JPS5855497B2 - photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to photographic materials, and more particularly to photographic materials having a photographic layer comprising a hydrophilic colloid on a support having a hydrophobic surface.

Conventionally, polyethylene terephthalate, cellulose triacetate, polystyrene, polycarbonate, polyolefin laminated paper, and the like have been widely used as photographic supports due to their excellent transparency and flexibility.

However, when these polymeric substances are used as supports, since all of the supports have hydrophobic surfaces, it is difficult to firmly adhere a photographic layer consisting of a support colloid, mainly gelatin, onto these supports. is extremely difficult.

Surface treatments of hydrophobic supports in conventional techniques attempted to overcome these difficulties include (1) chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge; (2) After surface activation treatment such as active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc., directly applying photographic emulsion to obtain adhesive strength; (2) Once these surface treatments have been applied, There are two methods, one is to provide an undercoat layer and then coat the photographic emulsion layer thereon.

(e.g., U.S. Pat. No. 2,698,241, 276,452
No. 0, No. 2864755, No. 3462335, No. 3475193, British Patent No. 78
No. 8365, No. 804005, No. 891469, etc.).

Among these methods, method (2) is more effective and widely used.

These surface treatments all involve creating more or less polar groups on the surface of the support, which was originally hydrophobic, and removing the thin layer that is a negative factor for the adhesion of the extreme surface.
It is thought that the adhesive strength of the surface is increased by increasing the crosslinking density of the surface and increasing the adhesive strength, and as a result, the affinity with the polar groups of the components contained in the undercoating liquid increases. This may be due to an increase in the fastness of the adhesive surface.

Various methods have also been used to apply the undercoat layer, including providing a layer that adheres well to the support as the first layer;
A so-called hydrophilic resin layer is applied as a second layer on top of that.
There is a multilayer method and a single layer method in which only one resin layer containing both a hydrophobic group and a hydrophilic group is applied.

All of these methods are well researched and include vinyl chloride, vinylidene chloride, butadiene methacrylate,
The suitability of many resins including copolymers starting from monomers selected from acrylic acid, itaconic acid, maleic anhydride, etc., as well as polyethyleneimine, epoxy resin-grafted gelatin, and nitrocellulose has been demonstrated. It has been considered.

However, these methods inevitably have the following drawbacks.

(A) Adhesive strength is not sufficient.

Field) Surface treatment must be applied.

(C) There are problems such as generation of toxic gas, adverse effects on the human body, and pollution.

(D) The flatness of the film is poor.

Sono It is difficult to control the temperature during the drying process of the base coat.

The present invention has been developed to overcome these drawbacks found in the prior art.

The first object of the present invention is to provide a photographic material having strong adhesive strength between the support and the photographic layer.

A second object is to provide a photographic material that has strong adhesion between the support and the photographic layer without surface treatment.

The third object is to provide a photographic material which allows a hydrophobic support and a photographic emulsion layer to be adhered even in a single layer undercoat.

Fourthly, it provides a photographic material that does not cause pollution problems.

That is, since the photographic material of the present invention does not necessarily require the use of organic solvents, harmful organic solvents are not released into exhaust gas or waste water.

Fifth, it provides a primer liquid that is less irritating to the skin.

Sixthly, it provides a photographic material with excellent flatness.

Seventhly, it is an object of the present invention to provide a photographic material that does not deteriorate the properties of the undercoat even under temperature fluctuations during the process.

When using the undercoating liquid of the present invention, there is no need to include an etching agent such as resorcin, orcin, or fluorocersin in the undercoating liquid.

However, if necessary, an etching agent as described above may be included in the undercoating solution.

In conventional undercoating liquids, it is essential to use an etching agent for the support, and the effect of this etching agent creates adhesion between the undercoat layer and the support layer due to the interlayer effect. A major feature of the undercoating liquid of the present invention is that sufficient adhesive strength can be obtained without using any etching agent.

