JPS5845248A - Coating composition - Google Patents

Abstract

PURPOSE:A composition to be applied to a photograph constituting layer, having improved stability of a coating solution, obtained by blending a carboxyl group- containing hydrophilic polymer with colloidal silica and polyvinyl pyrrolidone. CONSTITUTION:A carboxyl group-containing hydrophilic polymer, preferably a copolymer of >=4C ethylenic unsaturated copolymerizable monomer and maleic anhydride, is blended with colloidal silica obtained by dispersing ultrafine particles (particle diameters of 5-60mmu) of silicic anhydride into a dispersion medium consisting essentially of water and polyvinyl pyrrolidone (preferably a molecular weight of 8,000-400,000) in a weight ratio of (1:0.001)-(1:0.150). The composition has the total solid concentration of the individual components of 1.0-10wt% and has a pH of <=9. In mixing, the aqueous solution of the colloidal silica is pre-blended with the aqueous solution of the polyvinyl pyrrolidone, and preferably the blend is added to the aqueous solution of the hydrophilic polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel coating composition, and more particularly to an antistatic coating composition with improved coating liquid stability.
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However, insulating supports have been problematic in that static electricity accumulates in an undesired manner on the supports. tallate film,) 9 acetic acid cellulose film%
Hydrophobic supports are well known, such as films such as /IJ styrene film sl recarbonate film, and resin-coated paper made of a paper substrate coated on both sides with a film-forming resin, often a 4-lyolefin resin. Furthermore, it is well known that static electricity can be prevented by providing an antistatic layer on an insulating support.

However, although it is possible to prepare antistatic compositions that can be coated onto a support, it can be very difficult to combine antistatic properties with other desirable physical properties. .

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Furthermore, it is suitable for a photographic material consisting of a hydrophobic support and a photographic constituent layer provided on the support (for example, a photographic emulsion layer, a protective layer, a subbing layer, an Atsuk coat layer, etc., and a combination layer thereof). Preparing antistatic compositions is difficult due to the rigorous physical properties required of such materials.
9 It has become even more complex. An advantageous antistatic composition suitable for photographic materials comprising an insulating support is one obtained by copolymerizing an ethicine-based unsaturated copolymerizable monomer having carbon a4 or more, such as styrene, with maleic anhydride. A coating layer containing a water-soluble polymer compound, P-type silica, and a curing agent as main components is known. Specifically, there is a description in JP-A-55-32009, for example.

This coating layer has the following advantages.

Kana p is an excellent mourning thing. First, the rolling and coating process, which is a single coating layer, is simple. Second, since the coating layer adheres well to the hydrophobic support and hardens, photographic materials made of hydrophobic supports equipped with the coating layer do not suffer from problems such as film peeling during processing. I never wake up. Thirdly, because the coating layer has excellent antistatic properties, the photographic material comprising the hydrophobic support provided with the coating layer does not suffer from problems due to the accumulation of static electricity. Fourthly, it is a coating layer that does not have any adverse photographic effects. Point 1 as mentioned above: Although this coating layer has excellent properties, it has become clear that it has a more serious problem.

That is, by applying a single layer to an antistatic composition that can be coated on an insulating support, antistatic properties can be obtained.
In order to provide multi-purpose functions such as adhesion, photographic suitability, and other curl-fat retention properties, hydrophilic d9-mer and colloidal silica, which also have a cal-I group at q#, are often present. At times, there is a serious problem in that the stability of the coating solution deteriorates and coating solution components tend to settle, separate, agglomerate, etc. For this reason, it has been desired to develop an antistatic coating composition with excellent coating liquid stability and multipurpose functions.

Accordingly, an object of the present invention is, first, to provide a coating composition with excellent stability and antistatic properties. Second, it provides an antistatic coating composition for photographic constituent layers that has good coating stability and has multipurpose functions in a single layer, and therefore facilitates the production of superior photographic materials comprising hydrophobic supports. It is about making it possible. Other objects, features, and advantages of the present invention will be apparent from the following description.

As a result of intensive studies by the inventors, the purpose of the present invention is (@)
It is composed of a hydrophilic polyY-t<b>colloidal silica having a car-xyl group and (C)/snylpyrroline, and (J):=*a-P-type silica: (C )
The composition ratio of poly-nylzerorin is 1:O, OO1~l
: o, 150. To be more specific, in the present invention, if the composition ratio of (b) colloidal silica to (c) $txs, P4P is l:o, 1 or less than 001, the effects of the present invention cannot be obtained.

