JPH11174625A - Manufacture of photographic film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide even coating surface, charge preventing effect and excellent adhesiveness by using a coating liquid containing an acrylic polymer or gelatin and a specified ionic polymer and a specific silane group compound as a hardening agent. SOLUTION: After forming a base coating layer, at least one surface thereof is coated with a coating liquid containing an acrylic polymer or gelatin and ionic polymer having the structure expressed with formula I and single or two ore more mixture of the silane group compound having the structure expressed with formulas II, II. After forming a charge preventing layer, a photosensitive layer is formed. In formula I, R is hydrogen, carboxylic acid or 1-10C alkyl group, R1 is hydrogen or 1-10C alkyl group, R2 is hydrogen or a methyl group, (x), (y) air each positive number 1 or 2 or more, (z) is -phenyl-SO3 -G<+> , etc. In formulas II, R3 is a methyl group or an ethyl group, (n) is a positive number 1-5, A is -Cl-. In formula III, R4 is a methyl group or an ethyl group.

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 (PHOTOGRAPHIC) film for photography or printing, and more particularly to a film having excellent adhesive strength and permanent antistatic performance on at least one surface of the film. Antistatic layer (PERMANENT ANT
The present invention relates to a method for producing a photographic film, which is coated with ISTATICLAYER) and exhibits particularly excellent antistatic properties.

2. Description of the Related Art Conventionally, it has been known that a general synthetic film used for a photographic graphic has a high electric insulating property, so that static electricity is easily generated. 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. Among the prior arts for solving the problem of static electricity generated in such a photographic film, there is a so-called antistatic layer (ANTISTATIC LA).
YER) is coated on a photographic film. For example, U.S. Pat.
No. 25,665 discloses a water-soluble sodium salt of a copolymer of styrene having a sulfo group and a monomer having a carboxyl group (MONOMER), a hydrophobic polymer having a carboxyl group (HYDROPHOBIC), and a hardener (HARDENER). ) And a mixture of water-soluble polyfunctional aziridine (AZIRIDINE) or the like with an antistatic layer coating formulation (COATI).
NG FORMULATION), and U.S. 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, 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 or 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 of treating a film substrate by applying an electric treatment such as CORONA to both sides of the film substrate, or by using a water-soluble acrylic polymer and vinylidene chloride.
After forming a base coating layer by coating a water-soluble mixed solution containing a resin as a main component, at least one surface of an acryl polymer or gelatin and an ionic polymer (IONIC POLYM) having a structure represented by the following Chemical Formula 1
ER) and a coating solution containing a silane-based compound having a structure as shown in the following chemical formulas 2 and 3 alone or as a curing agent, to form an antistatic layer, and then to form a photosensitive layer and the like. The present invention provides a method for producing a photographic film characterized by being produced by:

Embedded image In the above formula, R is hydrogen, carboxylic acid, or C 1 -C 1.
R ₁ is hydrogen or C ₁ to C 1
0 is an alkyl group, R ₂ is hydrogen or a methyl group, x and y are 1 or more positive numbers, and Z is -phenyl-SO ₃ -G ⁺ , -alkyl-NH-CH _2- SO ₃
-G ⁺ , -CO-X- (CH ₂ ) _m -N ⁺ (R ₅ ) ₃ D
⁻ X is -NH- or -O-, m is a positive number of 2 to 4,
R ₅ is hydrogen, methyl or ethyl, D is OH,
Cl or Br.

Embedded image (R ₃ O) ₃ —Si— (CH ₂ ) _n -A In the above formula, R ₃ is a methyl group or an ethyl group;
n is a positive number from 1 to 5

