JPH11143022A - Manufacture of photographic film having antistaticness - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the photographic film coated with an antistatic layer uniform on the surface and superior in antistaticness and adhesiveness by using a coating solution containing an acrylic polymer or a gelatin and a specified anionic polymer and a specified silane compound. SOLUTION: The photographic film is coated with a base coating layer and then, coated with the coating solution containing the acrylic polymer or gelatin and the anionic polymer represented by formula I and as a hardening agent a mixture of the silane compounds represented by formulae II and II to form the permanently antistaticized layer. In formulae I-II, each of R and R1 is a methyl or ethyl group; R2 is an II atom or a 1-5C alkyl group; R3 is an H atom or a carboxylic acid or 1-10C alkyl group; M is a Na or Li atom or the like; Z is a -phenyl-sulfonate or -alkylaminomethyl sulfonate anion; A is a -Cl or -SH group or the like; and each of (x) and (y) and (n) is an integer.

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the production of a photographic or printing photographic (PHOTOGRAPHIC) film, and more particularly to a permanent antistatic layer having at least one surface having excellent permanent antistatic performance. (PERMANENT ANTISTATIC
LAYER) and a method for producing a photographic film exhibiting performance particularly excellent in antistatic properties.

2. Description of the Related Art Heretofore, it has been known that a synthetic film used for a photographic graphic has a high electric insulating property and easily generates static electricity. In particular, static electricity generated during a photographic process in which a photosensitive layer such as silver halide (SILVER HALIDE) absorbs and reacts to light may cause problems such as adsorption of dust or foreign substances, uneven printing, and reduced adhesiveness. This can cause poor quality, for example, if it occurs or the final photographic product is out of focus. In the prior art for solving the problem of static electricity generated in the photographic film, a method of coating a so-called antistatic layer on the photographic film has been proposed. For example, U.S. Pat. No. 4,225,665 discloses a sodium salt of a copolymer of styrene having a sulfo group and a monomer having a carboxyl group (MONOMER) which is soluble in water and a hydrophobic salt having a carboxyl group (HYDR).
OPHOBIC) polymer material and hardener (HARDE)
NER) and water-soluble polyfunctional aziridine (AZIRID)
INE) or the like to form a coating formulation of an antistatic layer (COATING FORMULATI).
ON), and US Pat. No. 4,701,403 discloses a sodium salt of a copolymer obtained by polymerization of styrene having a sulfo group and a monomer having a carboxyl group, which is a water-soluble sodium salt and a carboxyl group. A method has been proposed in which a mixture of a hydrophobic polymer having a group and the like is first coated and dried, and then a polyfunctional aziridine is coated thereon to suppress the generation of static electricity.

However, when the antistatic layer is coated as in the former case, there is a problem that it is difficult to obtain a sufficient antistatic effect and a uniform coating surface, and as in the latter case, it is multifunctional. When using an aziridine compound, during the manufacturing process of the coating liquid,
There is a problem that the coating surface is easily cured even by a weak heat and the coating property is deteriorated, resulting in an uneven coating surface. The present invention has been devised to solve the above problems, and provides a photographic film coated with an antistatic layer having a uniform coating surface and an excellent antistatic effect and adhesion. It is the purpose.

SUMMARY OF THE INVENTION The present invention relates to a method for treating both surfaces of a film substrate by using an electric treatment such as CORONA, or by using a water-soluble acrylic polymer and vinylidene chloride (VINYLIDENE CHLORID).
E) After forming a base coating layer by coating a water-soluble mixed solution containing a resin as a main component, an acrylic polymer or gelatin and an anionic polymer having a structure represented by the following chemical formula (I) are formed on at least one surface. After forming a permanent antistatic layer by applying a coating solution containing a silane-based compound having the structure represented by the following chemical formulas (II) and (III) alone or as a curing agent, or a mixture of two or more, a photosensitive layer and the like are formed. Provided is a method for manufacturing a photographic film characterized by being formed and manufactured. [Chemical formula I] In Chemical Formula _{II] (RO) 3 -Si- (} CH 2) n -A [ Formula _{III] (R 1 O) 4} -Si ( the formulas, R and _{R 1} is a methyl or ethyl group, _{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, and M is sodium, lithium, potassium,
A calcium or magnesium ions, Z is - phenyl -SO ₃ - or - alkyl -NH-CH2 And x, y, and n are positive numbers. )