That is, the present invention provides a photographic material using an emulsion polymer of an ethylene monomer using a single or copolymer of maleic anhydride or a derivative thereof as an emulsifier.

However, the prior art undercoating mentioned above has used organic solvents and etching agents in some form.

However, in recent years, it has become necessary to use an entirely aqueous undercoating method to obtain sufficient adhesion between these supports and hydrophilic silver halide emulsions for practical use.

The present inventors have been engaged in this research for several years, but there was a problem that among the above adhesive forces, especially in the adhesive force test described below, sufficient wet adhesive force could not be obtained, and one of the biggest causes of this was that We discovered that this is due to the use of a so-called low-molecular (in the sense that it does not polymerize) emulsifier used when synthesizing the undercoat material.

The present invention does not use this low-molecular emulsifier, and when a polymeric material that exhibits an emulsifying effect exhibits a thermosetting effect similar to that of an emulsion polymer during the film-forming process, the above-mentioned improvement in adhesive strength when wet can be achieved. The present invention was arrived at based on the idea that it works effectively.

As is well known, emulsion polymers are prepared using conventional emulsifiers such as alkylaryl sulfonates and ethylene oxide condensates of nonylphenols.

Unfortunately, although these materials are well known and commonly used in the art, these emulsifiers are surfactants.

Therefore, emulsion polymers containing these surfactants are
Sensitive to humidity when applied as a film or coating.

Especially when used as a photographic primer, developing, fixing,
The gelatin in the light-sensitive photographic emulsion on the undercoat layer expands and contracts approximately 2.3 times in the thickness direction while being washed with water and undergoes various chemical changes. It was extremely difficult to fully satisfy the so-called wet adhesive strength under these conditions.

Emulsion polymers that do not contain surfactants and are therefore not particularly sensitive to water are therefore desired.

Therefore, it is an object of the present invention to produce a novel emulsion polymer containing a specific emulsifier and to apply it as a photographic undercoat.

Specifically, when producing an emulsion polymer for use as an undercoat, a specific polymer is used as an emulsifier to increase water resistance.

The emulsion polymer thus prepared does not contain a surfactant and is therefore not sensitive to water.The specific polymer used as the emulsifier is a single or copolymer of maleic anhydride or its derivatives. .

Maleic anhydride or its derivatives include maleic anhydride, maleic anhydride substituted with 60 carbon atoms,
These hydrolysates, and esters and amides thereof.

The ester or amide moieties can include any organic group of 1 to 20 carbon atoms consisting of carbon and hydrogen with or without oxygen, nitrogen and other elements.

Preferably, it is selected from the group consisting of alkyl, oxaalkyl, aryl, alkaryl, aralkyl, and cycloalkyl groups.

Particularly useful are alkyl groups such as methyl, ethyl, propyl, butyldodecyl, etc.)) aromatic groups such as benzyl, diethylene glycol, xyethyl, proxyethyl, furfuryl, methyl ether, triethylene glycol, etc. Ether groups such as ether, thioether, etc.; as well as cycloalkyl groups.

The partner monomer for copolymerization includes vinyl or vinylidene compounds having about 2 to about 10 carbon atoms.

Among them, vinyl aromatic compounds are particularly suitable, such as Eva,
Styrene, alpha methyl styrene, vinyl toluene, vinyl xylene, 2,4-dimethyl styrene, 〇-
Included are 1m-1p-chlorostyrene, 2,5-dichlorostyrene, 2-methyl-4-chlorostyrene, and hyalphacyanostyrene.

In the present invention, particularly preferred emulsifiers are those having the following repeating units.

However, R1 is selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, halogen and nitrile, and mixtures thereof, and R2 is any organic group having 1 to 20 carbon atoms, and preferred examples include In the above formula, R
2 is an organic group having 48 carbon atoms.