If the composition ratio is 1:O, 150 or more -r@, the stability of the coating liquid deteriorates again, and the effects of the present invention cannot be obtained.

As the hydrophilic 4-limer having a carousel group used in the practice of the present invention, various types can be used. In particular, a water-soluble polymer compound or a salt thereof obtained by copolymerizing an ethylenically unsaturated copolymerizable monomer with a carbon content or higher and maleic anhydride is advantageously used. In addition, gelatin and gelatin derivatives, I-lyacrylamide having a carxyl group, mono-C-nyl alcohol having a carxyl group, and ethylenically unsaturated copolymerizable monomers with a carbon level or higher and maleic anhydride. With a copolymer of? Various kinds of products such as water-soluble processed products of sodium chloride or salts thereof can be used.

A water-soluble polymer compound or a salt thereof obtained by copolymerizing an ethylenically unsaturated copolymerizable monomer with a carbon content or higher and maleic anhydride, which is particularly advantageously used in carrying out the present invention, has a carbon content of α or higher. -Olefins, alkyl-elethers.

It is obtained by hydrolyzing a copolymer of an ethylenically unsaturated copolymerizable monomer such as styrene and maleic anhydride, optionally with an alkali such as sodium hydroxide, potassium hydroxide, or ammonia.

A copolymer of an ethylenically unsaturated copolymerizable monomer and maleic anhydride and a method for producing the same are disclosed in U.S. Patent No. 2,0
It is described in No. 47,398, etc.

Preferred ethylenically unsaturated copolymerizable monomers include α-oletuin, alkyl gel ether, styrene, and more preferably tL<a α-olefin having 5 or more carbon atoms, and alkyl having 3 or more carbon atoms. There is an alkyl-nyl ether with styrene. Further, the molecular weight of the ethylenically unsaturated copolymerizable monomer having 4 or more carbon atoms and the maleic anhydride copolymer is preferably 2,000 to 150,000. Specific examples of water-soluble polymeric compounds obtained by copolymerizing an ethylenically unsaturated copolymerizable monomer having 4 or more carbon atoms with maleic anhydride or their bases include inbutylene, 1-pene, etc. Butyl vinyl ether t+ is a solution obtained by hydrolyzing a copolymer of styrene and maleic anhydride with an alkali such as sodium hydroxide or potassium hydroxide. Examples include reaction products.

The colloidal silica used in the practice of the present invention is mainly composed of ultrafine particles of silicic anhydride (810) using water as a dispersion medium.
e (average particle size 6-60 mμ) A colloidal solution dispersed in water. In addition, the dispersion medium is generally water, but methanol or the like may be used in some cases.Also, the colloidal solution contains an alkaline component for the purpose of colloid stabilizer. A commercially available P-type silica preferably used in the present invention is Snowtex manufactured by Nichichi Kagaku.

Although various molecular weights and viscosities of the vinyl ♂ and viscosity used in the practice of the present invention can be used, those having a molecular weight of about 8,000 to 400,000 are useful. Mori, Gaff (G, A, F
) PVP K-30, PVP K-6
0, PVP K-90 is available.

In a preferred embodiment of the present invention, a preferred embodiment of incorporating L pylori P into the coating composition is to mix predetermined amounts of an aqueous solution of colloidal silica and an aqueous solution of L pylori P in pre-mixing, The mixture has hydrophilic properties that promote carxyl groups! Although it is preferable to add it to an aqueous solution of -1, the present invention is of course not limited to these embodiments.

The concentration or usage amount of each component in the coating composition used in carrying out the present invention is substantially determined by the coating method, required physical properties such as antistatic properties, additives in the coating composition, etc. Although not particularly limited, there is a useful range of the total solid content concentration of each component (,), (b), and (c) from 1.0 weight S to 10 weight H. Further, it is desirable that the - of the coating composition be 9.0 or less, preferably 7.0 or less.