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. As the filter film substrate used in the present invention, a film or the like obtained by modifying a natural substance such as a synthetic polymer film or a cellulose derivative film having optical properties usable for printing or for photography can be used. Polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) or triacetate cellulose (TAC) are particularly suitable for photographic applications. In the present invention, a hydrophobic film and a hydrophilic gelatin layer are formed by performing corona treatment on both surfaces of such a film substrate or coating a water-soluble mixed solution containing an acrylic polymer and vinylidene chloride resin as main components. Alternatively, the adhesion with the antistatic layer is improved. The vinylidene chloride resin used at this time includes a carboxyl group (CARBOX).
(YL GROUP), but at least 70% of vinylidene chloride component
The pH of the mixture is preferably about 5 to 1
It is preferably about 0, and the solid content is not limited to a specific range, but it is advantageous in terms of workability that the content is approximately 1 to 10% by weight. On the other hand, the antistatic layer, which is a feature of the present invention, is a laminated portion introduced to solve problems that occur during the process, such as generating static electricity in the film and attracting dust or causing sparks. As described above, the coating liquid used to form the polymer is selected from an acrylic polymer or gelatin, an anionic polymer having a structure such as Formula I, and compounds represented by Formula II and Formula III. A silane-based curing agent comprising a single or a mixture of two or more, water and other additives,
At this time, 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. is there. The silane-based curing agents of formulas I and II used in the present invention can be added alone, but can be added to another curing liquid (HA
It is more effective to manufacture and use RDENER SOLUTION) in terms of transparency or smoothness. A specific example of a method for preparing such a curing liquid is that 100 parts by weight of alcohol such as methanol or ethanol is added to one part of water.
A silane-based curing agent, which is a mixture of 0 to 100 weight and 1 to 20 weight of an acid component such as hydrochloric acid, nitric acid, sulfuric acid and acetic acid, or a mixture of two or more selected from a compound of formula II and a compound of formula III Is added at a temperature of about 30 ° C. or lower for several hours to obtain a curing liquid suitable for the present invention. Additives that can be used in a coating solution for forming an antistatic layer include acids, alkalis, alcohols, and wetting agents (WE) in order to adjust pH or improve coating properties.
TTING AGENT), a surfactant and the like can be selectively used. The present invention is characterized in that an antistatic layer is formed on one side or both sides of a film using a coating solution having such a composition, and this will be described with reference to the accompanying drawings. When the antistatic layer 4 is formed, the antistatic layer 4 is formed on the base coating layer 2 by corona treatment, an antihalation layer (ANTI HALATION LAYER) 7 is formed, and the opposite surface is corona treated. Alternatively, a photographic film of the present invention is manufactured by forming a gelatin sub-layer 3, a photosensitizer layer 5 and a protective layer 6 on a base coating layer 2, and as shown in FIG. When the antistatic layer is formed on the antihalation layer 7, the antihalation layer 7 is formed on the antistatic layer 4 similarly to the former.
Is formed on the opposite surface, an antistatic layer 4 is formed instead of the gelatin sub-layer 3, and a photosensitive agent layer 5 and a protective layer 6 are formed thereon, whereby the photographic film of the present invention is manufactured. You. The antihalation layer 7
Is a layer formed to protect the permanent antistatic layer, maintain the antistatic effect as it is, prevent the curl phenomenon of the film (CURL) phenomenon, and maintain the balance on both sides, and the binder of such a coating liquid is mainly Gelatin or acrylic resin is used, which optionally contains a dye or a matting agent. Also, a gelatin sub-layer (GELATINE SUBBING LA) formed on the side opposite to the permanent antistatic layer 4
YER) 3 is a layer that plays a role of supporting a stable photoreaction when the film substrate 1 and the photosensitizer layer 5 react with light, and a coating liquid used for forming the layer is used as a coating liquid. And a silane compound having the structure of formulas (II) and (III) used for the antistatic layer and a solvent such as water or an alcohol, as described above, which is usually made of hydrophilic gelatin as a binder and as a hardener. Use the prepared solution. The photosensitive agent layer 5 is formed of a silver halide-gelatin photosensitive solution (GELATIN-SILVER HALID) generally used for photographics.
E PHOTOSENSITIVE EMULSIO
N) to protect the photosensitive layer 5 and to protect the photosensitive layer 5 using a coating liquid containing a matting agent (PROTECTING LAY).
ER) 6 is formed. The matting agent used in the coating solution for the antihalation layer 7 or the protective layer 6 is such that the antihalation layer 7 or the protective layer 6 has a roughness (R)
OUGHNESS) to prevent the sticking phenomenon between the films and the scratch (SCRATCCH), and perform functions such as imparting a sufficient coefficient of friction to the film when applied to a high-speed automatic printing process. At this time, as the matting agent, organic particles or inorganic particles that are insoluble in water and have a particle size of about 5 μm or less can be used, and specific examples include polystyrene or organic matting agent. There is a plastic bead (BEAD) having excellent transparency such as polymethacrylate, and inorganic particles such as alumina, silica, calcium carbonate, barium sulfate, magnesium oxide, and germanium oxide can be used as the inorganic matting agent. Hereinafter, the present invention will be described more specifically based on Examples and Comparative Examples. Various physical properties of the films produced in the following examples were evaluated by the following methods. The coating film on which the adhesive coating solution has been sufficiently dried is measured for 3 m using a cross cut tester (CROSS-CUT TESTER) manufactured by BYK-Gardner.
At a distance of m, a scratch was formed to a size of 3 cm x 6 cm without damaging the film substrate. After that, the adhesive tape was instantaneously removed, and the area remaining on the film substrate without being attached to the tape was expressed in% to evaluate the adhesive strength. After the measurement film was left for 1 hour under the condition of a surface resistance of 23 ° C. and a relative humidity of 60%, the measurement was performed by applying an applied voltage of 500 V using a surface resistance measuring device model R-503 manufactured by Kawaguchi Japan.

