JPS63311347A - Photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the photographic characteristics of the titled material, by incorporating an aqueous emulsion which has the mean particle size of <=100nm and the cross-linking structure and the glass transition temp. lower than that calculated by a weight fraction method in a photographic sensitive layer as the constituting component of said layer. CONSTITUTION:The titled material comprises the aqueous emulsion which has the mean particle size of <=100nm and the cross-linking structure and the glass transition temp. lower than that calculated by the weight fraction method, in the photographic sensitive layer as the constituting component of said layer. The mean particle size of said emulsion is specified to <=100nm. Thus, the various kinds of the performances of the titled material each as the thermal fusible property, the transparent of the film, the smoothness and the gloss are improved. And, as the cross-linking structure is formed, the film having the excellent resistance to water and solvents is formed, and as the glass transition temp. of the formed film is reduced, the min film forming temp. is also reduced, thereby forming the film having the good mechanical strength.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a photographic light-sensitive material containing an aqueous emulsion as a forming component of a photographic light-sensitive layer.

[Prior art]

Traditionally, aqueous emulsions include a subbing layer, an intermediate layer, a dye image donor-containing layer, a scavenger layer, an S-retaining layer, an auxiliary layer,
Mordants, antistatic agents, color formers, ultraviolet absorbers, adhesion improvers, It is used as a film quality improver, etc.
Furthermore, a dispersion medium for filling or adsorbing photographic additives such as couplers, ultraviolet absorbers, antioxidants, brighteners, development inhibitors, development accelerators, and dye image additives, or for immobilizing them. A method of using it as a binder has been proposed.

Generally, when an aqueous emulsion is included in a photographic light-sensitive material, it is added to a coating solution and coated to produce a photographic light-sensitive material or film unit, and it has excellent surface gloss and improves dimensional stability, flexibility, etc. There is. However, since conventional aqueous emulsions still contain surfactants, etc., which have a negative effect on photographic performance, purification treatment using dialysis, ion exchange, synchrofilter, membrane filtration such as fibers, or electrodialysis is necessary. There are problems such as the need to perform

Furthermore, the aqueous emulsions obtained through these purification and treatments lack dispersion stability, and coarse particles are formed due to coalescence and agglomeration between particles, resulting in poor surface gloss, dimensional stability, There is a downside in that photographic properties such as flexibility deteriorate.

〔the purpose〕

The present invention is a photographic material that, unlike the conventional photographic materials described above, has good photographic properties and is capable of forming a photosensitive layer having excellent gloss, water resistance, solvent resistance, and mechanical strength. The purpose is to provide

〔composition〕

According to the invention, as a forming component of a photographic photosensitive layer.

A photographic light-sensitive material is provided, which contains an aqueous emulsion having an average particle diameter of 10 m or less, a crosslinked structure, and a glass transition temperature lower than the value calculated by the weight fraction method.

The photographic light-sensitive material of the present invention has an average particle diameter of 10
It is required that an aqueous emulsion having a particle diameter of 0 rv+ or less, preferably 80 nm or less, be used as a forming component of the photographic photosensitive layer.

In an aqueous emulsion, a film is essentially formed by filling and fusing particles, so the average particle size is required to be small; however, in the present invention, as described above, the average particle size is 10Or+I11 or less. , preferably 80
Because it is limited to nm or less, thermal fusion, film transparency,
It becomes possible to improve sheet performance such as smoothness and gloss by a factor of 111.

If the average particle diameter exceeds 1100 nm, the fusion properties (M density) when forming a film will be poor, and the impregnating property into conductive materials will also be reduced, and furthermore, the gloss, transparency, and Since the smoothness may be insufficient, the intended purpose of the present invention cannot be achieved.

A second feature of the aqueous emulsion used in the present invention is that it has a crosslinked structure within and/or between its particles.

That is, the aqueous emulsion according to the present invention has an ionic bond, a hydrogen bond, or a condensation reaction between the functional groups of the raw unsaturated monomers within the particles and/or between the particles, or between these functional groups and the functional groups of the emulsifier. Alternatively, since it is crosslinked by a polymerization reaction or the like, a film having excellent water resistance and solvent resistance can be formed.

Furthermore, the third characteristic of the aqueous emulsion used in the present invention is lower than the value calculated by the 1 weight fraction method.

It preferably has a glass transition temperature lower than 3°C, more preferably lower than 5°C.

Glass transition temperature (Tg) is the temperature at which a polymer changes from a glassy, hard state to a rubbery state when heated.If the glass transition temperature of a component, which is a structural factor of a polymer, is known, The glass transition temperature can be determined from the following equation using the weight fraction method.