Ar is one benzene ring, and Xl and X2 are selected from the group consisting of a hydrogen atom and a metal ion ammonium.

Substituted ammonium ions that are particularly useful in the practice of this invention include mono-, di-, and trimethylamines, mono-,
A mixture of di- and tri-ethylamine, mono-, di- and tri-isopropylamine, mono-, di- and triethanolamine, 2-methyl-2-amino-propanol-1 and solera.

Alkali metal ions include lithium, sodium, potassium, etc.

Particularly preferred in the present invention is that the unit of 1 is 5
~about 30 mole%.

Examples of suitable photographic covering materials for emulsion polymers using polymeric emulsifiers include emulsion polymer latexes with a weight of 1.0-4.
0% by weight of said polymer, especially with a molecular weight of 1000 to 2
0,000 is used as a sole emulsifier.

Instead of the butyl cellosolve ester of a styrene maleic anhydride copolymer as used in each example, the butyl cellosolve ester of a copolymer of maleic anhydride and the vinylidene aromatic compound described above can also be used.

Ethylene monomers that are emulsion polymerized using these polymeric emulsifiers include ethylene, propylene, inbutylene,
Mono-1 and di-olefins such as butadiene, isoprene; vinyl halides such as vinyl chloride, vinyl bromide; vinylidene halides such as vinylidene chloride; Esters of vinylidene monocarboxylic acid with monohydric alcohols having 1 to 18 carbon atoms; amides and nitriles of vinylidene monocarboxylic acid such as methacrylamide, acrylonitrile, methacrylonitrile, such as styrene vinylnaphthalene, alpha methylstyrene, Vinyltoluene, vinylxylene, 2,4-dimethylstyrene, 0-
Vinylidene aromatic hydrocarbons such as 1m-1p-chlorostyrene, 2,5-dichlorostyrene, 2-methyl-4-chlorostyrene, and their nuclear alkyl and...rogen derivatives; for example, vinyl such as vinyl methyl ether, vinyl isobutyl ether, etc. Alkyl ether: It can be any vinylidene heterodichlor compound such as vinylpyridine; vinyl ether of a monocarboxylic acid having 118 carbon atoms such as vinyl acetate, vinyl stearate, vinyl benzoate, etc.

Diesters of monohydric alcohols having 1 to 18 carbon atoms and maleic and fumaric acids, such as dibutyl maleate, can also be used.

The aforementioned polymer emulsifiers are used in emulsion polymerization using these monomers, but among these monomers, systems containing a small amount (40% by weight of styrene) are particularly suitable for use as undercoat materials for photographs. is desirable.

Preferred examples or combinations of monomers are as follows.

1, styrene/butadiene 2, styrene/isoprene 3, methyl acrylate 4, butyl acrylate 5, styrene/acrylonitrile/2-ethylhexyl acrylate 6, styrene/acrylonitrile/dibutyl fumarate 7, styrene/ethyl acrylate 8, methyl methacrylate/ Acrylonitrile/2-ethylhexyl acrylate 9, butadiene/acrylonitrile/styrene 10, butadiene/(meth)acrylate/styrene 11, vinyl chloride/vinyl acetate 12, vinyl chloride/ethyl acrylate 13, vinyl chloride/dibutyl fumarate of the present invention There are several characteristics that made it a pole.

First, the amount of emulsifier, which is a salt of a partial ester of a copolymer of maleic anhydride, must be within the range of 1.0-40% by weight, based on the total weight of solids of the system in which it is used.

If there is too little, the latex will clump together resulting in a totally unsatisfactory system.

Little or no benefit is obtained if more than 40% by weight is used in excess.

Secondly, the esters of the copolymers used include esters up to their half-esters.

If only a complete salt (formula 3 above) is used as the polymer emulsifier and its ester (formula 2 above) is not used, the latex will gel and become unusable.

Thirdly, the molecular weight of the emulsifier of the present invention must be controlled within a defined range.