Example 1 A 100 micron thick polyethylene terephthalate film was used as a base film, a vinylidene chloride monomer (MONOMER) component was 80%, an itaconic acid (ITACONIC ACID) monomer component was 10%, and an acrylic resin was used. Acid (ACRYLIC
ACID) Copolymer having 10% monomer component (COID)
20% of a 40% aqueous solution of POLYMER) and 44% aqueous solution of an acrylic resin of ROHM & HASS (ROHM & HASS).
EXP-3208 15cc and a wetting agent for improving coating properties (WETTING AGENT) 4.5c
c and distilled water (DISTILLEDWATER) 100
0 cc was mixed and the pH was adjusted to 6.5. This coating liquid is coated in a wet thickness (WET THICKNES).
Both sides of the base film were coated so that S) became 12 μm, and dried at 110 ° C. for 1 minute. Moreover,
Permanent antistatic layer (PERMANENT ANTISTA
(TIC LAYER) has a molecular weight of 20.000 and a solid content (SOLID CONTENT) of 25%
Sulfonated styrene (SULFONATED S
(TYRENE) is 75% mol and maleic anhydride (MALEIC ANHYDRIDE) is 25% mol. Sodium salt of the copolymer (SODIUM S)
ALT) National Starch (NATIONA)
L STARCH AND CHEMICAL COM
PANSA) 50 cc VERSA TL-4 and 44% aqueous solution of acrylic resin from ROHM & HASS (ROHM & HASS), RHOPLEX EMUL
5 cc of SION EXP-3208 and triethoxypropylthiolsilane (TRIETHOXY) as a curing agent
L PROPYL THIOLSILANE (HULS) DYNASYLAN 3201 dissolved in ethanol at a concentration of 20% was mixed with 10 cc of a hardener solution and 200 cc of distilled water, and mixed with 0.1N NaOH aqueous solution.
H was adjusted to 9 and the coating liquid was coated to 10
Dry at 5 ° C. for 60 seconds. Then, on the opposite side of the permanent antistatic layer, a gelatin sub-layer (GELATINE SUBB) is provided.
ING LAYER), 5 g of hydrophilic gelatin and triethoxypropylthiolsilane (TRI)
ETHOXYL PROPYL THIOL SILA
NE) DYNASYLA of HULS
N 3201 and pH with 0.1N NaOH aqueous solution
To 10 and dried at 105 ° C. for 60 seconds. At this time, the wet thickness of the coating liquid (WET THICKENESS) was set to 25 microns. Subsequently, an antihalation layer was formed on the permanent antistatic layer, and a silver chloride-gelatin photosensitive layer and a protective layer were formed on the gelatin sub-layer by a conventional method, to produce a photographic film.

Example 2 In Example 1, a mixture obtained by adding 50 g of water to 100 g of methanol, 15 g of 0.2N-nitric acid aqueous solution and stirring for 30 minutes was used as a hardener solution (HARDNER SOLUTION) for the permanent antistatic layer. Fluethoxy DY, a triethoxypropylthiolsilane
A photographic film was manufactured in the same manner as in Example 1 except that a curing agent liquid obtained by adding 30 g of NASYLANE 3201 was used.

Example 3 A film for photography was produced in the same manner as in Example 1, except that the film substrate was subjected to a corona treatment at 24 kW without forming a base coating layer.