Tg T'ga T'ga W^; Weight fraction W of component A, ; Weight fraction T of component B^; Glass transition temperature of component A T K n : Glass transition temperature of component This glass transition temperature is It is influenced by various structural factors, and in general, polymers with a crosslinked structure have a higher glass transition temperature, which can be 5 to 7°C higher depending on the degree of crosslinking, and adding a plasticizer to the polymer can increase the glass transition temperature. It is known that the temperature decreases.

On the other hand, for aqueous emulsions, the minimum film-forming temperature is known as the lowest temperature at which a film is formed by filling and fusing particles, and there is a proportional relationship between this minimum film-forming temperature and the glass transition temperature. Recently, the present inventors have developed ultrafine particles that have a crosslinked structure, have a minimum film-forming temperature or a glass transition temperature of the formed film that is lower than the value calculated by the weight fraction method, and form a film with excellent mechanical strength. An aqueous emulsion was discovered and found to be useful as a photographic material.

That is, the aqueous emulsion used in the present invention.

Despite having a crosslinked structure, it has the ability to form a film that exhibits a glass transition temperature lower than the value calculated by the weight fraction method as described above, so unlike conventional products, it exhibits an excellent plasticizing effect and is easy to form. As the glass transition temperature of the film decreases, the minimum film forming temperature also decreases proportionally, making it easy to create films with excellent transparency, adhesiveness, and smoothness even at room temperature, as well as hardness, tensile strength, and modulus. A film having good mechanical strength such as strength can be formed. In this case, as is clear from the comparative example below, if the glass transition temperature of the film to be formed is higher than the value calculated by the weight fraction method, the aqueous emulsion will not have sufficient plasticizing effect, so the minimum film forming temperature will be At room temperature, the film may not form, or even if it does, cracks or mesh-like streaks will form on the film, resulting in the formation of a film with excellent transparency, smoothness, and adhesion as in the present invention. Can not do it.

Furthermore, it is hard and lacks mechanical strength such as tensile strength and modulus strength, making it difficult to obtain a hard and strong film.

In addition, other characteristics of the aqueous emulsion used in the present invention are:
It has excellent dispersion stability over a long period of time.

That is, the aqueous emulsion used in the present invention has an average particle size of 100 nm or less;
Even when subjected to a forced heating dispersion stability test for one week, there was virtually no change in the average particle size, and even if there was a change, it was usually a single peak distribution of particles with an average particle size of 150 nm or less. Shows particle size distribution.

Also, even when the rate of change is large, the average particle diameter is 15
The particle size distribution of the first peak of less than 0n- is 97% or more, and the second peak due to particle aggregation is an extremely small peak of 3% or less that has a particle size distribution of 300 nm or more. , the particle size fraction of the average particle diameter is extremely small.

Furthermore, the aqueous emulsion used in the present invention is heated at 25°C and 6°C.
Even when subjected to long-term storage stability tests,
The rate of change in the average particle diameter is extremely small.

Therefore, the aqueous emulsion according to the present invention substantially does not coalesce or agglomerate particles with each other over time, and does not generate coarse particles. Since there is no change in viscosity or change in appearance, it shows excellent dispersion stability over a long period of time and has extremely high storage stability.

The reason why the photographic light-sensitive material of the present invention exhibits the excellent dispersion stability as described above is not necessarily clear, but it is because its average particle diameter is 10 Onp or less.

The Brownian motion between particles is relatively active, there is no polymerizable emulsifier remaining in the system, and the properties of each particle surface ensure that each particle is sufficiently preserved. The basic factor is presumed to be that coalescence and aggregation of particles are prevented and formation of coarse particles is not promoted.

In addition, in the present invention, in order to further improve the dispersion stability of the aqueous emulsion, for example, P-hydroxydiphenylamine, N,N'-diphenyldiamine,
Conventionally known polymerization inhibitors and polymerization terminators such as 2,5-di-tert-butylhydroquinone can also be added.

Further, the average molecular weight of the crosslinked aqueous emulsion used in the present invention is generally more than 100,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000, etc. It may have a molecular weight of about 100,000,000 or even higher.

The present invention will be explained in more detail below.

The aqueous emulsion used in the present invention can be obtained by emulsion polymerization of unsaturated monomers in the presence of a specific emulsifier described later.

