JPH0643510B2 - Material with improved antistatic layer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a material (element) having improved antistatic property.
It is about. More specifically, the present invention relates to a photographic material having an antistatic layer coated with a small coating amount (photogr
aphic element) shows improved physical properties in relation to the photographic layer.

[Prior art]

Many film supports actually used to make photosensitive elements consist of polymeric shaped supports, which have a high dielectric constant and thus tend to become charged during use. There is. This charging is unacceptable as it results in an undesired exposure effect on the photosensitive layer associated with such a support. It is well known to make antistatic compositions containing antistatic agents and other ingredients, and to layer these compositions on a film support during preparation of the photographic material. One such antistatic composition is described by Schastat III in US Pat. No. 4,225,665. A description of the state of the art relevant to this field is given in this example.

While Shyatuth's composition and layers made therefrom are suitable for preventing electrostatic charge in photographic materials, Shchatz suffered from some drawbacks that prevented it from making full use of this system. One of the drawbacks is that the Schutt layer must be coated with a fairly high coating weight, which adds to the cost of coating and also increases the inherent light scattering or fogging in the material. The transparency and usefulness of the photographic material made therefrom is impaired. This haze is especially troublesome in materials where the antistatic layer is not covered by a silver halide emulsion or gelatin layer. Another way of Mr. Siyatto
One drawback is the use of a multi-component system of binder and cross-linking agent in addition to the antistatic agent which results in premature cross-linking reactions prior to coating.

Separately filed by applicant, now withdrawn
Based on US Application No. 691,768 filed January 16, 1985, 1
US Application No. 875,251 filed June 17, 986, US Patent No.
In Miller's application, 4,701,403, an improvement on the Schatt method is described, in which the components are separated and the crosslinker is applied as a separate layer. Miller proposed a composition containing an antistatic agent and a crosslinking agent,
It has been found that when coated as a single layer with or without binder, the physical and electrical durability is reduced. The method described by Miller provides an overall thinner film antistatic coating, prevents premature crosslinking reactions associated with polymeric materials, and provides physical and electrical durability. However, Miller's method requires a two-step coating process, which requires additional investment and operating costs.

It is therefore necessary to have a relatively thin layer of photographic material that provides more durable antistatic properties, improved optical properties, and maintains transparency in the final material made therefrom. To be done.

[Main points of the invention]

According to the invention, (1) a water-soluble, electrically conductive polymer having a functionally bound carboxyl group integrated into the polymer, and (2) at least one hydrogen atom on the carbon atom of the aziridine ring. Is substituted with an alkyl substituent, the alkyl group having 1 to 6 carbon atoms, and the durability of at least one layer consisting essentially of the reaction product with a polyfunctional substituted aziridine compound. The antistatic layer is coated with a conductive polymer.
Provided is a material comprising a molded article of a polymer having an effective carboxyl group on its surface, which has a coating amount of 4.5 mg / dm ² or less based on the weight of (1).

According to another embodiment of the present invention, a polymer film support having effective carboxyl groups on its surface,
A photosensitive layer on the support, and a durable antistatic layer coated on at least one side of the support, the antistatic layer being (1) functionally integrated with the polymer. A water-soluble, electrically conductive polymer having a bonded carboxyl group, and (2) at least one hydrogen atom on a carbon atom of the aziridine ring is substituted with an alkyl substituent, and the alkyl group is 1 to 6 Consisting essentially of a reaction product with a polyfunctional substituted aziridine compound, which has a carbon atom of
Provided is a photographic material which forms an antistatic layer having a coating amount of 4.5 mg / dm ² or less based on the weight of the electroconductive polymer (1) by connecting between the carboxylic acid group and the carboxyl group on the surface of the support. It

[Detailed Description of the Invention]