It is preferable to include another type of antistatic agent in the antistatic coating composition of the present invention so that the antistatic ability of the coating composition can be more markedly exhibited. Preferred antistatic agents include cellulose sulfate alkali metal salts such as (species name), Ori♂-2 (trade name, manufactured by Six River Paper Co., Ltd.), Keko Stats) 6120 (trade name, manufactured by Sanyo Chemical Industries, Ltd.) /9 Alkaline salts of styrene sulfonic acid, sodium polyacrylates (e.g., sodium salts of polyacrylic acid, polymethacrylic acid, poly-alpha-ethyl acrylic acid, etc.),
Examples include alkali salts of polymerizable acrylic acids and acrylic acid copolymers, such as potassium 4-lyacrylate and sodium salts of acrylic acid and methyl acrylate copolymers. The amount of these antistatic agents to be used depends on the composition of the coating composition in the present invention (for example, composition/type of 9mer, coating amount of support).

Although it varies depending on the coating composition (e.g.) and the type of antistatic agent, it is preferable that the coating amount on the support is in the range of 0.01 Vwl to 3 Vwl. In addition to the water-soluble I remer used in the present invention, various I remers may be contained in combination within a range that does not impair the effects of the present invention. Examples of these remers include 4-lipinyl alcohol, 4-lyacrylic acid fP, starch or derivatives thereof, and cellulose derivatives.

Furthermore, the coating composition of the present invention may contain various matting agents. The matting agent is effective in eliminating adhesion between supports having coating layers made of the composition of the present invention, between photographic materials, or between objects that come into contact with the fins. These matting agents include water-insoluble inorganic or organic compound fine particles +1;
Particle size is 0.2μ to 6μ (0.5 to 3a in %)t″r
! Examples of inorganic compounds include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum ζium dioxide, nonlium sulfate, calcium carbonate, kaolinite clay, and glass powder.
Wear.

Examples of organic compounds include water-dispersible vinyl polymers such as methyl lyacrylate, methyl methacrylate, lystine, styrene and divinylbenzene copolymer, lysinyl acetate, I Examples of cellulose derivatives such as lyethylene carzenate and lyatrafluoroethylene! It is preferable to use starch grains such as cellulose and ethyl cellulose. These matting agents can be used in combination with different types of substances, if necessary.

The coating composition of the present invention may contain various additives. As a hardening agent, JP-A-55-6
As a surfactant, hardeners having two or more ethylene groups or linear dalidyl ether groups in molecules described or exemplified in No. 9139, Anionic surfactants such as ester salts, nonionic surfactants such as ?4-2, alkylene oxy-P compounds, az) acids 114*7t
Ampholytic surfactants such as esters of /sulfonic acids and aminoalols, fluorine-based surfactants as exemplified in JP-A No. 50-G) 9529, etc., as fluorescent brighteners, bone rI3
Compounds described or exemplified in 4δ-2 Yo068, JP-A-54-94318, etc., and copolymers with other ethylene group-containing monomers such as acrylic esters and -dyl esters as film property improvers. (J) a latex consisting of a copolymer of an ene monomer, a latex consisting of a copolymer of ene-based monomers, and a latex modified with xylene.

The coating composition of the present invention can be applied to one or both sides of a support using various coating methods! Wear.

At that time, a glow discharge occurs on the surface of the support.

It is preferable to apply the coating after performing other surface activation treatments such as electron impact, flame treatment, surface roughening, ultraviolet irradiation, and ozone oxidation. The coating can be performed using a squeeze coater, a spray coater, a flake coater, a gravure coater, an air knife coater, a slide hook coater, or a combination thereof.

Drying after application can be carried out by various methods such as hot air, infrared rays, heated R2 ears, and microwaves.

Furthermore, when applying the coating composition of the present invention to a support, the coating amount of the hydrophilic polymer having Cal I xyl ester is 0.01 to 101/
v? There is a useful range f, but preferably αl & so ~ convex,
There is a range of OIi coins. The coating amount of colloidal P-type silica is usefully in the range of 0.0111/rrl to 1011/lri, but preferably O,l 11/11 to 6
．． There is a range of 0 sq. Furthermore...

4S Vinyl Loli? The coating is applied in an appropriate amount commensurate with the location of the Colloy P silica.