Examples of this unsaturated monomer include (meth)acrylic esters represented by the following general formula (1) (wherein R1 and h
is hydrogen or a methyl group, R1 is an alkyl group having 1 to 18 carbon atoms), lower fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl acetate, acrylonitrile,
Nitriles such as methacrylonitrile, styrene, α-
Examples include styrenes such as methylstyrene and chlorostyrene, vinyls such as vinyl chloride and vinyl bromide, vinylidenes such as vinylidene chloride and vinylidene bromide, dienes such as butadiene, chloroprene and isoprene, and vinylpyridine. , (meth)acrylic acid esters, lower fatty acid vinyl esters, nitrile/l/l [and styrenes] are preferably used.

In addition, in the present invention, as an unsaturated jut to be copolymerized with the unsaturated monomer, in order to further strengthen the crosslinked structure within and/or between particles of the aqueous emulsion to be produced, and during film formation, Unsaturated 'P-Q monomers having reactive functional groups are preferably used to promote crosslinking, but even unsaturated monomers without reactive functional groups can be It is also possible to use unsaturated monomers which can be converted into compounds having .

Examples of such unsaturated 1p, mer having a reactive functional group include compounds represented by the following general formulas (n) to (■). These monomers can be used alone or in combination of two or more, and if necessary, other copolymerizable unsaturated monomers can also be used in combination.

R, OH (in the formula, 1s □IRZ lR4*Rs +R6+R?
, Its lR9, Al111DlrE, t+.

R2 and t are as follows.

R,, R2, i hydrogen atom or methyl group R4; carbon number 2
-4 alkylene group R9; direct bond, alkylene group having 1 to 3 carbon atoms, phenylene group or substituted phenylene group Rs; M elementary atom or -NH- R7; hydrogen, alkylol group having 1 to 5 carbon atoms R8; water C1-C5 alkylol group or C1-5 alkyl group R3; C1-4 alkylene group A; methylene group or carbonyl group B; -C11□0- or carboxyl group; hydrogen Atom, alkyl group having 1 to 3 carbon atoms, carboxyl group, -CO
NHCIIC113 or 0OH -CONI (CONH□ E; hydrogen atom, alkyl group having 1 to 3 carbon atoms, or
, COO11 tl; Real number of 1 to 20 R2; O or an integer of 1; Integer of 0 to 10) General formula (n), (III), (IV), (V), (V
Specific examples of compounds I), (■) and (■) include those shown in Fukishita.

Examples of general formula (II) Glycidyl acrylate Glycidyl methacrylate Glycidyl crotonate Glycidyl allyl ether Examples of general formula (III) Hydroxyethyl acrylate Hydroxyethyl methacrylate Hydroxyethyl crotonate Hydroxypropyl acrylate Hydroxypropyl methacrylate Hydroxypropyl crotonate Hydroxybutyl acrylate Hydroxybutyl MethacrylatePolyoxyethylene monoacrylatePolyoxyethylene monomethacrylatePolyoxyethylene monocrotonatePolyoxypropylene monoacrylatePolyoxybrobylene monomethacrylatePolyoxypropylene monocrotonatePolyoxybutylene monoacrylatePolyoxybutylene monocrotonateHydroxyethyl allyl ether hydroxy Propyl allyl ether Hydroxybutyl allyl ether Polyoxyethylene allyl ether Polyoxypropylene allyl ether Polyoxybutylene allyl ether Example of general formula (rV) Allylamine Acrylamine Methacrylamine Aminostyrene α-Methylaminostyrene Example of general formula (V) acrylamide methacrylamide aminoprobyl methacrylamide monomethyl acrylamide monoethylacrylamide diethylolaminoprobyl acrylamide general formula (V
Examples of I) Acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and its monoester or anhydride of an alkyl group having 1 to 5 carbon atoms, fumaric acid and its monoester or anhydride of an alkyl group having 1 to 5 carbon atoms, maleic acid Alanidofumarate Alanide N-carbamoylmaleic acid amide N-carbamoylfumaric acid amide Example of general formula (■) Methylallylthiol Methylmercaptostyrene Example of general formula (■) Crotonic acid amide N-(2-hydroxyethyl)acrylic acid amide N-(
2- and droxyethyl) methacrylic acid amide N-(2-
Hydroxypropyl) acrylic acid amide N-(2-hydroxypropyl) methacrylic acid amide The ratio of the unsaturated monomer having a reactive functional group to the above unsaturated monomer is 9.
9/l to 60/40 (weight), preferably 99/l
I ~ 90/10 (weight), this usage ratio is 997
If it is larger than 1, the degree of crosslinking within and between particles of the aqueous emuldimine produced will be small, and if it is smaller than 60/40, the emulsion copolymerizability will be poor, a large amount of aggregates will be formed, or the film forming property will be poor. Cracks may occur in the film formed.