In carrying out the present invention, preferably an aqueous solution of a water-soluble conductive polymer (1) and the above-mentioned polyfunctional substituted aziridine is prepared, and in order to disperse each component well, a small amount of a wetting agent or a coating agent is added thereto. Is added. This aqueous solution is then applied as a desired antistatic layer onto a support such as fiber, paper, plastic film or the like. For the support or polymer molding, the preferred material is polyethylene terephthalate, which will be referred to herein as (polyester base). The present invention is not limited to the use of polyester bases, but other supports having carboxylic groups available on their surface may be used. For example, a paper support with a plastic surface coating such as polyethylene can be flame treated or reacted to form carboxyl groups on its surface. In fact, the present invention can effectively provide an antistatic layer to any support having surface groups such as carboxyl, hydroxyl, amino or thiol. The base, which is preferably a film, receives the antistatic layer of the present invention for the subsequent coating with another layer, such as a gelatin subbing layer or a photographic emulsion layer.
A suitable undercoat, such as a resin undercoat, is applied. It was surprisingly found that the antistatic layer of the present invention could be an alternative to a gelatin subbing layer. The resin undercoat layer is unnecessary when the base is subjected to flame treatment, for example. Particularly preferred as the electroconductive polymer (1) is a copolymer of sodium salt of styrene sulfonic acid and disodium salt of maleic acid in a ratio of 3: 1 and at the same time, between the support and the above (1). The component (2) which can be linked to form a two-dimensional structure is an alkyl- or dialkyl-substituted polyfunctional aziridine.

Referring now to the drawings, the same reference numerals are used in each drawing, and FIG. 1 is a typical double-sided coated photographic material, in which layer (1) is a protective film; layer (2) ) Is, for example, a silver halide gelatin emulsion layer; layer (3) is a gelatin subbing layer; layer (4) is an antistatic layer of the present invention; layer (5) is a resin subbing layer; and (6) is a polyester base support. is there. A typical example of the illustrated element is a medical X-ray.

FIG. 2 shows a typical one-side coated photographic material, which is used, for example, in the field of graphic arts. In FIG. 2, the layers are from top to bottom: (1) protective film; (2) silver halide gelatin emulsion layer; (3) gelatin subbing layer; (5) resin subbing layer; (6) polyester base support; 4) Antistatic layer of the present invention; and (7) is the antihalation layer described in Chiyo, US Pat. No. 4,585,730, such as Example 1 of this patent.

The antistatic layer is preferably coated and dried and cured during manufacture of the polyester support, as shown in U.S. Pat. No. 2,779,684 to Ares, and Rawlins prior to coating the antistatic layer. U.S. Patent No. 3,567,45
It is preferred to coat a resin subbing layer such as the vinylidene chloride-itaconic acid mixed polymer subbing composition shown in No. 2. When polyethylene terephthalate is made for a photographic support, the polymer is shaped as a film and is coated with Rawlins' mixed polymer subbing composition on one or both sides, then stretched in two directions and then coated with a gelatin subbing layer. It Upon completion of the stretching and coating of the primer composition, it is necessary to remove the tension and strain in the support due to the heat treatment, corresponding to the annealing of the glass. An air temperature of 100 ° C. to 160 ° C. is typically used for this heat treatment, which is referred to as post-stretch thermal relaxation. If necessary, one or both gelatin subbing layers can be replaced by the formulation according to the invention, whereby equipment and heat treatments for the production of the support are used for the coating and the dry curing according to the invention. Sometimes, it can be effective for both productivity and economic purposes.

In a preferred embodiment, the electrically conductive, antistatic polymer (1) is a 3: 1 molar ratio copolymer of the sodium salt of styrene sulfonic acid and maleic acid, measured by gel permeation chromatography (GPC). It has a number average molecular weight of about 20,000. This molecular weight is suitable for rendering it water-soluble and for obtaining a cloud-free transparent coating. Higher molecular weight copolymers are possible if the ratio of styrene sulfonic acid to maleic acid is greater than 3: 1; for example, at this ratio of 9: 1 a useful number average molecular weight of about 70,000 (GP
C). In terms of carboxyl units, a larger amount of electrically conductive styrene sulfonic acid sodium salt is
It serves to balance the ability of the copolymer to be permanently attached to the support through these carboxyl groups and the requirement for antistatic performance.