That is, it is a low molecular weight type with a molecular weight of 1,000 to 20,000.

If the molecular weight of the emulsifier is too high, the latex becomes too thick and gelation occurs.

Therefore, the molecular weight also has an optimum value.

As mentioned above, the emulsifier of the present invention is a salt of a partial ester of a copolymer of maleic anhydride and a vinyl aromatic compound.

In the emulsion polymerization of the present invention, the polymerization initiation source is
For example, active light, photosensitizers and active light, ionizing radiation, ultrasound, organic or inorganic peroxides, sulfides, sulfines, sulfinic acids, sulfones, azo compounds, diaso compounds, nitroso compounds, persulfate compounds, A wide variety of water-soluble or oil-soluble redox initiators such as perchloric acid compounds are effectively used.

However, among these, those that impair photographic performance cannot be used.

The polymer used as an emulsifier in the present invention remains as it is in the polymer emulsion, and when this emulsion is turned into a film, a network structure is generated by the reaction between the polymer molecules to form a strong coating film. .

Therefore, in order to accelerate the curing reaction at this time, it is extremely effective to add a crosslinking agent.

As this crosslinking agent, crosslinking agents used in general oil-based paints or polybutadiene paints are suitable.

As for the addition method, the crosslinking agent may be added and dispersed after emulsion polymerization (or it may be dissolved in the polymerizable vinyl monomer before emulsion polymerization).

Furthermore, when using the emulsion polymer of the present invention, a matting agent,
Additives such as a crosslinking agent and an antistatic agent can also be used together.

Examples in which the latex obtained as described above was used as a photographic undercoat will be described below, but these are not intended to limit the present invention.

In addition, the test method for adhesion between the photographic film support and the emulsion layer carried out in the following examples is as follows.

(1) Adhesion test when drying Use a razor blade to make about 4 linear scratches on the emulsion side of the raw film, processed film, and dry film, and apply adhesive tape (e.g., Scotch Permacel) on top of the scratches. tape) and then peel it off instantly.

In this method, if the peeled part is 0 to 5% or more, it is classified as A grade.
If it is 5-30%, it is grade B, and if it is 30-100%, it is grade 0.

(2) Adhesion test during wet processing At each stage of development, fixing, and washing, use a metal pencil to make two scratches on the emulsion side of the film in the processing solution, and make two scratches at right angles to the lines. If the emulsion layer does not peel off on the scratch when rubbed in the direction with the tip of a finger, it is classified as Class A if the maximum peeling width is within 5 mm, and Class 0 if it is a dog.

Next, the method of the present invention will be specifically explained with reference to operation examples and examples.

However, the present invention is not limited to these examples.

Synthesis Example 1 The following emulsifier system is fed under stirring to a stirred reaction vessel equipped with a dropping funnel.

Water 55.4 parts Butyl cellosolve ester of styrene-maleic anhydride copolymer 71 parts Ammonium hydroxide (27% solution) 4.6 parts The above butyl cellosolve ester of styrene-maleic anhydride copolymer has the general formula 2. It is a partial ester containing 25 mol% of each of 3 and 3, and has a molecular weight of about 2500.

Ammonium hydroxide is added as a salt-forming component of the partial ester.

An initiator system having the following composition is then added to the stirred reaction vessel.

Ammonium persulfate 0.35 parts Sodium bisulfite 0.18 parts Water 6 parts Initiator and 28.6 parts styrene monomer are simultaneously added to the reaction vessel over a period of about 180 minutes with constant stirring and pressure.

Further, 2.86 parts of butadiene was added from another addition port over the styrene addition time.

During this time, the reaction temperature is maintained at 60°C. After addition of the initiator and both monomers, the reaction was continued for an additional 60 minutes to complete the reaction.

The obtained latex is cooled to room temperature and contains a surfactant to form an emulsion polymerized latex.