Various types of hydrophobic supports can be used in the present invention, such as synthetic paper such as lysolo♂lene and lystyrene, cellulose acetate, cellulose nitrate, polyethylene terephthalate, and vinyl paper. Films such as acetate, 4-lystyrene, 4-lystyrene, 4-lycarnates, 9-, α-olefin polymers, especially 4-lystyrene, lyso-pyrene, ethylene-butene, etc., containing 2 to 10 carbon atoms. Advantageously, paper or the like is used, which is electrified with In-Limer. These thermoplastic resin films, round wires, 4 lyolefin resin layers contain white additives such as titanium oxide, zinc oxide, Merck, and calcium carbonate; Pigments and dyes such as violet violet, fast iolet, manganese violet, etc., dispersants of fatty acid metal salts such as zinc stearate, calcium stearate, and calcium palmitate 1. , stabilizers, antioxidants, and antistatic agents that are mixed into resins.

Additives such as plasticizers, lubricants, fluorescent agents, and ultraviolet absorbers may also be added.

The coating composition of the invention is advantageously used in the preparation of photographic materials by applying it to photographic constituent layers. Such photographic constituent layers include a photographic emulsion layer, a protective layer, a subbing layer, an intermediate layer between emulsion layers, an anti-halation layer or a filter layer, a UV absorption layer containing an ultraviolet absorber, a silver Coatings of the present invention include coating layers for salt diffusion transfer, coating layers provided on the back side of the support, that is, the side of the support opposite to the photographic emulsion layer, and combinations thereof. The composition is advantageously applied in particular to coat layers and subbing layers. Photographic materials to which the coating composition of the present invention can be applied include various types of photographic materials such as complex salt photographic materials, diazo type photographic materials, bubble-forming photographic materials, and photopolymerizable photographic material bottles. It is useful to apply to silver salt photographic materials, especially silver halide photographic materials. Furthermore, silver halide photographic materials to which the present invention is effective include silver halide black and white photographic materials, silver halide black photographic materials,
Multilayer silver tetragenide color photographic materials, photographic elements for diffusion transfer methods, direct positive silver chloride photographic materials.

For general photographic paper, typesetting photographic paper, and copy photographic paper.

There are no particular restrictions on the type or use of printing materials, and the photographic constituent layers of such silver halide photographic materials may contain chemical sensitizers such as hypo, noble metal sensitizers such as gold salts, platinum, etc. agents, contrast enhancing agents such as hexahalogenorhodium complexes, hexahalogenorhodium complexes, nucleic acid decomposition products, JP-A-50-14792δ, JP-A No. 51-107
Mercazoto heterocyclized metals, color sensitizers, stabilizers, antifouling agents, cazolers for color photography, hardening agents, non-diffusible sialium dihydroxyl 4-benzene compounds, hydroquinone as described in Onishikke No. 129. , Methyl High P■ Quinone, Phenidone and other halogenated scissors developing agents, coating aids, fogging agents, direct? It can contain additives for direct positive photographic emulsions such as dyes for dyes, dye developers, and physical development nuclei for photographic elements for fine powder transfer.

Next, examples will be described in order to explain the present invention more specifically.

[Example 6 Example 1] A coating composition having the formulation shown in Table 1 was prepared as follows.

A 251 aqueous solution of styrene-maleic anhydride copolymer (trade name Mafourin M8-25, manufactured by Daido Kogyo ■) 80J9 and a 201 aqueous solution of colloidal silica (trade name Snowtex C)
1 (manufactured by Nissan Chemical ■) 315I and 25.2 g of an aqueous solution of δ-chi of 1-rivinylpyrrolidone (trade name: PvPK-90, manufactured by GAF) (in this case, the composition ratio of colloidal silica: polyvinylpyrroli-P) is 1:0.02*%)
Add. Furthermore, 10 of the compound (1) represented by the following formula f
- Add 60 oc of methanol solution and 14 I of aqueous solution of sodium P-decylbenzenesulfonate. Then, add water to adjust the total volume to 1000II (separately for comparison).

A coating composition is prepared without the addition of colloidal silica and/or L pylori P).

The coating composition thus prepared was used as a coating solution for Nonotsu Coat, and was coated on the back side of 9-polyethylene coated paper with a coating amount of 10% (moisture) f. Apply and dry.

