JPH05197071A - Photographic support - Google Patents

Abstract

PURPOSE:To improve coatability and antitackiness by incorporating a specified copolymer having repeating units. CONSTITUTION:This photographic support contains the copolymer having repeating units each represented by formula I in which R1 is H, Cl, or 1-3C alkyl; R is 1-30C alkyl, aralkyl, aryl, or alkylaryl, at least one H of each substituted by an F atom; X is -(R2)p-L- or -L-(R2)p-; R2 is 1-100 alkylene, arylene, or aralkylene; L is-O-, -S-, -N(R3)-, -CO-, -OCO-, -SCO-, -CON(R3)-, -SO2-, -N(R3)SO2-, -SO2N(R3)-, or-SO-; R3 is 1-4C alkyl; and P is 0 or 1.

Description

Detailed Description of the Invention

[0001]

The present invention has excellent coatability,
It also relates to a photographic support having improved adhesion resistance.

[0002]

2. Description of the Related Art A photographic support usually comprises an undercoat layer for providing an adhesive property with a silver halide emulsion layer and a back layer having properties such as antistatic property and slip property on the opposite surface. Set up.

When providing such an undercoat layer and a back layer,
In recent years, high-speed coating, especially in-line high-speed coating, has been performed in order to improve productivity, but rapid coating drying tends to cause coating failures such as cissing and unevenness. In order to prevent these failures, a method of adding a solvent having a relatively high boiling point to the coating liquid system has been carried out, but it is not a sufficient solution.

A method using a surfactant is also common, but US Pat. Nos. 2,240,476, 3,026,202 and 3,068,
In the case of the low-molecular weight active agents disclosed in No. 101, No. 3,220,847, No. 3,415,649, etc., the amount used is large in order to obtain the effect, and there is a drawback that bleed-out (precipitation) occurs in high humidity. Further, as a surfactant, JP-A-58-200
A method using a fluorine-based activator disclosed in No. 235 is known, but since the fluorine-based activator tends to be oriented on the surface after coating, it is wound into a roll like a photographic support. When the silver halide photographic emulsion layer is applied, it may cause fatalities such as orientation (when an activator is added to the undercoat layer) or transfer (when an activator is added to the back layer). Defects will occur.

[0005]

The present invention has been made to solve the above problems, and the object of the present invention is to:
An object of the present invention is to provide a photographic support having excellent coatability and improved adhesion resistance.

[0006]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that the above object of the present invention is to include a copolymer having a repeating unit represented by the following general formula [I]. It has been found to be achieved by a featured photographic support.

[0007]

[Chemical 3]

In the formula, R ₁ represents a hydrogen atom, a chlorine atom or an alkyl group having 1 to 3 carbon atoms, and R f represents an alkyl group having 1 to 30 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom. Represents an aralkyl group, an aryl group or an alkylaryl group.

X is

[0010]

[Chemical 4]

Represents Here, R ₂ represents an alkyl group having 1 to 100 carbon atoms, an arylene group or an aralkylene group.

L is --O--, --S--, --N (R ₃ )-, --C
O- group, -OCO- group, -SCO- group, -CON (R ₃₎ - group, -SO ₂
- _{group, -N (R 3) SO 2} - _{group, -SO 2 N (R 3)} - represents group, an -SO- group, R ₃ represents an alkyl group having 1 to 4 carbon atoms. p represents 0 or 1.

Y represents a hydrogen atom or an alkyl group having 1 to 24 carbon atoms, an alkenyl group, an aryl group, an alkylaryl group and a group represented by Rf. l is 0 or an integer of 1 to 4,
m represents 5 to 50 and n represents 0 or an integer of 1 to 20.

The present invention will be described in detail below.

In the general formula [I], R ₁ includes a hydrogen atom, a chlorine atom or an alkyl group having 1 to 3 carbon atoms (for example, methyl, ethyl, flopil etc.), and a hydrogen atom or a methyl group is preferable.