Preferred polyfunctional substituted aziridine (2) crosslinkers have the formula The pentaerythritol-tri- [β- (N
-Alkyl or dialkyl substituted aziridinyl) propionate], wherein R is alkyl or dialkyl, the alkyl having 1 to 6, preferably 1 to 4 carbon atoms, such as methyl, ethyl, propyl, Butyl, amyl or hexyl or their isomers. The aziridine compound represented by the above formula is preferred. An aziridine compound in which the R substituent is an aryl group of 6 to 10 carbon atoms, such as phenyl or naphthyl, or at least one on the second carbon atom of the aziridine ring.
Aziridine compounds in which one hydrogen atom has been replaced with an alkyl or aryl substituent as described above have not been tested,
It may be useful if an effective amount can be included in the coating solution to provide physical and electrical durability. A particularly preferred methyl-substituted polyfunctional aziridine of this type is a soluble, clear, amber colored liquid with an aziridine content of 5.5 milliequivalents per gram and an aziridine functionality of 2.6. Other multifunctional aziridine curing agents are Such as trimethylolpropane tri- [β- (N-
Alkyl or dialkyl-aziridinyl) propionate, wherein R is as defined above, and Trimethylolpropane-tri- [β- (N-methylaziridinyl) propionate] can also be used, and a polyfunctional aziridine of this type is preferable.

Other polyfunctional substituted aziridines can also be used as long as each component contains at least two crosslinkable groups. Although not limited to any theory, an electrically conductive polymer
The alkyl substituents of the polyfunctional substituted aziridine (2) present with (1) inhibit premature cross-linking reactions, thereby giving a practical "pot life" and further good cross-linking of the coated layers. It is thought to cause

Surfactants or wetting agents may be added to aid in the dispersion of (1) and (2) in water, and in fact this addition is preferred. Fluoro FC made by 3M is preferable.
127, solution of N-ethyl-[(perfluorooctyl) sulfonyl] potassium potassium 50%, ethanol 4% and water 32%; Triton X manufactured by Rohm and Haas
-200, 28% solution of sodium alkylaryl polyether sulfonate; Standapol ES 40 from American Cyanamide, anionic surfactant such as 58% solution of disodium alkyl sulfosuccinate, and Deupon products BCO, α-trimethylaminostearic acid, or Henkel Derifuart 15
1, an amphoteric surfactant such as sodium N-coca β-aminopropionate. Other useful surfactants include sodium lauryl sulfonate, sodium dioctyl sulfosuccinate, sodium octyl phenyl polyether sulfonate, and other sodium alkylaryl polyether sulfonates.

In the preparation of the coating liquid used for preparing the antistatic layer of the present invention, a mixing ratio of 100: 10 is preferable for (1) :( 2), but 100: 4 to 100: 30 by weight. Would also work within the scope of the invention. The antistatic layer is preferably a polyester-based support, which is suitably primed to receive the coating or is subjected to energy treatment such as discharge treatment, followed by a photosensitive layer. And as an intermediate layer. However, the antistatic layer of the present invention will exhibit its effect even when used, for example, as a backing layer (see FIG. 2). A dry coating weight of 4.5 mg / dm ² or less (based on the weight of component (1) in the mixture) is preferred, with a dry weight of 3.8 mg / dm ² or less being particularly preferred.

The antistatic layer of the present invention may contain an additive that does not impair the antistatic property. Typical examples are matting agents, plasticizers, lubricants, surfactants, pigments, and anti-fog agents. Both the antistatic polymer having a carboxyl group and the stabilizing surfactant, if necessary, are of the same charge type, that is, anionic type, and the surfactant may be nonionic or amphoteric type. Thus, the cross-linking reaction can occur without the incompatibility that would occur when the cationic and anionic components were mixed together.

The light-sensitive and / or radiation-sensitive layer useful in the present invention may be any of those commonly used for imaging and reproduction in areas such as graphic arts, printing, medical and information systems and the like. It will be appreciated that the elements made in accordance with the present invention do not have physical defects such as undesired haze and have a reduced tendency to produce electrostatic charges. The manufacturing cost of a structure as described above can be reduced by using a thin single antistatic layer that effectively retains physical and electrical durability. Photopolymers, diazos, bubble imaging compositions and other systems can be used in addition to silver halide. The silver halide photographic emulsion used is a commonly known halide such as bromide, chloride, iodide or dihalide.
Any of species or a mixture of several species can be used. These can have various contents and can be either negative and / or positive. The sensitivity of silver halide is borane, amine, polyethylene oxide,
It can be fortified and stabilized by chemical reagents such as tetraazaindene, benzotriazole, alkali halides, phenylmercaptotetrazole, and gold, mercury and sulfur compounds. In addition,
Phenomenon additive, covering power polymer, surfactant,
Lattice agents, hardeners and other addenda known in the photographic art can be used with the silver halide photographic emulsions. The preferred embodiment of the invention is described in Example 1.

