KR19990018541A - Method for manufacturing photographic film having excellent antistatic property - Google Patents

Abstract

The present invention relates to a process for producing a film for photographic purposes such as photographic use or printing, and aims to provide a film having improved antistatic properties and adhesiveness as compared with existing products.

The present invention is characterized in that a permanent antistatic layer is formed by using a coating solution containing an anionic polymer and a silane compound having a specific structure as a coating liquid for forming a permanent antistatic layer on a photographic film, The photographic film produced by the method is particularly useful for photographic use or printing because of its excellent antistatic properties and adhesiveness.

Description

Method for manufacturing photographic film having excellent antistatic property

More particularly, the present invention relates to a permanent antistatic film having excellent adhesion to one side of the film and having a permanent antistatic property. The present invention relates to a process for producing a film for photographic or photographic printing, LAYER

) Coated on the surface of the photocatalyst film, thereby exhibiting excellent antistatic properties.

Conventional synthetic films used for photographic purposes are known to have a high electrical insulating property, which makes it easy to generate static electricity. Particularly, static electricity generated during a photographic process in which a photosensitive layer such as a silver halide absorbs light reacts to cause problems such as adsorption of dust and foreign matter, non-uniformity of printing, deterioration of adhesiveness, The product is poorly focused and causes poor quality.

As a prior art for solving the problem of static electricity occurring in such a photographic film, there have been proposed methods of coating an antistatic layer on a photographic film. For example, in US Patent No. 4,225,665, styrene A water-soluble polymer as a sodium salt of a copolymer of a carboxyl group and a monomer having a carboxyl group (MONOMER), a hydrophobic (HYDROPHOBIC) polymer having a carboxyl group, and a water-soluble polyfunctional aziridine as a crosslinking agent (HARDENER) In US Pat. No. 4,701,403, a sodium salt of a copolymer obtained by polymerization of a styrene having a sulfonic acid group and a monomer having a carboxyl group is disclosed as a water-soluble and a hydrophobic Of polymeric materials, etc. After coating and drying, by coating a polyfunctional aziridine of the water-soluble thereon it proposed a method of suppressing the generation of static electricity.

However, when an antistatic layer such as an electron is coated, there is a problem that it is difficult to obtain a sufficient antistatic effect and a uniform coating surface, and when the multifunctional aziridine compound is used as in the latter case, There is a problem that the coating surface becomes uneven due to easy crosslinking and poor coating property.

It is an object of the present invention to provide a photographic film coated with an antistatic layer having uniform coating surface and excellent antistatic effect and adhesion.

1 is an exemplary view showing a constitution of a film for photographic purposes according to the present invention

2 is a view showing another example of the constitution of the film for photographic purposes according to the present invention

Description of Reference Numbers of Major Parts in the Drawings

1: Film substrate

2: Base coating

3: Gelatin sublayer

4: Antistatic layer

5: Photosensitizer layer

6: Protective layer

7: Anti-halation layer

The present invention is characterized in that the base substrate is formed by applying an electric treatment such as CORONA on both sides of a film substrate or by coating a water-soluble mixed liquid containing a water-soluble acrylic polymer and a vinylidene chloride resin as a main component, A coating liquid containing an acrylic polymer or gelatin and an anionic polymer having a structure represented by the following formula (I) and a silane compound having a structure represented by the following formulas (II) and (III) as a crosslinking agent or a mixture of two or more thereof is applied to the surface of the permanent antistatic layer And then forming a photosensitive layer or the like on the photoresist layer.

(RO) ₃ - Si - (CH ₂ ) _n - A

(R < ₁ > O) ₄ -Si

(Wherein R and R ₁ are methyl or ethyl, R ₂ is hydrogen or an alkyl group having 1 to 5 carbon atoms, R ₃ is hydrogen, a carboxylic acid or an alkyl group having 1 to 10 carbon atoms, M is sodium, Potassium, calcium or magnesium ion, Z is -phenyl-SO ₃ ^- or -alkyl-NH-CH ₂ -SO ₃ ^- , A is -Cl, -SH, -NH ₂ or , And x, y, and n are integers)

Hereinafter, the present invention will be described in detail.