The used ethylene-coated paper is made of low-density polyethylene containing titanium dioxide (10% by weight of polyethylene), an appropriate amount of dispersant, and a blue tint (the polyethylene before adding pigment has a density of 0.9211A and a melt index of 5) as a sizing agent. 0.4 weight of ketene dimer for Norruzo, cationized starch of 2 weight for Nordi as a dry strength agent, and A
Schiff 1wt carboxy-modified Isenyl alcohol,
Polyamide P/glup 0.4 wt. as a wet strength agent
A photo paper with a basis weight of 16011/d consisting of a 1:1 mixture of hardwood bleached clarato pulp and softwood bleached sulfide pulp containing a 4-hydrohydrin resin and an appropriate amount of fluorescent whitening agent was prepared in advance. After corona discharge treatment, it is coated with extra-VZ to a thickness of 30μ, and the back side of the blade is coated with low-density FR polyethylene (density 0.92, melt index δ) and high-density polyethylene (density 0.9).
As with the surface, the surface was coated with a 1:1 mixture of 6C, Melt Index). nine,
The surface of the ethylene film is completely flat, so-called a greasy surface, while the image quality of the ethylene film with the back surface is that of a matte surface.

The surface of the ethylene-coated paper coated with these layers was subjected to electrical discharge treatment, and then the silver chlorobromide gelatin emulsion containing the yellow coupler and its protective layer were extruded.
A silver tetragenide color photographic material was prepared by coating method 1 and drying.

The stability of the coating solution for the /sec;-t layer was evaluated by the method described below.

[Evaluation of stability of coating solution for layer stage] Take the same amount of each coating solution into a test tube, store it in a constant temperature bath at 40°C for 1 day, and then observe the condition of the coating solution. Evaluate the stability. At that time, the evaluation criteria are: ○ mark (& good), Δ mark (fairly good),
1 x mark (not allowed) was displayed.

In addition, the round can sample obtained as described above was heated at 50°C and 60°C.
After being stored in a constant temperature and humidity chamber for one day, it was evaluated using the method f described below. At that time, the evaluation standard for the antistatic performance of the Nonotsu coat layer is the value 1, and the me value of the back coat layer.
The evaluation criteria for retouchability and photographic suitability are indicated by O (good), Δ (slightly good), and X (unsatisfactory).

[Evaluation of the antistatic performance of the coating layer], 20°C,
The surface resistivity of the sample at 35tIIIRH is 1cm.
The measurements were made using electrodes with a length of locm placed at a distance of .

[Evaluation of the readability of the back coat layer] Write with pencils of different hardness, observe the recording state on the surface, and judge the effectiveness.

[Photography aptitude]

The photographic emulsion layer and the dtsukbu 1 layer were overlapped, rolled into a roll, and stored in a constant temperature and humidity bath at 50°C and 80°RH for 2 days, followed by color development (30°C).

5 minutes), - Bath bleach-fix treatment and fog judgment.

The results obtained are shown in Table 2.

As can be seen from Table 2, in the case of a coating layer without =roidal silica (&(3), Na(4)), instability of the coating solution is not caused, but the pencilability is poor and the electrification is poor. There is a problem with poor prevention performance.

Also, even if there is P-type silica, poly-nyl tq
vP yf)lIRhCoating layer (1'k(2)) In the case of O, there is a problem with poor stability of the coating liquid.

However, the coating layer (&(1)) in the present invention shows good results in all evaluation criteria, and has excellent antistatic performance, good interwoven writing ability, photographic suitability, and good coating liquid stability. It can be clearly seen that this is a coating composition.

[Example 2] In the arrangement of coating liquid 1 of Example 1, the composition of polyvinyl vinyl silica (9)% was adjusted so that the composition ratio of cotetraid silica:polyvinyl vinyl pyriP was as shown in Table 3. Six coats were applied in the same manner as in Example 1 except that the amount was changed.

As a result, colloidal silica: Polypier pylori ryo
The stability of coating compositions with a composition ratio of 1:0.001 to 1:050'1% was good1, but the stability of coating compositions with other composition ratios was poor11. The utility of the present invention is well understood.

In Example 1 of Table 3, instead of polyvinylpyrrolidone PVP K-9Q manufactured by GAF, I
Example 1 was carried out in exactly the same manner as in Example 1, except that ribinylpyrrolidone PVPK Begen and FVPK-■ were used, and the same results as in Example 1 were obtained.

Claims (1)

[Claims] It is composed of colloidal silica and (c) It is ♂ Nilze ■ Ridone, and (b); Roy P-like silica: (
C)! The composition ratio of 1N, 9♂nylpyrrolidone is l:cl
A coating composition characterized in that the ratio is ool~1:0.150.