Example 4 In Example 1, triethoxypropylthiolsilane, DYNASYLANE 3201 by Tris and TRIMETHOXY SILA, which are triethoxypropylthiolsilanes, are used as the curing agent liquid for the permanent antistatic layer.
NE) in the same amount in 20% ethanol
A photographic film was produced in the same manner as in Example 1 except that 0 cc was added.

Example 5 Example 1 was repeated except that the pH of the coating solution was adjusted to 10 with 0.1N NaOH aqueous solution during the preparation of the coating solution for the permanent antistatic layer.
A photographic film was produced in the same manner as described above. [Comparative Example 1] A photoconductor was manufactured in the same manner as in Example 1, except that a base coating layer containing vinylidene chloride copolymer as a main component was not formed on a polyethylene terephthalate film having a thickness of 100 microns. Graphic films were manufactured. The physical properties of the films obtained in Examples and Comparative Examples were measured and are shown in Table 1 below.

[Table 1]

As can be seen from the above Examples and Comparative Examples, when a photographic film is manufactured according to the present invention, it has excellent antistatic properties and excellent adhesive strength as compared with existing films. Usefulness such as possession can be obtained.

[Brief description of the drawings]

FIG. 1 is an exemplary view showing a configuration of a photographic film according to the present invention.

FIG. 2 is another exemplary view showing a configuration of a photographic film according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Film base material 2 Base coating layer 3 Gelatin sub-layer 4 Antistatic layer 5 Photosensitizer layer 6 Protective layer 7 Antihalation layer

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 125/18 C09D 125/18 127/06 127/06 133/02 133/02 139/00 139/00 183/04 183/04 (72) Inventor Jun La, Kim South Korea, Seoul, Sotsook, Bang Po Dong, 33-503 (72) Inventor Weilpred Bite Germany, Desai, De 06849, Bernese Renbindenlin 50 (72) Inventor Christop Ross Harle, De 06118, Germany, Hopberok Subrik 11 (72) Inventor Detoto Teile Harle, De 06120, Germany Dorothey-Eloxleben-Escha 13

Claims (5)

[Claims] A base coating layer (2) in which both surfaces of a film substrate (1) are subjected to corona treatment or coated with a water-soluble mixed solution containing a water-soluble acrylic polymer and vinylidene chloride resin as main components. ), A permanent antistatic layer (4) and an antihalation layer (7) are formed on one side of the film, and a gelatin sub-layer (3), a photosensitizer layer (5) and a protective layer are formed on the other side. In producing a photographic film by forming the layer (6), an acrylic polymer or gelatin is used as a coating liquid for forming the permanent antistatic layer (4) and an anionic polymer having a structure represented by the following chemical formula (I). As a polymer and a curing agent, a coating liquid containing a silane-based compound having a structure represented by the following chemical formulas (II) and (III) alone or as a mixture of two or more is used. A method for producing a photographic film having an antistatic property. [Chemical formula I] In Chemical Formula _{II] (RO) 3 -Si- (} CH 2) n -A [ Formula _{III] (R 1 O) 4} -Si ( the formulas, R and _{R 1} is a methyl or ethyl group, _{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, and M is sodium, lithium, potassium,
A calcium or magnesium ions, Z is - phenyl -SO ₃ - or - alkyl -NH-CH ₂ And x, y, and n are positive numbers. ) 2. A base coating layer (2) in which both surfaces of a film substrate (1) are subjected to corona treatment or coated with a water-soluble mixed solution containing a water-soluble acrylic polymer and vinylidene chloride resin as main components. ) Is formed, a permanent antistatic layer (4) and an antihalation layer (7) are formed on one side of the film, and on the other side, the antistatic layer (4), the photosensitive agent layer (5) and the protective layer are formed. In producing a photographic film by forming the layer (6), an acrylic polymer or gelatin and an anionic resin having a structure represented by the above formula (I) are used as a coating solution for forming the permanent antistatic layer (4). As a polymer and a curing agent, a coating solution containing a silane-based compound having the structure represented by the chemical formulas (II) and (III) alone or as a mixture of two or more is used. A method for producing a photographic film having an antistatic property, characterized by comprising: 3. The antistatic photographic graphic according to claim 1, wherein the pH of the coating liquid for forming the permanent antistatic layer (4) is in the range of 8 to 11. Film production method. 4. The antistatic photo according to claim 1, wherein the solid content of the coating solution for forming the permanent antistatic layer (4) is 0.5 to 10% by weight. Manufacturing method of graphic film. 5. The method for producing an antistatic photographic film according to claim 1, wherein the photosensitive agent layer (5) is formed by using a silver chloride-gelatin photosensitive solution.