The emulsion of the present invention can be used in a conventional photographic system such as a negative type or a positive type. Therefore, these may contain additives used in the respective systems. For example, when used as a direct positive emulsion, the emulsion can be chemically fogged using a metal such as rhodium or iridium or other chemical fogging agent such as borane, as is well known by those skilled in the art. it can.

EXAMPLES In all examples, this description is not a limitation of the invention and parts and percentages are by weight and the antistatic layer is 0.004 inch 0.10 mm thick polyethylene terephthalate film base. This layer was applied under the conditions shown below using conventional coating equipment. The coverage was adjusted by changing the pressure of the air knife and is shown below. Other tests common to these examples are as follows: Coverage: The coverage of component (1) was measured by Sulfur fluorescence X-rays using a PW 1400 X-ray spectrometer from Phillips.

Cloudy: Measured with a C light source using a haze meter UX10 type manufactured by Gardner.

Surface resistance: Measured at a applied voltage of 500 V at 50% RH, 72 ° F (21 ° C) using a 240A type power source and a 610 type electrometer in a Keithley 6105 type device.

Discharge 1/2 hour: Using a 276A static discharge analyzer from Monroe, applied voltage 160
It was measured at 0 V (initial stage) and 20% RH.

Example 1 The following solutions, representative of the present invention, were prepared by thoroughly mixing the following components: This mixture (Sample 1) has a weight ratio of (1) :( 2) of 10 parts / part.
It is 0:10. For comparison, a known mixture (Sample 2) was prepared from the following components: In sample 2, the ratio of the crosslinking agent (2) to the weight of the carboxyl group-containing polymers (1) and (3) was 100: 10. Both sample solutions then have a normal resin subbing layer on both sides, thickness 0.
Coated on a 004 inch (0.10 mm) polyethylene terephthalate film support. Each sample was then heat relaxed to achieve dimensional stability. Each sample was tested for fog, tendency to develop charging, and physical and electrical durability and the results are shown in Table 1 below: This example demonstrates the utility of the present invention. The sample representative of the present invention shows almost no haze as compared with the samples of the known examples. Although the surface resistance is about the same value, Sample 1 of the present invention has a remarkably high discharge rate, which shows a good antistatic property. When each sample was rubbed circularly 10 times with a water moistened teus, then dried with another teus, no physical damage was observed, and as shown in Table 1 above. In addition, the surface resistance remained substantially unchanged.

Example 2 The same antihalation backing layer was prepared as described in Example 1 of Chiyo U.S. Pat. No. 4,585,730. Sodium polystyrene sulfonate (a conductive polymer) was added to the backing layer in an amount sufficient to make up 1% by weight of the mixture. 2 pieces 0.004 inch thick
Samples of (0.10 mm) polyester film support were prepared. Sample 1 (control) was coated on both sides with a conventional resin subbing layer and a gelatin subbing layer. Sample 2 of the present invention has a conventional resin subbing layer on one side and an antistatic layer of the present invention as prepared in Example 1 above, and a conventional resin subbing layer / gelatin subbing on the other side. Layers and applied. The above-mentioned anti-halation backing layer was applied to the side of Sample 2 on which the antistatic layer was applied, and in Sample 1, one of the resin undercoat layer /
It was applied to the gelatin undercoat layer application side. Both elements were then dried. On the opposite side of both elements a silver halide emulsion layer (see Example 4 of Chiyo U.S. Pat. No. 4,585,730) was coated with a conventional gelatin overcoat. After drying, both samples were tested for propensity to charge by measuring the surface resistance (see Chiyo's patent above), with the results shown in Table 2 below: Table 2 Sample Resistance Values (Ohm / Square) 1 (Control)> 1 × 10 ¹⁸ 2 3.5 × 10 ^{11 The} smaller the value, the better antistatic property is obtained.