As the film substrate used in the present invention, a synthetic polymer film having optical properties which can be used for printing or photographic use, a film modified with a natural substance such as a cellulose derivative film, and the like can be used. Of these, polyethylene terephthalate (PET ) And polyethylene naphthalate (PEN) or triacetate cellulose (TAC) are particularly suitable for photographic applications.

In the present invention, the adhesion between the hydrophobic film and the hydrophilic gelatin layer or the antistatic layer is improved by corona treatment on both sides of the film base, or by coating a water-soluble mixture liquid containing an acrylic polymer and a vinylidene chloride resin as a main component Respectively. The vinylidene chloride resin used at this time is preferably a copolymer with a compound having a carboxyl group (CARBOXYL GROUP), but it is preferable that the vinylidene chloride component is at least 70% or more. The pH of the mixed solution is preferably about 5 to 10, Although the content of the solid content is not limited to a specific range, it is advantageous from the viewpoint of workability that it is approximately 1 to 10% by weight.

Meanwhile, the antistatic charge, which is a feature of the present invention, is a lamination part which is introduced to solve the problems that occur during a process of generating static electricity in the film to attract dust or cause sparks, Is composed of an acrylic polymer or gelatin, an anionic polymer having a structure represented by the formula (1), a silane crosslinking agent consisting of a mixture of two or more selected from the compounds represented by the formulas (2) and (3), water and other additives, In this case, the pH of the coating liquid is preferably in the range of about 8 to 11, and the concentration of the solid content is not particularly limited, but is preferably in the range of about 0.5 to 10 wt%.

The silane crosslinking agents of the formulas (1) and (2) used in the present invention may be added alone, but it is more effective in terms of transparency and smoothness to make a separate solution. Specifically, 10 to 100 parts by weight of water and 1 to 20 parts by weight of an acid component such as hydrochloric acid, nitric acid, sulfuric acid and acetic acid are mixed with 100 parts by weight of alcohol such as methanol or ethanol, 5 to 100 parts by weight of a silane crosslinking agent selected from the group consisting of a compound represented by the general formula (2) and a compound represented by the general formula (3) is added and the mixture is stirred at a temperature of about 30 DEG C or lower for several hours to obtain a crosslinking solution suitable for the present invention .

As an additive which can be used for a coating solution for forming an antistatic layer, an acid, an alkali, an alcohol or a wetting agent, a surfactant, and the like may be optionally added to improve the pH control and the coating property.

In the present invention, an antistatic layer is formed on one side or both sides of a film using a coating solution having such a composition. Referring to FIG. 1, In the case of forming the antistatic layer 4, an antistatic layer 4 is formed on the corona treatment or the base coat layer 2 to form an antihalation layer 7, A photographic film according to the present invention is prepared by forming a gelatin sublayer 3, a photosensitive agent layer 5 and a protective layer 6 on a coating layer 2, The antistatic layer 4 is formed on the antistatic layer 4 on one side and the antistatic layer 4 is formed on the other side of the antistatic layer 4 in place of the gelatin sublayer 3, Photoresist on top A film for photographic purposes according to the present invention is produced by forming a layer 5 and a protective layer 6. [

The anti-halation layer 7 is a layer formed to protect the permanent antistatic layer and to maintain the antistatic effect as it is and to prevent the curl of the film to maintain the balance of both surfaces, Gelatin or an acrylic resin is mainly used, and a dye or a matting agent is selectively contained therein.

The gelatin sublayer 3 formed on the layer opposite to the permanent antistatic layer 4 is formed of a material such that the film substrate 1 and the photosensitive layer 5 are supported by a support The coating liquid used for forming the coating layer is usually composed of a hydrophilic gelatin as a binder and a silane-based compound having a structure of the formulas (2) and (3) used as an antistatic layer as described above as a cross- Use a solution composed of a solvent such as water or alcohol.

The photosensitizer layer (5) (GELATINO-SILVER HALIDE PHOTOSENSITIVE EMULSION), which is generally used for photographic printing. In order to protect the photosensitive layer 5, a coating liquid containing a matting agent is used to form a protective layer (6).