Rf represents an alkyl group, aralkyl group, aryl group or alkylaryl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, and among these, perfluoromethyl Group, perfluoroethyl group, perfluoropropyl group, perfluorohexyl group, perfluorooctyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,4,4,5, 5-octafluoroamyl group, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl group, 2,2,2-trifluoroethyl group, 2,2 , 3,3,4,4,
4-heptafluorobutyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, 1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl group , 1,1,2,2-tetrafluoro-2-hydroxyethyl group, p-fluorophenyl group, p-trifluoromethylphenyl group, 3,3,4,5,6-pentatrifluoromethylphenyl group, etc. preferable.

X is

[0018]

[Chemical 5]

Represents Here, R ₂ represents an alkylene group having 1 to 100 carbon atoms, an arylene group or an alkylene group. L is -O- group, -S- group, -N (R ₃₎ - group, -CO- group, -OCO-
Group, -SCO- group, -CON (R ₃₎ - group, -SO ₂ - group, -N (R ₃₎ SO
₂ - group, -SO ₂ N (R ₃₎ - represents group, an -SO- group, R ₃ represents an alkyl group having 1 to 4 carbon atoms (e.g. methyl, ethyl, propyl, butyl, etc.). p represents 0 or 1.

L is 0 or an integer of 1 to 4, preferably 0 or 1.

M is 5 to 50, preferably 5 to 20. n
Is 0 or an integer of 1 to 20, preferably 0 to 10.

The alkyl group having 1 to 24 carbon atoms represented by Y is preferably an alkyl group having 4 to 18 carbon atoms.

Y is, for example, a hydrogen atom, a linear or branched alkyl group such as methyl, ethyl, butyl, dodecyl, tetradecyl or hexadecyl group, an alkenyl group such as oleyl group, an alkylphenyl group such as pentylphenyl group or octylphenyl group. Etc.

The molecular weight of the copolymer used in the present invention is 3,000.
It is 0 to 200,000, preferably 5,000 or more and 50,000 or less.

It is essential that the copolymer used in the present invention has the above-mentioned two comonomers as repeating units, but it may contain a third comonomer as long as the effect of the present invention is not impaired. Good. Examples of the third comonomer include alkyl acrylate (alkyl having 1 to 3 carbon atoms), styrene, ethylene and the like.

The copolymer preferably used in the present invention is a copolymer represented by the following general formula [II].

[0027]

[Chemical 6]

In the formula, R ₁ , Rf, X, Y, 1, m and n have the same meanings as described in the general formula [I].

X: y = 10: 90 to 80:20 (mol%), preferably 20:80 to 50:50.

Next, specific examples of the copolymer used in the present invention will be shown, but the present invention is not limited thereto.

[0031]

[Chemical 7]

[0032]

[Chemical 8]

In applying the compound of the present invention to a photographic support, it is dissolved in water or an organic solvent such as alcohols such as methanol and isopropanol, ketones such as acetone and methyl ethyl ketone, or a mixed system of water and an organic solvent. Or more preferably, it is effective in an organic solvent system, particularly preferably a mixed system of two or more organic solvents having different boiling points.

The addition layer of the compound of the present invention is an undercoat layer or a back layer for coating a silver halide emulsion layer, and the back layer is 2
When it is composed of layers, any of the layers may be used.

The effect of the present invention is most remarkably exerted on the back layer containing various additives such as antistatic agents, matting agents and slip agents. In this case, the compound of the present invention is used as such an additive. It exerts the effect of working so as to obtain good coatability without agglomeration or precipitation during the coating / drying process.

In particular, when the additive is an antistatic agent, the uniformity after coating has an important effect on the antistatic performance.

As the antistatic agent, for example, JP-B-57-560
Ionene type polymers as disclosed in JP-A-59-223736, cross-linked polymers having vinylbenzyl quaternary ammonium salt at the polymer position as disclosed in JP-A-61-223736, JP-B-57-12979. Alumina sol having an electrolyte as disclosed in JP-A-56-143431, or crystalline metal oxide fine particles as disclosed in JP-A-56-143431, or as disclosed in Japanese Patent Application No. 3-306360. Examples thereof include metal oxide sols containing different kinds of metal elements.

