/rit
/).

"Introduction to Emulsion" by Sadao Hayashi (/ri70), Mune Muroi -
Author: “Chemistry of Polymer Latex J (/970).

Motoyama Jlhiko1'r Vinyl Emulsion J (zrJt
) %Mike, Scheider, Jua et al. [Journal of Science, Polymer Chemistry-1 Daisyon J
ngetal: Journal of Polym
er 5science.

Polymer Chemistry Editor
n)/II.

It is convenient to carry out this process with reference to the methods described in 201-2107 (/976) and the like. It goes without saying that the initiator for one polymerization, the concentration of one polymerization source, the reaction time, etc. can be varied widely and easily depending on the purpose.

For example, monopolymerization is generally carried out at 2Q to 1tro 0c, preferably aO to /λo'c. Polymerization weight%
radical polymerization initiator and optionally O/, 70% by weight
This is done using an emulsifier. Examples of the polymerization initiator include azobis compounds, peroxides, hydroperoxides, redox catalysts, etc., such as potassium chloride, ammonium chloride, tert-butyl octoate, benzoyl peroxide, isopropyl ξ-carbonate, Co, dichlorobenzoyl peroxide, methyl ethyl ketone 1 oxide, cumene hydroperoxide, dicumyl peroxide, azobisisobutyronitrile%2. -2'-azobis(,7
-amidinopropane) and hydrochloride.

As an emulsifier, it is anionic, cationic, and amphoteric.

In addition to nonionic surfactants, there are also water-soluble polymers. For example, sodium laurate, sodium dodecyl sulfate, sodium /-octoxycarbonylmethyl-7-octoxycarbonylmethanesulfonate, sodium laurylnaphthalenesulfonate, sodium laurylbenzenesulfonate.

Sodium diuryl phosphate, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan lauryl ester, polyvinyl alcohol & Tokko Sho r3-
Examples include emulsifiers and water-soluble polymers described in A/RI No. 0.

The above-mentioned quaternization reactions generally range from 17O0C to about ioo
It is carried out at a temperature of °C, particularly preferably 200C to rO0C. The entire manufacturing process of the aqueous polymer 2tex used in the present invention can be carried out in one container, and there is no need to use a water-miscible organic solvent during the quaternization reaction. It has the characteristics that it can be produced stably and easily without causing agglomeration or destabilization.

Next, examples of the aqueous polymer latex used in the present invention will be shown.

a:b:c:d=J-2 4--7. j: j, evening
: (-Tomoe2a:b:c:d=j:Jt;♂:jComi:b:c:d=Evening:2j:10:l.

-CHCL3- x:y:z-ta:μ7. ! Nige 7, -CHCL3- a: b: c: d = evening: 3j: 32: 1 - C
HCL3- a:b:c:d=, 2:3:10:Evening.

a: b: c: d = 2 nee cHcH2- x : y = ! : Tatax:y:z=3:jA ,e X:y:Z=μ:4t,! ': I- -O (220-C)-12-C- H3 x:y:z='A:! 2: 4H9 3 -CHCl-12- x:y:z=2:31:Aθ x:y:z=/ :, t, 2:47 ■-2' CHa C
Ha■ CH2 C=0 -(-C)-] 2 C-)- CH3 x:y:z=4L:60:3A i-27CH3 x: y: z=g:4'J':! ZA C=O H -1 113 ■ Cl-12c+ z -0? x:y:z=4:4tza:μg 1: a:b:c:d-,2:lA2:20:3/and 9C Otsu-CHCH2-Cl2C/ a:b:C-=! r:30: 01Ct(2- a:b:c:d=2:≠ri;j:≠≠ a:b:C:d=+:4(Ir:4L:!!H3C-N
-CI-1: (When performing ultrafiltration membrane treatment, use the same amount of ion-exchanged water as the permeate. A higher average water permeation rate is desirable for practical purposes, but in reality, the liquid properties of the filtration membrane and polymer latex In the case of the present invention, the average water permeation rate yo, i ~
/θm37m It can be done in 2 days. At this time, it may be carried out under pressure (approximately +-, r hours, preferably /-, t#/an2 for about l/am2~/vaginal/an2), or it may be carried out under reduced pressure. good.