The matting agent used for the coating solution of the anti-halation layer 7 or the protective layer 6 provides a roughness to the anti-halation layer 7 or the protective layer 6, (SCRATCH), and provides a sufficient friction coefficient required for the film when applied to a high-speed automatic printing process. Wherein the matting agent may be organic or inorganic particles insoluble in water and having a particle size of about 5 microns or less. Specific examples of the organic matting agent include plastic beads (BEAD) having excellent transparency such as polystyrene or polymethacrylate. The inorganic matting agent includes alumina, silica, calcium carbonate, barium sulfate, magnesium oxide, germanium oxide Inorganic particles can be used.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. Various physical properties of the films prepared herein were evaluated according to the following methods.

Adhesion

The coated film, from which the coating liquid was sufficiently dried, was measured with a cross-cut tester (CROSS

-CUT TESTER) at 3 mm intervals to prevent damage to the substrate film 3 cm x 6 cm

On the surface of the scratched film, use a test adhesive tape to measure 2.5 cm x 5 cm

After the adhesive tape is completely peeled off, the adhesive tape is momentarily peeled off

Evaluate the adhesive strength by showing the area remaining in the film in%

Respectively.

Surface resistance

The measurement film was allowed to stand for 1 hour under conditions of a relative humidity of 60% at 23 DEG C,

Measured by application of an applied voltage of 500 V using the Model R-503, a surface resistivity meter

Respectively.

(Example 1)

A 100 micron thick polyethylene terephthalate film was coated with a vinylidene chloride monomer (MO) with a vinylidene chloride copolymer (VINYLIDENECHLORIDE COPOLYMER)

(20%) of a 40% aqueous solution of a copolymer (COOMOLYMER) having 80% of the monomer component (NOMER), 10% of the ITACONIC ACID monomer component and 10% of the monomer component of the acrylic acid (ACRYLIC ACID) 15 cc of RHOPLEX EMULSION EXP-3208, a 44% aqueous solution of acrylic resin, and 4.5 cc of a wetting agent and 1000 cc of distilled water were mixed to adjust the pH to 6.5. The coating solution was coated on both sides of the substrate film so that the wet thickness (wet thickness) became 12 microns and dried at 110 DEG C for 1 minute. A permanent antistatic layer was formed thereon with 75 mol% of sulfonated styrene having a molecular weight of 20,000 and a solids content of 25% and 25 mol% of maleic anhydride (MALEIC ANHYDRIDE) The sodium salt of the copolymer (SODIUM SALT), NATIONAL STARCH AND CHEMI

5 cc of RHOPLEX EMULSION EXP-3208, which is an aqueous solution of 44% of acrylic resin of ROHM HASS Co., Ltd., VERSA TL-4 of CAL COMPANY, and 5 g of TRIFETHOXYL PROPYL THIOL SILANE HUL

-S) DYNASYLAN 3201 in 20% ethanol was mixed with 10 cc of a crosslinking agent solution and 200 cc of distilled water were mixed, and the coating solution was adjusted to pH 9 with 0.1 N NaOH aqueous solution, followed by drying at 105 ° C for 60 seconds. At this time, the wet thickness of the coating liquid (wet thickness) was 25 microns. On the opposite side of the permanent antistatic layer, 5 g of hydrophilic gelatin as a gelatin sublayer (GELATINE SUBBING LAYER) and 20 g of a crosslinking agent DYNASYLANE 3201 of Hulsusa as a crosslinking agent were dissolved in 20% 6 cc, distilled water 50 cc and methanol 250 cc were mixed and adjusted to pH 10 with 0.1 N NaOH solution and dried at 105 ° C for 60 seconds. At this time, the wet thickness of the coating liquid (wet thickness) was set to be 25 microns.

Next, an anti-halation layer was formed on the permanent antistatic layer, and a silver chloride-gelatin photosensitive layer and a protective layer were formed on the gelatin sublayer by a conventional method to prepare a photographic film.