The styrene-butadiene ratio calculated from the refractive index is approximately 94.
: It was 6.

Synthesis Example 2 A stirred reactor equipped with a dropping funnel is charged with the following emulsifier system.

Water 3oo1rll
Methyl and secondary butyl 1:1 mixed ester of styrene-maleic anhydride coelectrolyte (25 mol% is 20 units of the above general formula) 351 Ammonium hydroxide (27% aqueous solution) 25 TfLl This stirred reactor Add 1 i of cumene hydroperoxide initiator to.

At the same time, 1.75 f of additional initiator and 105 parts of styrene monomer and 10.5 parts of butadiene monomer are added.

During this time, the reaction temperature is maintained at 80°C.

After 90% of the monomer has been added, an additional 51 rLl of ammonium hydroxide is added into the reactor.

The solids content was 277% compared to the theoretical value of 28%, indicating almost complete conversion.

Example 1 Unstretched polyethylene terephthalate base with a thickness of 5μ
The latex prepared in Synthesis Example 1 was applied so that

A film base was obtained by stretching the polyethylene terephthalate having this undercoat layer 3.2 times in the longitudinal direction and 3.4 times in the transverse direction.

The thickness of the undercoat layer after stretching was 0.46μ.

Gelatin 0.66wt% on the base coated with this one layer
saponin 0. OIS', chrome alum 0.01, water 10
An undercoat liquid consisting of 0CC was applied at a rate of 20CC/rrl and dried at 110°C for 3 minutes.

The base was coated with a silver halide emulsion.

When drying the photosensitive film thus obtained,
Both adhesive strengths when wet were A class.

Moreover, the photographic performance of the photographic film was good.

Example 2 In Example 1, the latex prepared in Synthesis Example 2 was used.

A silver halide emulsion was applied to the base.

When drying the photosensitive film thus obtained,
Both adhesive strengths when wet were A class.

Moreover, the photographic performance of the photographic film was good.

Example 3 A biaxially stretched, oriented crystallized polyethylene terephthalate film with a thickness of 200 μm and a width of 30 cm had a dry film thickness of 0.
．． The following composition was undercoated to a thickness of 45μ.

Synthesis Example 1 Primer (solid content) 2.2 Hexamethylene bisethyleneiminoureide 0.14 Water
The film of No. 97.6 was dried at 120° C. for 1 minute.

A silver halogen emulsion was applied onto this undercoat layer.

When drying the photosensitive film thus obtained,
Both adhesive strengths when wet were A class.

Moreover, the photographic performance of the photographic film was good.

Example 4 A dry film thickness of 0.45 μ on biaxially stretched crystallized polyethylene terephthalate with a thickness of 200 μ and a width of 30 cfrL.
The following composition was applied as an undercoat.

Synthesis Example 1 Primer (solid content) 2.2 2,4-dichloro-6-oxyto 3,5-triazine sodium salt 0.1 water 77 This film was dried at 130°C for 5 minutes.

A silver halide emulsion was coated on this undercoat layer.

When drying the photosensitive film thus obtained,
Both adhesive strengths when wet were A class.

Moreover, the photographic performance of the photographic film was good.

Example 5 Biaxially stretched and oriented crystallized polyethylene terephthalate with a thickness of 200 μm and a width of 30 crrL, with a dry film thickness of 0.45
The following composition was undercoated so that the thickness was μ.

Synthesis Example 1 Primer (solid content) 2.2 Trimethylene dimethane sulfone)
0.
22 Water 9758 This film was dried at 110° C. for 1 minute.

A silver halide emulsion was coated on this undercoat layer.

When drying the photosensitive film thus obtained,
Both adhesive strengths when wet were A class.

Moreover, the photographic performance of the photographic film was good.

Claims (1)

[Claims] 1. A photographic material characterized by having an undercoat layer containing an emulsion polymer of ethylene monomer using maleic anhydride or a derivative thereof as an emulsifier.