As the emulsifier used when emulsion polymerizing the aqueous emulsion of the present invention using the unsaturated monomer described above, a film exhibiting a glass transition temperature lower than the value calculated by the weight fraction method as described above is used. Any emulsifier can be used as long as it forms, but particularly preferred emulsifiers are:
Polyoxyalkylene ethylenically unsaturated carboxylic acid polyesters represented by the following general formula (IX) (hereinafter abbreviated as poly(meth)acroyl emulsifier), general formula (
X).

Betaine ester type emulsifier represented by (XI), (XI), (XI) and (XIV) and general formula (XV)
, (XVI) and (X■).

(In the formula +1111R21RIL+1RL1t111Z
IR1)lR+41111s+R1611ti 7+R
ts 18+ 1a2 +a:+ la41as +F
la +'ll+a1Qg raha +GrJ tL
, M, T, X, Y, and V are as follows.

R1+n2; Hydrogen or methyl group 1 (,.; Alkylene having 2 to 4 carbon atoms J&R1□; Alkyl group or alkenyl group having 8 to 30 back atoms, which may be linear or branched, preferably 8 carbon atoms ~18 R, □; Alkylene group having 1 to 5 carbon atoms R111R14tR1s; Alkyl group having 1 to 3 carbon atoms or -C,840+1, which may be the same or different.

R, &, Rnia: an alkyl group having 6 to 20 carbon atoms or hydrogen, at least one of which is alkylene having 6 to 20 carbon atoms, (R1,; hydrogen 5 alkyl having 1 to 30 carbon atoms) group or alkenyl group at +az yaJla4 +as 9aG+av
1ilI-represents the number of moles of alkylene oxide added; a4; a real number from 1 to 50; preferably the number of moles of alkylene oxide added in the molecule is 8 or more; a2; a real number from 0 to 20; a; t+□; and R□. When one is an alkyl group, a real number from 0 to 20; when both RLS and nts are an alkyl group, a real number a from 1 to 30; a real number a from 1 to 30; a real number a5 from 0 to 20; Real number a7 from 0 to 20; Real number a from 0 to 20; Integer a9 from 0 or 1; Real number p from 2 to 20; Integer from 2 to 5 -o-po-o- 0R7X OCnHzn-&(Rat)F- a-〇-R□91R2
0; hydrogen or alkyl group with 1 to 2 carbon atoms R2□; hydrogen or +R, a Oh-If or gl; integer ga of 0 to 5; integer n of 0 to 10; integer axo of 1 to IO; Real number (C11,), -C11-〇- or (C1l,),
-CI+-0-C11,- and y: real number 1 of 1 to 5 (2□+Rzi; hydrogen or alkyl group having 1 to 20 carbon atoms Y'; alkylene group having 3 to 8 carbon atoms, carbonyl with oxygen spanning Nitrogen 1.CI+-0- or )-〇-L; Alkylene group having 1 to 5 carbon atoms or -011-CIl
□COOM T; Direct bond, oxygen, sulfur; Hydrogen or inorganic anion In order to obtain an ultrafine-particle pre-crosslinked aqueous emulsion that has a dense, more advanced crosslinked structure within the particles and/or between the particles and forms a film that exhibits a glass transition temperature lower than the value determined by the calculation formula, As an emulsifier used in the emulsion polymerization of the above unsaturated monomer, (a) poly(meth) represented by the above general formula °(■);
Acroyl emulsifier, (b) the above general formula (X), (XI
), (XO), (xm).

Betaine ester emulsifier represented by (XIV) and (
e) The ether carboxylic acid type emulsifier represented by the above general formulas (XV), (XVI), and (X■) is prepared by (a)/(b)=
179-971 or (a)/(C)=1/9-9/1
, preferably in a weight ratio of 1/4-471. If this ratio is less than 179, the degree of crosslinking within and/or between particles of the aqueous emulsion produced may be small, and if it is greater than 9/1, the average particle diameter of the aqueous emulsion produced may become large. The appropriate amount of the emulsifier used is about 0.1 to 15% by weight, preferably 0.5 to 10% by weight, based on the unsaturated Quit compound to be emulsion polymerized.

Additionally, known anionic, nonionic and cationic surfactants may be added as necessary, specific examples of which include higher alcohols, higher alcohol oxidized alkylene adducts, alkylphenol oxidized alkylene adducts, and styrenated surfactants. Sulfate type of phenol alkylene oxide adduct, olefin sulfonate type such as α-olefin, long chain alkyl amine alkylene oxide adduct and di-long chain alkyl amine alkylene oxide adduct
Examples include ammonium salt type, sodium salt of N-(1,2-dicarboxyethyl)-N-octadecylsulfonic acid monoamide, and dialkylsulfosuccinate.