Example 3 The following solution representative of the present invention was prepared and 6 inches of water
(152.4mm) air knife pressure, 250 feet per minute (76.2m /
Min), dried and heat relaxed as described in Example 1: The haze, surface resistance, electrical durability and discharge rate were good.

Example 4 A solution of the following composition was prepared and coated as described in Example 3: The haze, surface resistance, electrical durability and discharge rate were good.

The present invention has been described in detail above, but the present invention can be summarized and shown by the following embodiments.

1) (1) a water-soluble, electrically conductive polymer having a functionally bound carboxyl group integrated into the polymer, and (2) at least one hydrogen atom on the carbon atom of the aziridine ring is alkyl-substituted. Substituted with a group, the alkyl group having 1 to 6 carbon atoms, at least one layer of durable antistatic consisting essentially of the reaction product with a polyfunctional substituted aziridine compound The antistatic layer is coated with a layer of a polymer having an effective carboxyl group on its surface, which is a coating amount of 4.5 mg / dm ² or less based on the weight of the conductive polymer (1). Material that consists of.

2) The material according to 1) above, wherein the ratio of (1) to (2) is 100: 4 to 100: 30 based on the weight.

3) The material according to 1) above, wherein the ratio of (1) to (2) is 100: 10 based on the weight.

4) The material according to the above item 1), wherein a hydrogen atom on one carbon atom of the aziridine group of the polyfunctional aziridine is substituted with a methyl group.

5) A polymer film support having effective carboxyl groups on its surface, a photosensitive layer on the support, and a durable antistatic layer coated on at least one side of the support. The antistatic layer comprises (1) a water-soluble, electrically conductive polymer having a functionally bound carboxyl group integrated into the polymer, and (2) at least one hydrogen atom on the carbon atom of the aziridine ring. Substituted with an alkyl substituent, which alkyl group is one having 1 to 6 carbon atoms, consisting essentially of the reaction product with a polyfunctional substituted aziridine compound, wherein the aziridine is ( Based on the weight of the conductive polymer (1) connecting between 1) and the carboxyl group on the surface of the support, 4.5.
A photographic material for forming an antistatic layer having a coating amount of mg / dm ² or less.

6) The photographic material as described in 5) above, wherein the ratio of (1) to (2) is 100: 4 to 100: 30 on the basis of weight.

7) The photographic material as described in the above item 5), wherein the ratio of (1) to (2) is 100: 10 based on the weight.

8) The photosensitive layer is a silver halide photographic emulsion layer.
5) Photographic materials described.

9) The preceding paragraph, wherein the photosensitive layer is a photopolymer composition layer.
5) Photographic materials described.

10) The photographic material as described in 5) above, wherein the support is a polyester film.

11) The photographic material as described in 10) above, wherein the polyester support is polyethylene terephthalate.

12) The photographic material as described in 10) above, wherein the polyester support is resin-coated.

13) The photographic material as described in 10) above, wherein the polyester support has been subjected to energy processing.

14) The photographic material according to the above item 5), wherein the copolymer (1) is a copolymer of styrenesulfonic acid sodium salt and maleic acid disodium salt.

15) The photographic material as described in the above item 5), wherein the coating amount of the antistatic layer is 3.8 mg / dm ² or less based on the weight of the conductive polymer.

16) The photographic material according to the above item 5), wherein a hydrogen atom on a carbon atom of one aziridinyl group of the polyfunctional aziridine is substituted with a methyl group.

17) The photographic material according to the above item 5), wherein a hydrogen atom on a carbon atom of one aziridinyl group of the polyfunctional aziridine is substituted with an ethyl group.

18) The photographic material according to the above item 5), wherein hydrogen atoms on carbon atoms of both aziridinyl groups of the polyfunctional aziridine are substituted with methyl groups.

19) The photographic material as described in the above item 5), wherein the durable antistatic layer is coated on the same side of the support below the photosensitive layer.