Embedded image (R ₄ O) ₄ —Si In the above formula, R ₄ is a methyl group or an ethyl group.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. As the film substrate used in the present invention, a film 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 (CARB).
(OXYL GROUP), but at least a vinylidene chloride component of 7
0% or more, and the pH of the mixed solution is approximately 5%.
The solid content is not limited to a specific range, but it is advantageous from the viewpoint of workability that the solid 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 ink may be an acrylic polymer or gelatin, an ionic polymer having a structure represented by Formula 1, or a compound selected from the compounds represented by Formula 2 and Formula 3. Or a silane-based curing agent consisting of 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 approximately 8 to 11, and the concentration of the solid content is particularly limited. But not
It is advantageous from the viewpoint of workability that the content be about 0.5 to 10% by weight. Although the silane-based curing agents of formulas 2 and 3 used in the present invention can be added alone, another curing agent liquid (HARD
It is more effective to produce and use ENER SOLUTION) in terms of transparency or smoothness. A specific example of the method for preparing such a curing agent 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 that is a single or a mixture of two or more selected from a compound of Formula 2 and a compound of Formula 3 in a diluent obtained by mixing 0 to 100 weight and 1 to 20 weight of an acid component such as hydrochloric acid, nitric acid, sulfuric acid, and acetic acid. Is added and the mixture is stirred at a temperature of about 30 ° C. or lower for several hours to obtain a curing agent liquid suitable for the present invention. Additives that can be used in the coating solution for forming the antistatic layer include acids, alkalis, alcohols, and wetting agents (WET) in order to adjust pH or improve coating properties.
TING AGENT), a surfactant and the like can be selectively added. The present invention is characterized in that an antistatic layer is formed on one or both surfaces of a film by using a coating liquid having such a composition. This will be described with reference to the accompanying drawings. When the antistatic layer 4 is formed on one surface of the material 1, corona treatment is performed or the antistatic layer 4 is formed on the base coating layer 2,
Antihalation layer (ANTI HALATION L
AYER) 7 and the opposite side is treated with corona or the gelatin sub-layer 3, photosensitive agent layer 5 and protective layer 6 are formed on the base coating layer 2 to produce the photographic film of the present invention. As shown in FIG. 2, when forming an antistatic layer on both surfaces of the film substrate 1, one surface is formed with an antihalation layer 7 on the antistatic layer 4 as in the former, and the opposite surface is formed on the opposite surface. By forming an antistatic layer 4 in place of the gelatin sub-layer 3 and forming a photosensitive layer 5 and a protective layer 6 thereon, the photographic film of the present invention is manufactured. The antihalation layer 7 protects the antistatic layer, maintains the antistatic effect as it is, and curls the film (CURL).
This layer is formed in order to prevent the phenomenon and maintain the balance between both sides. As a binder of such a coating solution, gelatin or acrylic resin is mainly used, and a dye or a matting agent (MATTINGAGENT) is used.
Is selectively contained. In addition, a gelatin sub-layer (GELATINESUB) formed in a layer opposite to the antistatic layer 4
BING LAYER) 3 is a layer that plays a role of supporting a stable photoreaction when the film substrate 1 and the photosensitive agent layer 5 react with light, and is used as a coating liquid for forming the layer. Is a solution composed of a silane-based compound having the structure of Chemical Formulas 2 and 3 and a solvent such as water or an alcohol, which is used as a hardener in a binder made of hydrophilic gelatin and used as an antistatic layer as described above. Use 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 a roughening agent (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 or inorganic particles which 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, and evaluation of various physical properties of films produced therefrom was performed 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 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 coated on a vinylidene chloride copolymer (VINYLIDENECHLOIDE COPO).
LYMER), a 70% vinylidene chloride monomer (MONOMER) component, and a 55% solids sol IXAN W which is a copolymer with monomers and the like.
A50 20cc and ROHM & HUS (ROHM & H
ASS) RHO which is a 44% aqueous solution of acrylic resin
PLEX EMULSIONEXP-3208 20c
c and a wetting agent for improving coating properties (WETTIN)
GAGENT) 3.0 cc and distilled water (DISTILL)
(ED WATER) 1000 cc, and adjust the pH to 6.
Adjusted to zero. This coating solution is coated on both sides of a film substrate so that the wet thickness (WET THICKNESS) is 20 microns,
For 1 minute. In addition, an antistatic layer (PERM
ANENT ANTISTATIC LAYER) as ammonium salt of ethyl methacrylate (AMMO
NIUM SALT OF ETHYLMETHCRY
LATE) and Acrylic Acid Copolymer, INDUNAL ECR71 from INDULOR
10g and 44% of ROHM & HUS acrylic resin
HOULEX EMULSIONONE
P-3208 6cc and triethoxypropylthiolsilane (TRIETHOXYYLPROPYL) as a curing agent
THIOL SILANE) (HULL)
S) DYNASYLAN 3201 in ethanol 2
A mixture of 15 cc of a 0% dissolved solution, 150 cc of distilled water and 100 cc of methanol is mixed with 0.1N NaOH aqueous solution.
H was coated with a coating solution adjusted to 9.3 and dried at 105 ° C. for 60 seconds. At this time, the wet thickness of the coating liquid (WETTHICKNESS) is 2
5 microns. Then, a gelatin sub-layer (GELATINE SUBBIN) is provided on the opposite side of the antistatic layer.
7 cc of a solution prepared by dissolving 20% of DYNASYLAN 3201 from HULS in ethanol with 100 g of distilled water and 5 g of hydrophilic gelatin as GLAYER) and triethoxypropylthiolsilane as a hardener.
Then, 200 cc of methanol is mixed with 0.1 N NaO
H solution to adjust the pH to 9.6,
Dried at 05 ° C for 60 seconds. At this time, the wet thickness of the coating liquid (WET THICKENESS) was set to 25 microns. Then, an antihalation layer was formed on the 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, 50 g of water was added to 100 g of methanol as a hardener solution (HARDNER SOLUTION) used for the antistatic layer, 15 g of a 0.2N aqueous solution of nitric acid was added, and the mixture was stirred for 30 minutes. Ethoxypropylthiol silane, DY from Flus
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 photographic film was produced in the same manner as in Example 1, except that the film substrate was subjected to a corona treatment at 2.5 kW without forming a base coating layer. did.

Example 4 In Example 1, as a curing agent liquid used for the antistatic layer, DYNASYLANE 3201 by Tris and TRIMETHOXY SILA which are triethoxypropylthiolsilane were used.
NE) in the same amount in 20% ethanol
A photographic film was produced in the same manner as in Example 1 except that 5 cc was added.