Also, when obtaining the aqueous emulsion of the present invention.

When using betaine ester as an emulsifier, it is desirable to adjust the pH in the emulsion polymerization step to less than 6, preferably 3 to 6. If the pll is 6 or more, the physical properties of the aqueous emulsion of the present invention will be improved in the emulsion polymerization step. This is undesirable because a large amount of aggregates exhibiting physical properties that are significantly different from those of the conventional method are produced.

In obtaining the aqueous emulsion of the present invention,
Conventionally known emulsion polymerization methods can be used as they are in the presence of the above-mentioned unsaturated lit M form and the emulsifier. For example, an unsaturated 111 M polymer is emulsified and dispersed in water at a concentration of 20 to 60% by weight in the presence of a polymerization initiator corresponding to 0.1 to 5 weight percent of the unsaturated monomer, and emulsion polymerization is carried out. All you have to do is make it happen.

As the polymerization initiator, water-soluble independent initiators and water-soluble redox initiators used in ordinary emulsion polymerization are used, such as hydrogen peroxide alone or hydrogen peroxide and tartaric acid, citric acid, Combinations with carboxylic acids such as ascorbic acid, hydrogen peroxide, oxalic acid, sulfinic acids and their salts or oxydialdehydes,
In addition to combinations with water-soluble iron salts, persulfates, percarbonates,
Peroxides such as perborates and 2,2'-azobis(2
-amidinopropane) and its salts, 2,2'-azobis(
Water-soluble azo initiators such as N,N'-dimethylene-isobutyramidine) and its salts, and 4°4'-azobis(4-cyanovaleric acid) and its salts can be used.

Furthermore, water-soluble nonionic polymer substances, anionic polymer substances, cationic polymer substances, and the like can be used in combination. Furthermore, plasticizers and PU regulators commonly used in conventional methods can also be used in combination, if necessary.

Examples of nonionic polymeric substances include polyvinyl alcohol, dextrin, hydroxyethyl starch, human starch derivatives such as roxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and the like.

Examples of anionic polymeric substances include polymers such as anionized hydroxyethyl cellulose, anionized starch, anionized guar gum, anionized chitosan, carboxymethyl cellulose, and anionized polyvinyl alcohol.

Further, as the cationic polymer substances, cationized hydroxyethyl cellulose, cationized starch, cationized guar gum, cationized chitosan, and cationic (meth)acrylic acid amide.

Examples include polymers such as dimethyldiallylammonium chloride.

These nonionic polymeric substances, cationic polymeric substances, and anionic polymeric substances can be used alone or in combination of two or more, but the amount added is 0 to 100% of the monomer to be emulsion polymerized. .05-5 weight 2. Preferably 0.
It is appropriate to use 1 to 3% by weight.

Further, as the plasticizer, phthalate ester, phosphate ester, etc. can be used. Furthermore, as a PL+ adjuster, salts such as sodium carbonate, sodium bicarbonate, sodium acetate, etc. may be used in combination in the range of 0.01 to 3 weight stones, but as described above, when a betaine ester type emulsifier is used as an emulsifier. It is desirable to adjust the pH to less than 6.

To prepare the photographic light-sensitive material of the present invention, for example, the aqueous emulsion prepared as described above and the light-sensitive material silver bromide, silver iodide, silver chloride, silver chlorobromide, silver chloroiodide, Photosensitive silver halide such as silver chloroiodobromide, gelatin, and other color formers, ultraviolet absorbers, optical brighteners, antifoggants, stabilizers, dispersants, etc. are added as necessary to form an emulsion. This emulsion is applied to paper-based supports such as baryta-coated paper, document paper, and resin-coated paper, natural fiber esters such as nitrocellulose, diacetate cellulose, polyester, polycarbonate, polyester,
A synthetic polymer film such as polystyrene may be coated on a support by an extrusion coating method or the like and dried.

〔effect〕

The photographic light-sensitive material of the present invention contains, as a forming component of the photographic light-sensitive layer, an aqueous emulsion having an average particle diameter of 1100 nm or less, a crosslinked structure, and a glass transition temperature lower than the value calculated by the weight fraction method. Therefore, the surface of the photographic photosensitive layer has excellent gloss, does not cause delamination from the support, and has excellent water resistance, solvent resistance, and mechanical strength.