Of these, particularly in the case of alumina sol, crystalline metal oxide fine particles, and metal oxide sol containing different metal elements, these antistatic agents are likely to aggregate during coating and drying, so that the compound of the present invention is used. Is effective.

The amount of the compound of the present invention used per 1 m ^{2 of the} photographic support is preferably 0.01 to 3.0 mg, particularly preferably 0.05 to 2.0 mg. The total amount used is preferably 3.5 mg or less.

Substrates applicable to the support of the present invention include polyolefins such as polyethylene; polystyrene,
Cellulose derivatives such as cellulose triacetate; films such as polyester such as polyethylene terephthalate, or baryta papers, synthetic papers, substrates made of sheets of which both surfaces are coated with these polymer films, and the like, and the like are used.

As a method for coating each of the back layer and the undercoat layer containing the compound of the present invention and the layer adjacent to these layers, various known methods such as curtain coating, reverse roll coating, fountain air doctor can be used. Coating, slide hopper coating, extrusion coating, dip coating and the like are used.

The silver halide photographic light-sensitive material to which the support of the present invention can be applied is a normal black-and-white silver halide light-sensitive material (for example, a black-and-white light-sensitive material for photographing, a black-and-white light-sensitive material for X-ray, a black-and-white light sensitive material for printing). Examples of the material include various silver halide light-sensitive materials such as ordinary multilayer color light-sensitive materials (eg color reversal film, color negative film, color positive film, etc.).

[0043]

The present invention will be described in more detail with reference to the following examples, but the embodiments of the present invention are not limited thereto.

Example 1 US Pat. No. 2,271, on cellulose triacetate film
The undercoat shown in No. 228, Example 4 was applied.

Next, on the opposite side, 20 parts of the following composition for the first layer was applied.
It was applied at a volume of ml / m ² and dried at 90 ° C. for 3 minutes.

(Composition for the first layer) Ionene type polymer (below) 3.5 g Ethylene glycol 27 ml Methanol 600 ml Acetone 400 ml

[0047]

[Chemical 9]

20% of the following composition for the second layer is formed on the first layer.
Apply so that the volume becomes ml / m ² and the air temperature is 100 ℃. Overall heat transfer coefficient is 100.
Sample N was dried for 1 minute in a vertical flow of dry air at kcal / m ² · hr · ° C.
o.1-9 were obtained.

(Composition for Second Layer) Diacetylcellulose 5 g SiO ₂ fine particles (average particle size 0.1 μm) 0.7 g Acetone 500 ml Ethyl acetate 500 ml Compounds of the present invention (shown in Table 1) Evaluation of Samples Visual observation was made on the backside coating property. The sample was wound with a tension of 300 g / cm and stored under the condition of 40 ° C. and 80% RH for 14 days, and then the area of the part which was adhered when the sample was peeled off was measured to evaluate the adhesion resistance.

Table 1 shows the evaluation results of the above coating properties and adhesion resistance.

[0051]

[Table 1]

Adhesion Resistance Evaluation Criteria Rank Area Ratio (%) of Adhesive Part A 0-40 B 41-60 C 61-80 D 81 or more The structures of Comparative Compounds II-1 and II-2 are as follows. is there.

[0053]

[Chemical 10]

As is clear from Table 1, it was found that Sample Nos. 1 to 5 using the compound of the present invention showed excellent coatability even with a small amount and had good adhesion resistance.

Example 2 US Pat. No. 2,271,228 on cellulose acetate film
The undercoat shown in No. 4 was applied.

Next, 20 ml of the following composition for the first layer is applied on the opposite side.
/ M ² so that the air temperature is 90 ℃ and the overall heat transfer coefficient is 100kca
It was dried for 1 minute in a vertical stream of dry air of 1 / m ² · hr · ° C.