The forms of filtration membranes are flat membrane type and pleated type.

Spiral wound type, tube type, hollow type, etc.

Either is fine.

The molecular weight cutoff of the filtration membrane is approximately 5oo-t.

o, ooo is suitable, /, 000~100°00θ
is friendly.

The chemical composition of the filtration membrane is cellulose ester polymer and acrylonitrile copolymer.

Regenerated cellulose, polysulfone, polyamide, vinyl chloride copolymer (for example, a copolymer of vinyl chloride and vinyl acetate, etc.), polyphenylene ocquindo.

Polyol S polyvinyl alcohol, polyester, polycarbonate, polyamide, polyimide.

polyvinylpyridine, polyolefin, polystyrene,
Examples include polyacrylic acid and polyacrylic ester. More details are described in Japanese Patent Publication Sho Tako-31ior.

Good luck, at least the degree of acetylation! IJ
It is a copolymer with

The particle size of the polymer latex to be treated with an ultrafiltration membrane is generally about 0.0/μ to i,oμ, but preferably 0.03μ to 0.311μ from the viewpoint of stability.

The appropriate solid content concentration of the polymer latex is approximately /-J'0% by weight (the same applies hereinafter), but considering stability and pressure loss at the appropriate time of ultraponics, 1.2-μo% is preferable.
% K 2-30% is preferred.

The degree of ultrap membrane treatment depends on the type of latex used,
Although it is difficult to make a general statement because it varies depending on the composition, counterion species, purpose, use, stability, etc., it is preferable to judge it by the electrical conductivity before and after the filtration membrane treatment and adjust it according to the use.

When used as a mordant, the electrical conductivity is preferably less than tt-ooμΩ/rule, particularly preferably less than 2jOμΩ/clT+, in terms of latex concentration (7 layers, 1 cl).

Pretreatment can also be performed in advance to prevent the polymer latex from changing during storage and adversely affecting photographic performance. As a preprocessing method, for example, ≠θ0C is a false joC.
or add acids such as hydrochloric acid and nitric acid (hydroxide); alkalis such as potassium hydroxide, sodium carbonate, and sodium bicarbonate; ammonia; amines, etc. Then heat it up. There are several methods that can be mentioned.

Furthermore, as described in Japanese Patent Application Laid-Open No. 57-202-3, it is also possible to fill a polymer latex with a hydrophobic substance by means of adsorption and then to perform ultrafiltration membrane treatment.

Furthermore, it is also possible to partially replace the counter ions of the ionic groups by adding an ionic substance such as a saccharic acid, an alkali, or a salt, and then treating the mixture with an ultrafiltration membrane.

Even after membrane treatment of polymer latex, hydrophobic substances can be adsorbed or filled into the latex.
Alternatively, it is also possible to replenish the emulsifier that has been partially removed, if necessary.

The ultrafiltration membrane treatment according to the present invention can also be used to concentrate Bolimar latex.

The photographic light-sensitive material used in the present invention can be applied to both black-and-white photography and color photography, and silver halide or other light-sensitive materials can be used as the light-sensitive material. Silver halide photographic emulsions can also be 0 negative emulsions.

A positive emulsion may be used. Silver halide color photography may include, for example, a coupler one-type photography or a photography method that forms an image using diffusion transfer of a dye or its precursor.The latter image As the most typical photographic method of formation,
There is a "color diffusion transfer method", which will be described below, but is not limited to this photographic method or mode.

The photographic light-sensitive material of the present invention is a photographic film unit.

That is, in the case of a film unit that can be processed by passing the film unit between a pair of juxtaposed suppressing members, it consists of the following elements.

One embodiment of this film unit is as follows.

After exposure, a light-sensitive element comprising one or more 7-silver halide emulsion layers coated on a support is superposed face-to-face with an image-receiving element having at least one layer comprising a mordant on the support. The alkaline treatment composition is then spread between these two elements for treatment. Preferably, the film unit is shielded from light on both sides of the photosensitive element or film unit when it is removed from the camera.

