JP2000303039A - Supporting member and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a supporting member which exhibits assured tight adhesiveness by forming on a support a layer of an adhesive containing a polymer having a specified or lower weight-average molecular weight. SOLUTION: Provided is a supporting member prepared by forming a layer of an adhesive containing at least 50 wt.% polymer having a weight-average molecular weight of at most 50,000 and a film-hardening agent on a support (e.g. one made of a polyester). The adhesive layer is applied in a coating weight of, desirably, 5-100 mg/m2. To improve the adhesiveness of the support, it is subjected to e.g. treatment with a plasma at atmospheric pressure. When the substrate is subjected to a plasma discharge treatment with a mixed gas comprising an inert gas and a polar-group-imparting gas selected from among nitrogen, oxygen, hydrogen, or the like, atmospheric pressure or near, its surface energy, as compared with the initial value, is lowered by at least 3 mN/m by the nonpolar component and is increased by at least 10 mN/mm by the polar component. A polymer for forming the adhesive layer is exemplified by gelatin, casein, or polyvinyl alcohol. The film-hardening agent is exemplified by 1,2-bis(vinylsulfonylacetamide)ethane or glycidyl ether.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a support and a method for producing the support, and more particularly, to a support having improved adhesion between the support and a coating layer provided on the support, and to a method for manufacturing the support. It relates to a manufacturing method.

[0002]

2. Description of the Related Art Conventionally, as a method of adhering different types of films (layers) which are not familiar with each other, a method of providing an adhesive layer therebetween, that is, a primer method has been used.

For example, in the case of a support for a photographic light-sensitive material, strong adhesion between an undercoated resin-based support and a photographic constituent layer having gelatin as a main binder is required. It causes various troubles. In particular, when the film of the photographic constituent layer is peeled off during development or the like, not only the product itself is spoiled, but also a trouble of the developing machine is caused.

[0004] Various methods have heretofore been attempted as a method for enhancing the adhesion between the support and the photographic component layer. For one thing,
As disclosed in US Pat. No. 3,475,193, after a substrate is subjected to an energy treatment such as a discharge treatment or an ultraviolet treatment, an undercoating first layer is applied, and further an undercoating second layer made of a hydrophilic polymer is applied. There is a method in which a photographic constituent layer is provided thereon. However, there is a disadvantage that the production cost is increased because two undercoat layers are required. For this reason, attempts have been made to further increase the undercoat layer.

For example, as disclosed in US Pat. No. 4,135,932, there is a method of performing a corona discharge treatment before and after coating an undercoat layer. However, due to the principle of corona discharge, there are drawbacks such as that it is difficult to uniformly treat the entire surface of the substrate and that affinity with a hydrophilic polymer such as gelatin as a main binder constituting a photographic component layer is not always good.

Further, as a method for improving the uniformity of these treatments and the affinity with gelatin, Japanese Patent Application Laid-Open No. 8-19428
As described in Japanese Patent Publication No. 6, a method has been devised in which a substrate is subjected to vacuum plasma treatment, and then an undercoat layer containing gelatin as a main component is provided.

However, vacuum plasma processing requires a vacuum chamber, so equipment costs are high, and there is an unstable operation in the initial stage of operation peculiar to a vacuum system, and the substrate processed from the start of processing to stable operation. Has the disadvantage that it may have to be discarded.

Accordingly, processing can be performed uniformly and stably while continuously transporting a long substrate, and can be processed with good affinity for gelatin, which is the main binder of the photographic constituent layer, and at a low cost and excellent productivity. A processing method was required.

Further, in the case of a support for a photographic light-sensitive material which is processed with a high pH developing solution, a support capable of securing stronger adhesiveness has been required.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a support capable of securing a strong adhesiveness. Another object of the present invention is to provide a method for producing a support which is uniform, stable, inexpensive and has high productivity while continuously transporting a long substrate.

[0011]

The object of the present invention has been attained by the following constitutions.

1. On a substrate, a weight average molecular weight of 50,0
A support having an adhesive layer containing a polymer of 00 Mw or less.

2. A support having, on a substrate, an adhesive layer containing gelatin in which the viscosity of a 10% aqueous solution of gelatin alone at 20 ° C. is 0.2 Pa · s or less.

3. The support according to the above 1 or 2, wherein the substrate has been subjected to energy treatment.

4. The support according to the above item 3, wherein the energy treatment is a plasma treatment.

5. The support according to the above item 4, wherein the plasma treatment is an atmospheric pressure plasma treatment.

6. The support according to the above item 5, wherein the gas used for the atmospheric pressure plasma treatment is a mixed gas of an inert gas and a reactive gas.