20) The photographic material according to the above item 5), wherein the durable antistatic layer is coated on the side of the support opposite to the photosensitive layer.

21) The photographic material as described in the above item 5), wherein the photosensitive layer and the antistatic layer are coated on each side of the support.

22) A polyethylene terephthalate support having on its surface an effective carboxyl group and a layer of a photosensitive silver halide or photopolymer coated on one side, and a support below the photosensitive layer. It consists of a durable antistatic layer coated above, which comprises (1) a copolymer of styrene sulfonic acid sodium salt and maleic acid disodium salt in a 3: 1 molar ratio, and (2) an aziridine ring. 1 hydrogen atom on a carbon atom of is substituted with an alkyl substituent, which alkyl group is one having 1 to 4 carbon atoms, which is essentially a product of the reaction with a polyfunctional substituted aziridine compound. Is configured, where this aziridine is
The (1) and the carboxyl groups on the surface of the support are connected to form an antistatic layer having a coating amount of 3.8 mg / dm ² or less based on the weight of the copolymer (1), and the component (2 ) Is a photographic material which can range from 4 to 30 parts per 100 parts by weight of (1).

23) The durable antistatic layer is independently coated on the side of the support opposite to the side bearing the photosensitive layer 22).
Described photographic material.

24) The second durable antistatic layer is coated on the side of the support opposite to the side bearing the photosensitive layer 22).
Described photographic material.

25) The photographic material as described in 1) above, wherein a surfactant or a wetting agent is present in the coating film for antistatic layer.

26) The photographic material as described in the above item 22), wherein a surfactant or a wetting agent is present in the antistatic layer coating film.

[Brief description of drawings]

The accompanying drawings show cross-sections of photographic materials of the present invention. FIG. 1 shows a photographic material having a photographic emulsion coated on both sides of a support in which at least two antistatic layers of the invention are used. FIG. 2 shows a photographic material coated on one side with a photographic emulsion and uses only one antistatic layer of the invention on the back side of the support.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location H05F 1/02 K 7028-5G // C08L 67:00 H05K 9/00 X 7128-4E

Claims (3)

[Claims] 1. A water-soluble, electrically conductive polymer having (1) a functionally bound carboxyl group integrated into the polymer, and (2) at least one hydrogen atom on the carbon atom of the aziridine ring. Is substituted with an alkyl substituent, the alkyl group having 1 to 6 carbon atoms, and the durability of at least one layer consisting essentially of the reaction product with a polyfunctional substituted aziridine compound. Is coated with a conductive antistatic layer, and this antistatic layer is based on the weight of the electroconductive polymer (1) and has a coating amount of 4.5 mg / dm ² or less. A material consisting of a molded product. 2. A polymer film support having effective carboxyl groups on its surface, a photosensitive layer on the support,
And a durable antistatic layer coated on at least one side of the support, the antistatic layer being (1) water-soluble with functionally bound carboxyl groups integrated into the polymer. And (2) at least one hydrogen atom on the carbon atom of the aziridine ring is substituted with an alkyl substituent.
It is essentially composed of the reaction product of a polyfunctional substituted aziridine compound, which has 6 carbon atoms, wherein this aziridine connects the (1) and the carboxyl group on the surface of the support. A photographic material for forming an antistatic layer having a coating amount of 4.5 mg / dm ² or less based on the weight of the conductive polymer (1). 3. A polyethylene terephthalate support having effective carboxyl groups on its surface and coated on one side with a layer of a photosensitive silver halide or a photopolymer, and below the photosensitive layer. It consists of a durable antistatic layer coated on the support of
(1) a copolymer of styrene sulfonic acid sodium salt and maleic acid disodium salt in a 3: 1 molar ratio, and (2) one hydrogen atom on a carbon atom of an aziridine ring is substituted with an alkyl substituent. The alkyl group is essentially composed of the reaction product of a multifunctional substituted aziridine compound, which has 1 to 4 carbon atoms, wherein the aziridine is (1) and on the surface of the support. 3.8 mg based on the weight of the copolymer (1) linked to the carboxyl groups
A photographic material which forms an antistatic layer with a coverage of less than / dm ² and component (2) can range from 4 to 30 parts by weight per 100 parts of (1).