At this time, the image receiving element may be peeled off after the transfer.

US Patent 3. ≠/j, as stated in the tgeta issue,
You may be able to view one rack without peeling it off.

In another embodiment, the support, the image receiving element and the photosensitive element in the film unit are arranged integrally. A transparent support with an image receiving ttti < mordant), a substantially opaque light-reflecting layer (e.g. T i
02 layer, carbon black layer) and one or more photosensitive layers are effective. After the photosensitive layer is exposed, it is placed face-to-face with an opaque cover sheet 5 and a processing composition is spread between the two.

Another embodiment of the overlapping and integrated type to which the present invention can be applied is disclosed in Belgian patent No. 7, R! It is disclosed in the No. According to this embodiment, a transparent support is coated with a receiver layer (containing a mordant), a substantially opaque light-reflecting 1m (eg, as described above), and one or more photosensitive layers. Then, a transparent cover sheet is placed on the surface. A rupturable container containing an alkaline processing composition including an opacifying agent (eg, carbon black) is placed adjacent the top layer of the photosensitive layer and the transparent cover sheet. A film unit like this,
The processing composition (
(containing an opacifying agent) is spread across the surface between the photosensitive layer and the cover sheet. This blocks the film unit from light.

Development progresses. The transferred image can be viewed through the transparent support on the side opposite to the side with mixed light.

Examples of the present invention will be described below.

Part 1% is based on weight.

Example 2 (1) Preparation of polymer latex and ultrafiltration membrane treatment A polymerization tank equipped with a reflux condenser, a thermometer, a stirrer, and 5 dropping funnels was charged with 73% water. μ parts, 2 parts of sodium polyoxyethylene alkyl sulfonate, and 0.1 part of styrene were charged, and then θ and j parts of a 2-thiol aqueous solution of potassium supermyelate as a polymerization initiator were added at about to 0c.

While stirring, the W stage was stirred for 1 hour, and stirring was continued.
While keeping the liquid temperature at 600c, add 2 parts of potassium perchain acid aqueous solution 1
2 parts and 5 parts chloromethylstyrene.

A mixture of 3 parts of styrene and 1 part of divinylbenzene was added dropwise over 1 hour to effect emulsion polymerization. After the dropwise addition was completed, 3 parts of N-methylpiperidine as a neutralizing agent was added at 300C and heated at 700C/hour to reduce the solid content/3. , f%.

A polymer latex with a pH of 7.7 was obtained. To 100 parts of this latex, 0.3 parts of sodium bicarbonate and 2.0 parts of deionized water. Add the mixed solution in the evening for pretreatment, solid content 10, pH 7.0, 3 gas conductivity, 100 μΩ/mo, remaining amine λ, /λ 2/polymer 2, chlorine ion 3.0 melO. A polymer latex was obtained with equivalent weight/polymer f, sodium ion 17θ ppm, potassium ion ≠ 7 ppm, ash content 0.!f%, styrene ≠ Oppm (GC method). ) Ultrafiltration was performed using a tube-type ultrafiltration device using an IJ Sill ultrafiltration membrane (DUY-L membrane manufactured by Daicel Chemical Industries, Ltd.) under a pressure of 3 releases/rule 2, while removing the same amount of ions as the permeate. Treatment was performed by adding exchange water. The average water permeation rate is 0, 2
The treatment was completed 6 hours after the start of operation after 3 m37 m2 days. The obtained polymer latex has a solid content of %, p
H7,,A.

Ti conductivity tsiμΩ/(2), residual amine not detected, chlorine ion λ, 0x10 equivalent/polymer 9゜sodium ion 23ppm, potassium ion tppm, ash content 0.02%, styrene not detected (GC method), polymer latex It was found that the purity of the product was extremely high.

(11) Preparation of photosensitive material (sheet) on polyethylene terephthalate transparent support.

A photosensitive sheet was prepared by coating each layer as follows.