[7] The inert gas contains 50 argon gas.
7. The support according to the above 6, wherein the support is contained at a pressure of not less than%.

8. The support according to the above item 6 or 7, wherein the reaction gas is nitrogen, oxygen, carbon dioxide or hydrogen.

9. The surface energy of the substrate subjected to the plasma treatment is reduced by 3 mN / m or more in the non-polar component compared to before the plasma treatment.
9. The support according to any one of 8.

10. The surface energy of the substrate subjected to the plasma treatment is such that the polarity component is increased by 10 mN / m or more as compared with before the plasma treatment.
9. The support according to any one of items 1 to 8.

11. The support according to any one of the above items 1, 3 to 8, wherein the polymer is gelatin, polyvinyl alcohol (PVA), an acrylic resin or a polyester resin.

12. The adhesion amount of the adhesive layer is 5 to 100.
The support according to any one of the above 1 to 11, wherein the support is mg / m ² .

13. The adhesive layer is made of 1,2-bis (vinylsulfonylacetamide) ethane (BVSAE), bis (vinylsulfonyl) methane (BVSM), bis (vinylsulfonylmethyl) ether (BVSME) and bis (vinylsulfonylethyl) ether (BVSEE) ),
1,3-bis (vinylsulfonyl) propane (BVS
P), 1,3-bis (vinylsulfonyl) -2-hydroxypropane (BVSHP), 1,1-bis (vinylsulfonyl) ethylbenzene sodium sulfate, 1,1,
1-tris (vinylsulfonyl) ethane (TVSE),
Tetrakis (vinylsulfonyl) methane, tris (acrylamide) hexahydro-s-triazine, acrolein-methacrylic acid copolymer, glycidyl ether, acrylamide, dialdehyde, blocked dialdehyde, α-diketone, active ester, sulfonic ester, active halogen Compound, s-triazine, diazine,
Epoxides, formaldehyde, formaldehyde condensation products, acid anhydrides, aziridine, activated olefins, blocked activated olefins, halogen-substituted aldehyde acids, vinyl sulfones having other hardening functional groups, polymer hardeners, polymer aldehydes, polymer vinyls 13. The support according to any one of the above items 1 to 12, wherein the support is hardened with a hardener selected from the group consisting of sulfone, polymer blocked vinyl sulfone and polymer active halogen.

14. 14. The support as described in any one of 1 to 13 above, wherein the substrate is a polyester substrate.

15. 15. The support as described in any one of 1 to 14 above, wherein the support is a support for a photographic light-sensitive material.

16. The method for producing a support comprises a step of performing a plasma treatment on a substrate, and a step of providing an adhesive layer containing a polymer having a weight average molecular weight of 50,000 Mw or less on the substrate subjected to the plasma treatment. A method for producing a support, which is characterized in that:

17. In the method for producing a support, a step of subjecting a substrate to plasma treatment; and a step of subjecting the substrate subjected to the plasma treatment to gelatin containing a 10% aqueous solution of gelatin alone at 20 ° C. and having a viscosity of 0.2 Pa · s or less. Providing a bonding layer to be formed.

18. The plasma processing is an atmospheric pressure plasma processing, a gas used for the atmospheric pressure plasma processing is a mixed gas of an inert gas and a reactive gas, and the inert gas contains 50% by weight or more of argon gas, The method for producing a support according to the above item 16 or 17, wherein the reaction gas is nitrogen, oxygen, carbon dioxide or hydrogen.

19. The plasma processing is an atmospheric pressure plasma processing, wherein a gas used for the atmospheric pressure plasma processing contains a reaction gas at 40% by pressure or more, and the atmospheric pressure plasma processing generates plasma with a pulsed electric field. 16 or 1 above, wherein
8. The method for producing a support according to 7.

Hereinafter, the present invention will be described in detail.

The substrate used for the support of the present invention is not particularly limited, but is preferably a resin substrate such as a resin film or a resin-coated paper, the surface of which is in contact with the adhesive layer, particularly a polyester substrate. Is preferred.

As the substrate used for the support of the present invention,
Cellulose ester substrate such as cellulose triacetate, polyester substrate, polycarbonate substrate, polyimide substrate, polystyrene (syndiotactic) substrate, polyolefin substrate, polyolefin resin-coated photographic paper substrate melt-coated on paper substrate, or polyester resin-coated photographic paper substrate And the like.