Since it also exhibits good photographic properties, it can be used not only as a photosensitive silver halide emulsifier layer but also as an undercoat layer, an intermediate layer, a dye image donor-containing layer, a scavenger layer, a protective layer, an auxiliary layer, a backing layer, an image-receiving layer, a timing layer, Barrier layer, release layer, antistatic layer,
It has extremely high practical value when used in antihalation layers, etc.

〔Example〕

Next, in order to explain the present invention in more detail, Examples are shown below.

Example 1 Emulsifier 8 shown in Table 1 was placed in a glass reaction vessel equipped with a thermometer, stirrer, reflux condenser, nitrogen introduction tube and dropping funnel.
The heavy electric section and 150 tons of water were charged and dissolved, and the system was replaced with nitrogen gas. Separately, 75 parts by weight of ethyl acrylate and 75 parts by weight of methyl methacrylate.

4.5 parts of N-methylolacrylic acid amide and 1 part of water
．． 156 parts by weight of an unsaturated monomer mixture consisting of 5 parts by weight was prepared, 15 parts by weight of this was added to the reaction vessel, and 4 parts by weight were added.
Emulsification was carried out at 0°C for 30 minutes, and then the temperature was raised to 60°C. OX 10-
'no Qe/water phase a' was dissolved in 48.5 parts of water and added to the reaction vessel, and immediately the remaining unsaturated monomer was continuously poured into the reaction vessel for 30 minutes. and polymerization was carried out at 60°C. After dropping the unsaturated monomer, the mixture was aged at 60° C. for 60 minutes.

[Evaluation of water-based emulsion]

The average particle diameter, crosslinking properties, film forming properties, and glass transition temperature of the aqueous emulsion thus obtained were measured by the following methods.

Average particle size: Coulter Submicron Particle Analyzer (Coulter Electronics, Inc., USA, Coul
The average particle diameter was measured using a ter Model N4 type.

Crosslinking property: 30 g of an aqueous emulsion adjusted to have a v4 content of 40% by weight was uniformly cast onto a 12 cm x 14 c+s glass plate and air-dried at 25°C. The film obtained in this way is 2co+X4c
The film was cut into pieces of 5.0 m and immersed in a petri dish filled with benzene at 20°C for 48 hours, and the degree of swelling of the film was determined. ? The evaluation was made as follows based on the ¥ dissolvability.

0; Film area before immersion in benzene (2ci+X4cI
It is the same as or slightly better than 11).

Δ: The degree of swelling is large and the film shape is impaired.

×: The film was dissolved in benzene and became a uniform liquid.

Film forming property: A film was formed by air drying at 25°C, and the condition of the formed film was visually evaluated.

0: Forms a smooth and uniform film.

Δ: Forms a film with a mesh pattern.

×: No film is formed.

Glass transition humidity (Tg) Seiko Electronics Co., Ltd. thermal analysis measurement device (SSC5000)
Tg was measured using DSC200). The calculated value of Tg was calculated by the weight fraction method (described above).

[Evaluation of film characteristics]

The above aqueous emulsion 3 whose solid content was adjusted to 20% by weight
0 parts by weight was uniformly cast onto a 12 cm x 14 cm glass plate, air-dried at room temperature to form a film, and the film properties were evaluated. Film properties were evaluated based on the following criteria.

Transparency: According to JIS K 6714, the haze value of the film was measured using an integral light transmittance measuring device.

Water resistance: The film was cut into pieces of 20 pieces x 4 cm, immersed in a petri dish filled with water at 20°C, and the state of whitening of the film was visually judged.60; The film was transparent. be.

Δ: The film is translucent.

×: The film is opaque.

Adhesion: The surface of the film was touched with a finger and the sticky feeling was evaluated based on the following criteria.

0; No sticky feeling Δ; Slightly sticky was measured.

(Evaluation of photographic properties) A silver halide gelatin emulsion consisting of 90 mol% silver chloride, 9 mol% silver bromide and 1 mol% silver iodide was chemically sensitized using a sulfur sensitizer and a gold sensitizer. Add the aqueous emulsion to this silver halide emulsion so that the solid content of the aqueous emulsion is 50% by weight based on gelatin, and mix uniformly.6 Next, the silver halide emulsion thus obtained is resin coated. A sample was prepared by coating on a paper support using an extrusion coating method so that the amount of silver was 1.5 g/if and drying.

A part of this photographic material was exposed to tungsten light through a step tablet for a certain period of time, and a roller general feed automatic development processing material and a developer and fixer having the following composition were used.
After developing at 20°C for 30 seconds and fixing at 28°C for 20 seconds, the film was washed with running water at 20°C for 20 seconds and dried with hot air at 45°C.