(1) The mordant latex treated with the ultrafiltration membrane according to (1) above was prepared with a solid content of 397 m2. Image-receiving layer containing gelatin 32/m2 and as coating aid.

(2) Titanium dioxide 2097m2. Seratin 2.0? /
A white reflection containing m.

(3) A light-shielding layer containing 2.097 m of carbon black and seratin/, r9/m.

(4) The following cyan dye-releasing redox compound 01lA
II? /m,) linkhexylphosphate)0.
0? ? /m, 2,! -Gt-Nia Layer (5) containing tadecylhydroquinone θ, 00197m and gelatin 0, I9/m
Red-sensitive red-sensitive inscribed positive beautifying silver emulsion (in amount of silver / , 0
397m2), gelatin 7/#9/'m2゜The following nucleating agents 0, 01iyrui/m2 and 2-sulfo-
j-n--'f: Red-sensitive emulsion layer containing ntadecylhydroquinone sodium salt Q, /3/m2.

, q (61,2,J'-Gi 6-tadecylhydroquinone O5≠3?/m2.) Lihexyl phosphate o
,/? /m2 and a layer containing gelatin 0,4' 97m2.

(7) Magenta dye-releasing redox compound of the following structural formula I (0,2/9/m2), magenta dye-releasing redox compound of structural formula II (0,//P/m2), tricyclohexyl phosphate (0019/m2) 2) b”
+ '-Gt, -pentadecylhydroquinone (0
,00? ? /m2) and gelatin (0,!Pr/m2)
).

Structural formula I Structural formula 1 (8) Edge-sensitive latent direct positive silver emulsion (0 in the amount of steel)
, f , 2 f / fn2) , gelati 7 (0, P9
/m2).

Same nucleating agent as layer (5) (0, θ3 nrq/m2)
'm and 2-Sulfo-! -n-: Edge-sensitive emulsion layer containing ntadane hydroquinone sodium salt (O, or ?/rn2).

(Same layer as 9+ +6+.

(11 Yellow dye color-emitting redox compound with the following structure (
0, evening 3f? /rr+2') b F lycyclohexyl phosphate (θ, 1397m2), 2
, T-t-pentadecylhydroquinone (0,0
/ II fl 7m2) and gelati 7 (0,79
7 m2).

0CH20] 2(ICII3 \ (11J Blue-sensitive blue-sensitive inscribed positive silver bromide emulsion (silver amount i, ori 9/m2.L gelatin (/ , / S?
7m2) %+m (same nucleating agent as 51 (0, Oli
ly 7m2) and coarse hot, , 0
Hydroquinone sodium salt (0,07?
A night-sensitive emulsion layer containing 7 m2).

(Royal gelatin/, Ofl 7m2 layer.

As a comparative example, the same photosensitive notebook was prepared except that the mordant F-Tex of layer (1) was coated, but untreated.

In addition, a cover 7-t was made as follows.

Cover Note A cover note was prepared by coating the following layers (/') to (3') on a transparent polyethylene terephthalate support.

(/') 10 pairs of acrylic acid and butyl acrylate λ1M
Acid polymer (//, Yu! 7'/m
2) and/or j- containing 4t-bis(2,3-epoxypropoxy)-phthane (0,,2,2?/m2)
0 (-2') acetylcellulose (hydrolyzes iooy acetylcellulose to produce 31..1? acetyl groups) (+, -29/m2) and to pair of styrene and maleic anhydride ≠ Copolymer of O (M amount ratio) (
methanol ring-opened product (molecular weight approximately 50,000) (0,235//
m ) and ter(2-anor/-methylethylthio)-/-phenyltetrazole (o, is≠?/m
) containing 1 threat.

(J') 19.7 pairs of styrene-n-butyl acrylate-acrylic acid-N-methylolacrylamide≠2.
3 to 3 copolymer latex and methyl methacrylate to acrylic acid to methylol acrylamide
A 2μ thick layer of 3:g:3 (weight ratio) copolymer latex mixed so that the solid content ratio of the former latex and the latter latex was t:h.