(Example 2)

In Example 1, 50 g of water was added to 100 g of methanol as a crosslinking agent used in the permanent antistatic layer, 15 g of a 0.2N-nitric acid aqueous solution was added, and the mixture was stirred for 30 minutes. To the resulting mixture was added DYNASYLANE of triethoxypropylthiol silane 3201 as a crosslinking agent solution was used in place of the crosslinking agent solution obtained in Example 1 to prepare a photographic film.

(Example 3)

A photographic film was produced in the same manner as in Example 1, except that the film substrate was subjected to corona treatment at 2.4 kW without forming a base coating layer in Example 1.

(Example 4)

A cross-linking agent solution obtained by dissolving 20% of DYNASYLANE 3201 and trimethoxysilane (TRIMETHOXY SILANE) in the same amount of triethoxypropylthiol silane as a crosslinking agent used in the permanent antistatic layer in Example 1 in ethanol was added , A photographic film was produced.

(Example 5)

A photographic film was prepared in the same manner as in Example 1 except that the pH of the coating solution was adjusted to 10 with 0.1 N NaOH aqueous solution to prepare a coating liquid for the permanent antistatic layer in Example 1.

(Comparative Example 1)

A photographic film was prepared in the same manner as in Example 1, except that a base coat layer composed mainly of a vinylidene chloride-based copolymer was not formed on a 100-micron thick polyethylene terephthalate film in Example 1.

The physical properties of the films obtained in the above Examples and Comparative Examples were measured and are shown in Table 1 below.

Surface Resistance (Ω) Adhesion (%) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 5.4 x 10 ⁹ 1.8 x 10 ¹⁰ 3.9 x 10 ¹⁰ 1.0 x 10 ¹¹ 6.3 x 10 ⁹ 9.1 x 10 ⁹ 10010098100850

As can be seen from the above Examples and Comparative Examples, when the photographic film is produced according to the present invention, it is more excellent in antistatic property than the existing film, and also has the advantage of having a high adhesive strength.

Claims (5)

A base coating layer 2 is formed on both sides of the film substrate 1 or by coating a water-soluble mixture liquid containing a water-soluble acrylic polymer and a vinylidene chloride-based resin as main components, In forming the gelatin sublayer 3, the photosensitive agent layer 5 and the protective layer 6 on the other side by forming the antistatic layer 4 and the anti-halation layer 7, (4), an anionic polymer and a crosslinking agent having a structure represented by the following formula (I), a silane compound having a structure represented by the following formulas (2) and (3), or a mixture of two or more thereof By weight based on the total weight of the coating liquid. (Formula 1) (2) (RO) ₃ - Si - (CH ₂ ) _n - A (Formula 3) (R < ₁ > O) ₄ -Si (Wherein R and R ₁ are methyl or ethyl, R ₂ is hydrogen or an alkyl group having 1 to 5 carbon atoms, R ₃ is hydrogen, a carboxylic acid or an alkyl group having 1 to 10 carbon atoms, M is sodium, Potassium, calcium or magnesium ion, Z is -phenyl-SO ₃ ^- , A is -Cl, -SH, -NH ₂ or , And x, y, and n are integers) A base coating layer 2 is formed on both sides of the film substrate 1 or by coating a water-soluble mixture liquid containing a water-soluble acrylic polymer and a vinylidene chloride-based resin as main components, The antistatic layer 4 and the antihalation layer 7 are formed on the other side of the antistatic layer 4 and the photoconductive layer 5 and the protective layer 6 are formed on the other side of the antistatic layer 4, (4), an acrylic polymer or gelatin, an anionic polymer having the same structure as the above formula (I) and a crosslinking agent, or a mixture of two or more of the silane compounds having the structure of the above formulas (2) and (3) A method for producing a film for photographic purposes The method according to claim 1 or 2, wherein the pH of the coating solution for forming the permanent antistatic layer (4) is in the range of 8 to 11 The process for producing a photographic film according to claim 1 or 2, wherein the solid concentration of the coating liquid for forming the permanent antistatic layer (4) is in the range of 0.5 to 10 wt% The process for producing a photographic film according to any one of claims 1 and 2, wherein the photosensitive layer (5) is formed using a silver chloride-gelatin sensitizer