[Developer OjK solution]

Potassium bromide; 2.5 g ethylenediaminetetraacetic acid-disodium salt; 1 g potassium sulfite (55% aqueous solution); 90 g potassium carbonate; 25 g hydroquinone: 10 g 5-methylbenzotriazole; 100 mg 5-nitrobenzitriazole; 100 g 1-phenyl-
5-Mercaptotetrazole; 30mg 5-nitroindazole; 50mg 1-phenyl-4-methyl-4-hydroxymethane; 0-13g thyl-
3-pyrazolidone diethylene glycol; 60g sodium hydroxide; P! ! I'm going to adjust it to 10.6.

The above stock solution, which is made up to 500 mQ by adding water, is diluted twice with water before use.

[Delivery liquid]

(Part A) Ammonyl thiosulfate As; 170
g Sodium sulfite; 15 g Boric acid; 6.5 [Glacial acetic acid
: 12mQ Sodium citrate (dihydrate); Add 2.5g water to make 275mQ (Part B) Aluminum sulfate (18hydrate) : 15
g sulfur M (98%);
Add 2.5g of water to make 40mQ. Adjustment method during use is as follows: Add about 600m of water to Part A Part 275+* Q, then add 40m of Part B Part Q, then add more water. Finish to I 000mΩ.

The photographic characteristics of each photographic sample processed using these processing solutions are summarized below. It was evaluated by

Appearance: The gloss of the photographic layer was judged by visual 'It' and evaluated according to the primary standard.

O: Good gloss and excellent appearance.

Δ: Slightly poor gloss.

X: Lack of luster.

Abrasion resistance, water resistance or solvent resistance: Apply a load pressure of about 200 to 300 g to the photographic layer directly or apply a load pressure of about 200 to 300 g with your index finger dipped in 0.5 g of water or benzene oil droplets for 5 minutes and trace the photograph. The layers were visually judged using the following criteria.

0: A clear photographic layer was maintained.

Δ: Some peeling is observed in the photographic layer.

×: Peeling is observed in the photographic layer.

Blackening density: The blackening density of the photographic layer was measured using a Macbeth densitometer (RD-519), and the maximum density was evaluated.

Properties of the aqueous emulsion obtained by the method below,
The properties of the film formed and the photographic properties are shown in Tables 1 and 2.

Samples Nos. 1 to 4 are examples of the present invention, and Samples Nos. 5 to 7 are comparative examples. From Tables 1 and 2, it can be seen that the sample of the present invention is good as a photographic material.

In addition, samples Nos. 1 to 4 also showed excellent dimensional stability (curl degree) and high contrast.

Table 2 In accordance with JIS-6781, dumbbells were prepared from the aqueous emulsions of Sample Not (invention) and Sample No. 5 (comparative example), and a stress stress test was conducted. The results are shown in the drawing. As is clear from the drawings, the product of the present invention forms a film that is harder and more durable than that of the comparative example. Example 2 From 8.0 parts by weight of the emulsifier shown in Table 3, 90 parts by weight of ethyl acrylate, 60 parts by weight of methyl methacrylate, 4.5 parts by weight of N-methylolacrylamide, and 2.5 parts by weight of water. 157 parts by weight of an unsaturated compound and 3.0 parts by weight of potassium persulfate as a polymerization initiator. OX 10-'mole/water phase Ω, sodium thioxide3. OX 10-3mole
/Aqueous phase Q and copper sulfate5. OX 10-'5ole/aqueous phase Q
It will be 47.5! ! ! The mixture was dissolved in a certain amount of water, and emulsion polymerization was performed in the same manner as in Example 1 to prepare an aqueous emulsion.

Properties of the aqueous emulsion thus obtained, 20
The characteristics and characteristics of the film formed by air drying at ℃ were measured and evaluated in the same manner as in Example 1.The results are shown in Tables 3 and 4
Samples Nos. 8 to 11 shown in are examples of the present invention, and samples Nos. 12 to 14 and 14' are comparative examples.

Table 4 Example 3 11-butyl acrylate 60 parts (parts, styrene 901
Unsaturated 111 M body mixture consisting of tM parts and 4.5 parts 2-hydroxyethyl methacrylate + tt parts 15/1.
5 parts by weight, 8.0 parts by weight of the emulsifier shown below, 4.0 parts by weight and 9.0 x 10-' mol of the polymerization initiator shown in Table 5.
Table 5: Dissolve in 50 parts by weight of water to form e/water phase Q
Emulsion polymerization was carried out in the same manner as in Example 1 at the polymerization temperature shown in , to prepare an aqueous emulsion. The properties of the obtained aqueous emulsion, the properties of the film obtained by air drying at 20°C, and the properties of the film are shown in Tables 5 and 6.