After the photosensitive sheet was exposed to light through a color test chart, the cover sheet was placed on top of the sheet, and 1. It was rolled out to a thickness of tμ (rolling was done with the help of a pressure roller). The treatment was carried out at /j'C and the results of 1H were obtained.

Treatment liquid No. / Table Untreated (for comparison) /, 72 2.10 /, 9
4 from the results in Table 1, the photosensitive sheet of the present invention using the mordant treated with an ultrafiltration membrane has a higher maximum medium degree of transferred image I understand.

Example 2 The photosensitive sheet of Example 1 was subjected to a forced storage test using the Hakunaka listed in Table 2, and then the processing solution was developed in the same manner as in Example 1 at 0C for 2 nights. From the results in Table 1, it can be seen that the photosensitive sheet of the present invention using a mordant treated with an ultrafiltration membrane exhibits little decrease in maximum density even under high temperature and high humidity conditions.

Table 2 Fresh mordant Fresh AO″CB G
B, 'B Untreated (relatively soft) l, 10 2. /2. 2,
02 /, al (-0,3F) Ultrafiltration membrane treatment /, 12 2. /l, 2.
// /, 12 (present invention) (-0, 2o) Large concentration aO%R,HJ[4jt 'C7o %I too 1
31yo OR, B G R.

/, 741 /, jj /, Otsu 7
/, 11 /, 70 (-0, 31) (-017
) (-0,73) (-〇,,24m) (-0
,32)/,9t/,tag/,7. t
/, 9ta /, 93(-0,20') (-0,/
7) (-0,07) (-0,/7) (-θ, l) Example 3 The polymer latex used in Example 1 was pretreated with sodium hydrogen carbonate, and the solid content? , diluted to 3%. This material has electrical conductivity of 00μΩ/cm and residual amine λ.
, /2%/polymer 2% chloride ion 3.0 me10-3 equivalent/polymer? , Styrene 4/Temperature 1) pm (GC method)
Met.

This polymer latex 27 was subjected to ultrafiltration using a cellulose acetate outside limit P1 membrane with a molecular weight cut off of ≠ 10,000, applying a pressure of /ky/m2, and adding the same amount of ion-exchanged water as the filtrate to the membrane. The average water permeation rate during treatment is θ, /m3/m
The membrane treatment was completed r hours after the start of operation in 2 days.

Although there was no change in the solid content of the obtained polymer latex, the electrical conductivity significantly decreased to 100 μΩ/■, and the residual amine and styrene (GC method) were reduced to such an extent that they could not be detected. .Chlorine ion is 2.0>10 equivalent/
Polymer 9. Sodium ion/3ppm, potassium ion fd-tppm.

The purity of the polymer latex was extremely good, with an ash content of 0.02%.

When this ultra-filter treated polymer latex is used in the mordant layer in the same manner as in Example 1, the photographic properties are improved as in Example 1.
and 2.

Claims (9)

[Claims] (1) A photographic light-sensitive material comprising a polymer aqueous latex treated with an ultrafiltration membrane (excluding the ultrafiltration membrane treatment of the silver halide dispersion). (2) The photographic material according to claim 1, wherein the aqueous polymer latex is cationic or anionic. (3) The polymer aqueous latex is cationic. A photographic material according to claim 1. (4) The photographic light-sensitive material according to claim 1, which contains a polymer aqueous latex as a mordant or an antistatic agent. (5) The photographic light-sensitive material according to claim 1, which is used to form an image using diffusion transfer of a dye or its precursor. (6) The photographic light-sensitive material according to claim 1, wherein the ultrafiltration membrane is 1% of cellulose acetate or an acrylonitrile copolymer. (7) The photographic photosensitive material according to claim 1, wherein the ultrafiltration membrane is made of cellulose acetate having an acetylation degree of at least μO% or a copolymer of a non-electrolyte water-soluble monomer and acrylonitrile. material. (8) The aqueous polymer latex is a vinyl-based aqueous polymer latex. A photographic material according to claim 1. (9) The photographic light-sensitive material according to claim 1, wherein the silver halide photographic emulsion layer contains a polymer aqueous latex treated with an ultrafiltration membrane.