A white pigment may be mixed into the polyolefin resin-coated photographic paper substrate, or the polyester resin-coated photographic paper substrate, polyester substrate, or polyolefin substrate, depending on the application. This application is a photographic paper substrate, and the substrate surface is white for viewing as a reflection image. As the white pigment, barium sulfate, titanium oxide, magnesium carbonate, zinc oxide and the like are preferable, and among them, titanium oxide is particularly preferable. Two types of titanium oxide, rutile type and anatase type, are often used, and among them, anatase type is preferable from the viewpoint of whiteness stability.

The polyolefin substrate or polyolefin resin-coated substrate used in the present invention includes high-density polyethylene, medium-density polyethylene, low-density polyethylene, and polypropylene.

The cellulose ester substrate comprises cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose phthalate half ester, cellulose acetate phthalate, cellulose nitrate, cellulose acetate nitrate, polycaprolactone grafted Cellulose derivatives such as cellulose acetate can be mentioned, and among them, aliphatic esters and mixed fatty acid esters can be suitably used.
2.0% cellulose acetate, with a degree of acetylation of 57.0
It is preferable to use a cellulose triacetate film of up to 62.0 because a film having good mechanical strength, dimensional stability, and moisture and heat resistance can be obtained. These cellulose esters preferably have a weight average degree of polymerization of 200 to 800, particularly preferably 250 to 400.

The polyester base containing polyester as a main component is very preferable because it has higher mechanical strength than the above base and excellent dimensional stability.

The polyester constituting the polyester substrate may be further copolymerized with another copolymer component, or may be mixed with another polyester or a polymer other than the polyester.

The polyester substrate is a substrate obtained by biaxially stretching a sheet obtained by melting a polyester obtained by esterification and polycondensation of a dicarboxylic acid and a diol as constituent components.

One of the constituent dicarboxylic acids is
In terms of transparency, mechanical strength, dimensional stability, etc., terephthalic acid and 2,6-naphthalenedicarboxylic acid are used. As another component diol, ethylene glycol and 1,4-naphthalene are used in the same manner as described above. Cyclohexanedimethanol is preferred. A polyester obtained by esterification and polycondensation by appropriately combining these dicarboxylic acids and diols is preferable. Among them, polyethylene terephthalate (PE
T): polyethylene naphthalate (PEN); poly (terephthalate-co-2,6-) comprising terephthalic acid and 2,6-naphthalenedicarboxylic acid and ethylene glycol
Naphthalate); a copolyester obtained by transesterifying a mixture of PET and PEN having different molecular weights at the time of melting; a copolyester of ethylene terephthalate, cyclohexanedimethanol and ethylene glycol;
Copolyesters of 2,6-naphthalate, cyclohexanedimethanol and ethylene glycol; mixed polyesters of diols of ethyleneglycol, cyclohexanedimethanol, terephthalic acid and dicarboxylic acids of 2,6-naphthalenedicarboxylic acid are preferred. Of these,
When an ethylene terephthalate unit and / or an ethylene-2,6-naphthalate unit is contained in an amount of 70% by weight or more based on all polyesters, a polyester film excellent in transparency, mechanical strength, dimensional stability, and the like can be obtained. preferable.

Further, a polyester having a laminated structure as described in JP-A-6-240020 may be used. In this case, as a copolymerization component as a polyester, sodium sulfophthalate, a hydrophilic polyester is obtained by incorporating the copolymerization component such as polyethylene glycol, and the hydrophilic polyester is provided on the outside and a core such as polyethylene terephthalate or polyethylene naphthalate. By using a highly rigid material, a polyester substrate having hydrophilicity can be produced, and is preferably used in the present invention.

Of the above, polyethylene terephthalate,
Polyethylene naphthalate, especially polyethylene-2,6
Naphthalate, polyolefin resin film substrates and resin-coated photographic paper substrates are particularly preferred for use in the present invention.

In the support of the present invention, the adhesive layer provided on the substrate may be a low molecular weight polymer having a weight average molecular weight of 50,000 Mw or less, or a 10% aqueous solution of gelatin alone at 20 ° C. having a viscosity of 0.2 Pa · s or less of gelatin.

Usually, the polymer used in the photographic constituent layer of the photographic light-sensitive material is gelatin or the like as a main binder, and the weight-average molecular weight is generally 100,000 or more. In addition, since a 10% aqueous solution of gelatin used for a photographic component layer of a photographic material usually solidifies at 20 ° C. and the viscosity cannot be measured, the polymer or gelatin used for the adhesive layer of the present invention is not used. It is of low molecular weight or low viscosity.