(Composition for First Layer) Alumina sol As-100 (manufactured by Nissan Chemical Industries, Ltd.) 7.5 g Diacetyl cellulose 7.5 g Acetone 400 ml Methanol 500 ml Dimethylformamide 100 ml Compound of the present invention (shown in Table 2) The first layer The following coating solution for the second layer was applied onto the above so as to be 20 ml / m ² and dried at 80 ° C. for 3 minutes to obtain sample Nos. 10 to 16.

(Composition for Second Layer) Diacetylcellulose 5 g SiO ₂ fine particles (average particle size 3.0 μm) 0.2 g Acetine 500 ml Ethyl acetate 500 ml The coating properties and adhesion resistance of each obtained sample were the same as in Example 1. evaluated. Further, the sample was conditioned at 23 ° C and 20% RH for 24 hours, and then under the same conditions, Kawaguchi Denki's teraohm meter VE-30.
Was used to measure the surface resistivity at an applied voltage of 100V.

The results are shown in Table 2.

[0060]

[Table 2]

As is apparent from Table 2, when the compound of the present invention was not added (Sample No. 16), there was an increase in haze which was considered to be aggregation of the alumina sol, and unevenness occurred. Moreover, although the surface resistivity was inferior for this reason, the sample Nos. 10 to 14 to which the compound of the present invention was added have good coatability and excellent surface resistivity, and also have excellent adhesion resistance. I understood it.

[0062]

According to the present invention, it is possible to provide a photographic support having excellent coating properties and improved adhesion resistance.

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[Procedure amendment]

[Submission date] January 29, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0019

[Correction method] Change

[Correction content]

Represents Wherein R ₂ is table an alkylene group, an arylene group or an alkylene group having 1 to 100 carbon atoms, preferred
It is preferably a methylene group or an ethylene group. L is an -O- group,
-S- group, -N (R ₃₎ - group, -CO- group, -OCO- group, -SCO-
Group, -CON (R ₃₎ - group, -SO ₂ - _{group, -N (R 3) SO 2} - group, -SO
₂ N (R ₃ )-group, represents a -SO- group, preferably -N (R ₃ )-
A group, a —N (R ₃ ) SO ₂ — group, and a —SO ₂ N (R ₃ ) — group. R ₃ represents an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, butyl, etc.). p represents 0 or 1.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

M is 5 to 50, preferably 5 to 20.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

N is 0 or an integer of 1 to 20, preferably
It is 0-10.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction content]

The number average molecular weight of the copolymer used in the present invention is 3,000 to 200,000, preferably 5,000 or more and 50,00.
It is 0 or less.

Claims (1)

[Claims] 1. A photographic support comprising a copolymer having a repeating unit represented by the following general formula [I]. [Chemical 1] [In the formula, R ₁ represents a hydrogen atom, a chlorine atom or an alkyl group having 1 to 3 carbon atoms, and R f is an alkyl group having 1 to 30 carbon atoms, aralkyl having at least one hydrogen atom substituted with a fluorine atom. Represents a group, an aryl group or an alkylaryl group. X is Represents. Here, R ₂ represents an alkyl group having 1 to 100 carbon atoms, an arylene group or an aralkylene group. L is -O- group, -S
- group, -N (R ₃₎ - group, -CO- group, -OCO- group, -SCO-
Group, -CON (R ₃₎ - group, -SO ₂ - _{group, -N (R 3) SO 2} - group, -SO
₂ N (R ₃ )-group and -SO- group are represented, and R ₃ represents an alkyl group having 1 to 4 carbon atoms. p represents 0 or 1. Y represents a hydrogen atom or an alkyl group having 1 to 24 carbon atoms, an alkenyl group, an aryl group, an alkylaryl group and a group represented by Rf.
l is 0 or an integer of 1 to 4, m is 5 to 50, and n is 0 or 1
Represents an integer of 20. ]