Sample No! Samples Nos. 5, 16, 17, 19, 20 and 21 are examples of the present invention, and Samples No. 18 and 22 are comparative examples.

In addition, the mechanical strength of the films of Sample No.+5-17. On the other hand, all had good film-forming properties at temperatures below 20°C.

Table 6 Example 4 The following emulsifiers [-1-IE-5C,
2If,,()(,,II,,0-311.0)-,C
Unsaturated monomer mixtures 11 to 3 shown below were prepared separately for OONa E-2, and emulsion polymerization was performed in the same manner as in Example 1 to prepare an aqueous emulsion. 81) The properties of the resulting aqueous emulsion and the properties of the film formed by air drying at 25°C are shown in Table 7.

Samples Nos. 23 to 34 are examples of the present invention. In addition, the mechanical strength of the films of samples Nos. 23 to 34 all have an elongation rate of 1.
50% or more, tensile strength (strength at break) 150Kg/c+
#That's all.

Further, in the same manner as in Example 1, photographic properties were measured and evaluated using the aqueous emulsions of Samples Nos. 23 and 24.

The results showed that all the samples had excellent appearance, abrasion resistance, and solvent resistance, had a maximum density of 2.14 to 2.18, and exhibited good photographic properties.

Example 5 The dispersion stability of the aqueous emulsions of Samples Nos. 1 to 34 was evaluated in the following manner. The results are shown in Table 8. The dispersion stability test was conducted as follows.

[Dispersion stability]

After putting 150 g of an aqueous emulsion whose solid concentration was adjusted to 40 weight and bt% in a 220 + m Q glass bottle and sealing it, it was left standing in a constant temperature room at 25 ° C for 6 months and in a constant temperature room at 45 ° C for 1 week, respectively. The appearance, transmittance, viscosity, and average particle diameter were measured to evaluate the dispersion stability of the aqueous emulsion. The appearance, transmittance, viscosity, and average particle diameter were measured by the following methods.

Appearance was evaluated by visual judgment at 25° C. according to the following criteria.

O: Transparent or translucent liquid Δ: Cloudy liquid wave light 8
Determine the absorbance under 00 nm light irradiation and calculate the light transmittance (%)
was calculated.

Viscosity The viscosity at 25° C. was measured using a Nibruckfield viscometer (B-type viscometer manufactured by Tokyo Keiki Co., Ltd.).

Average particle size: Coulter Submicron Particle Analyzer (Coal Tar Electronics, Inc., USA, Cou
The average particle diameter was measured using the following method (Model N4 type).

The results are shown in Table 8 (1), (2) and (3).

In addition, the sample was subjected to a forced heating dispersion stability test that was left in a constant temperature room at 45°C for one week! ~4.8~11.15~17.1
Example 1 Aqueous emulsions of 9-21 and 23-34
A sample of the skin was formed according to Example 1, and the properties of the film were measured according to Example. Good results were obtained in terms of transparency, water resistance, adhesive, solvent resistance (crosslinking) and mechanical strength, which were almost the same as those of Examples 1.2.3 and 4.

Graphs showing changes in particle size distribution before and after the dispersion stability test are shown in FIG. 2 (A) and FIG. 2 ([1)].

In addition, sample No. 7 in Table 8 (1) had a large number of extremely large particles and was found to be undetermined or acceptable due to poor dispersion after being left standing for one week at 45°C. Therefore, both sample No. 1 and sample No.
Changes in particle size distribution after standing at 5°C for 6 months were illustrated and compared.

[Brief explanation of drawings]

Figure 1 shows the measurements obtained when dumbbells were made from aqueous emulsions of the present invention product (sample No. 1) and comparative product (sample No. 5: film forming temperature: 35°C) in accordance with JISK-6781, and a stress-strain test was performed on the dumbbells. This is the result. Solid line: Defective product of the present invention M: Comparative product Figure 2 (A) and Figure 2 (B) are the product of the present invention (sample N).
This is a graph showing the change in particle size distribution of aqueous emulsions of o1) and a comparative product (sample No. 1) after they were allowed to stand at 25° C. for 6 months.

Claims (1)

[Claims] (1) As a forming component of the photographic photosensitive layer, the average particle diameter is 10
1. A photographic light-sensitive material comprising an aqueous emulsion having a glass transition temperature of 0 nm or less and a glass transition temperature lower than the value calculated by the weight fraction method when the emulsion has a crosslinked structure.