Example 5 A photoconductor was prepared in the same manner as in Example 1 except that the antistatic layer was formed using a coating solution obtained by adding 2 g of gelatin to the coating solution composition for the antistatic layer. Graphic films were manufactured.

Example 6 In Example 1, an antistatic layer (PE
RMANENT ANTISTATIC LAYER)
Has a molecular weight of 20,000 and a solid concentration (SOL
(IDCONTENT) is 25% and sulfonated styrene (SULFONATEDSTYLENE) is 75% /
Moles of maleic anhydride (MALEICANHYD
(RIDE) is a sodium salt of a copolymer (SODIUM SALT) composed of 25% / mol (NATIONAL STARCH AND AND)
VERSA of CHEMICAL COMPANY
TL-450cc and ROHM & HUS (ROHM & H
ASS) RH which is a 44% aqueous solution of acrylic resin
OPLEX EMULSION EXP-3208 5
cc and DYNASYLAN 3 from HULS, which is triethoxypropylthiolsilane as a curing agent.
10 cc of a curing agent solution obtained by dissolving 201 in ethanol 20%
And 200 cc of distilled water, coated with a coating solution adjusted to pH 9 with 0.1N NaOH aqueous solution, dried at 105 ° C. for 60 seconds to form an antistatic layer, and gelatin sub-layer (GELATINE SUBBI)
NGLAYER), 5 g of hydrophilic gelatin as a curing agent, and DYNASYLAN 3201 manufactured by HULS, which is a triethoxypropylthiolsilane as a hardening agent, are mixed with 0.1N NaOH aqueous solution to adjust the pH to 10, and the mixture is coated at 105 ° C with 60%. A photographic film was manufactured in the same manner as in Example 1 except that the gelatin sub-layer was formed by drying for 2 seconds.

Comparative Example 1 In Example 1, instead of the triethoxypropylthiolsilane solution added to the coating solution used to form the antistatic layer and the sublayer, Cibron (AZIRIDINE) -based compound was used. SYBRON) was prepared in the same manner as in Example 1 except that 4 cc of PFAZ-322 (SYBRON) was added to the coating solution for the antistatic layer and 3 cc to the coating solution of the gelatin sub-layer.

Comparative Example 2 A photographic film was produced in the same manner as in Example 1, except that the base coating layer was not formed.

Comparative Example 3 A photographic film was produced in the same manner as in Example 6, except that the base coating layer was not formed. 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

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Jun La, Kim South Korea, Seoul, Sotsok, Bang Po Dong, 33-503 (72) Inventor Weilpred Bite Germany, Desai, De 06849, Bernese Renbinden-Lin 50 (72) ) Inventor Christop Ross Germany, Harle, DE 06118, Hopberok Sbrik 11 (72) Inventor Detoto Teile, Harle, DE 06120, Germany Dorothey-Eloksleven-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. ), An 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 (6), an acrylic polymer or gelatin as a coating liquid for forming an antistatic layer (4), an ionic polymer having a structure represented by the following chemical formula 1, and a curing agent Photo coating characterized by using a coating liquid containing a single or a mixture of two or more silane compounds having a structure represented by the following chemical formulas 2 and 3. Manufacturing method of traffic for the film. Embedded image In the above formula, R is hydrogen, carboxylic acid, or C 1 -C 1.
R ₁ is hydrogen or C ₁ to C 1
0 is an alkyl group, R ₂ is hydrogen or a methyl group, x and y are 1 or more positive numbers, and Z is -phenyl-SO ₃ -G ⁺ , -alkyl-NH-CH _2- SO _{3
^{- G +, -CO-X- (}} CH 2) m -N + (R 5) 3 D
− Potassium, calcium or magnesium, and X is-
NH- or -O-, m is a positive number of 2 to 4,
₅ is hydrogen, methyl or ethyl, and D is OH, C
1 or Br. Embedded image (R ₃ O) ₃ —Si— (CH ₂ ) _n -A In the above formula, R ₃ is a methyl group or an ethyl group;
n is a positive number from 1 to 5 Embedded image (R ₄ O) ₄ —Si In the above formula, R ₄ is a methyl group or an ethyl group. 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. ), An antistatic layer (4) and an antihalation layer (7) are formed on one side of the film, and the antistatic layer (4), the photosensitive layer (5) and the protective layer are formed on the other side. In producing a photographic film by forming (6), an acrylic polymer or gelatin is used as a coating liquid for forming an antistatic layer (4), and
A coating solution containing an ionic polymer having a structure as described above and a silane-based compound having a structure as represented by Formula 2 or 3 alone or a mixture of two or more as a curing agent. Production method. 3. The method for producing a photographic film according to claim 1, wherein the pH of the coating solution for forming the antistatic layer (4) is in the range of 8 to 11. . 4. The method for producing a photographic film according to claim 1, wherein the concentration of the solid content of the coating solution for forming the antistatic layer (4) is 0.5 to 10% by weight. . 5. The method for producing a photographic film according to claim 1, wherein the photosensitive agent layer (5) is formed using a silver chloride-gelatin type photosensitive solution.