Polymers having a weight average molecular weight of 50,000 Mw or less include vinyl chloride, vinylidene chloride, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride,
Copolymers such as diolefin, gelatin, cellulose nitrate and the like can be mentioned. Either a hydrophilic polymer or a hydrophobic polymer may be used, but a hydrophilic polymer more effectively exerts the effects of the present invention.

The weight average molecular weight of the present invention is 50,000M
w or less hydrophobic polymer, a thermoplastic polymer,
Examples include radiation curable polymers, thermosetting polymers, and other reactive polymers. As the thermoplastic polymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride polymer, vinyl acetate-vinyl alcohol copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene -Vinyl polymers or copolymers such as vinyl chloride copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-vinyl alcohol terpolymer, cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate Cellulose derivatives such as, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated poly Styrene - styrene terpolymer, methyl methacrylate - butadiene - styrene terpolymer, polyacrylic ester, polyvinyl acetal, polyvinyl butyral, polyester polyurethane copolymer, polyether polyurethane copolymer, polycarbonate polyurethane copolymers, polyesters, polyethers,
Examples thereof include polyamide, styrene-butadiene copolymer, butadiene-acrylonitrile copolymer, silicone-based polymer, and fluorine-based polymer. These can be used alone or in combination of two or more. Tg (absolute temperature) of thermoplastic polymer is 170-4
Preferably in the range of 20 ° K, 210-400 ° K
Is more preferable.

The radiation-curable polymer is a polymer which is cured by radiation such as an electron beam or an ultraviolet ray, and includes acrylic type, maleic anhydride type, urethane acrylic type, ether acrylic type, epoxy acrylic type, epoxy type and the like. .

The thermosetting polymer and other reactive polymers include phenol polymer, amino polymer, epoxy polymer, polyurethane-based curing polymer, isocyanate-based curing polymer, melamine polymer, urea polymer, alkyd polymer, silicone-based curing polymer. Polymer, oxazoline-based curable polymer and the like. These can be used alone or in combination of two or more.

The weight average molecular weight of the present invention is 50,000M
Examples of the hydrophilic polymer that can be used in the present invention include, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (hereinafter abbreviated as No.), page 26, and pp. 18716, 651
Examples thereof include water-soluble polymers and latex polymers described on the page.

The water-soluble polymers other than gelatin include
Casein, agar, sodium alginate, natural processed products such as starch, polyvinyl alcohol, acrylic acid copolymer,
Examples include addition-polymerized polymers such as maleic anhydride copolymers, and water-soluble polyesters of dicarboxylic acids containing metal sulfo-substituted dicarboxylic acids and diols such as ethylene glycol. In addition, a part of gelatin is colloidal albumin, casein, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, cellulose derivatives such as cellulose ethers such as carboxymethylcellulose, agar, sodium alginate, starch derivatives, sugar derivatives such as dextran, synthetic. It may be replaced by a hydrophilic colloid, for example, polyvinyl alcohol, poly N-vinylpyrrolidone, an acrylic acid-based copolymer, polyacrylamide or a derivative thereof, a partial hydrolyzate, or a gelatin derivative. Water-soluble polyesters are also useful. The water-soluble polyester is a polyester obtained by combining terephthalic acid, naphthalene carboxylic acid, phthalic acid, etc. as a dicarboxylic acid component and ethylene glycol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, etc. as a diol component. As the water-soluble component, a component in which metal sulfophthalic acid and polyethylene glycol are incorporated as a copolymer component is preferable.

Examples of the latex polymer include a latex polymer obtained by emulsion polymerization of a suitable combination of monomers such as vinyl chloride, vinylidene chloride, acrylate, vinyl acetate, butadiene, styrene and styrene derivatives.

The hydrophilic polymers or hydrophobic polymers listed above may have a polar group in the molecule. As the polar group, an epoxy group, -COOM, -OH, -N
_{R 2, -NR 3 X, -SO} 3 M, -OSO 3 M, -PO
₃ M ₃ , —OPO ₃ M (M is a hydrogen atom, an alkali metal or ammonium, X is an acid forming an amine salt,
R each represents a hydrogen atom or an alkyl group), which promotes crosslinking in the polymer binder layer, stabilizes the mixed state of various additives, and has an affinity with an upper layer. Can be increased.

The weight average molecular weight of the present invention is 50,000
Among polymers having a molecular weight of 0 Mw or less, preferred are gelatin, polyvinyl alcohol (PVA), acrylic resin,
It is a polyester resin. Particularly preferred is gelatin. These polymers are easily available commercially.

The content of the polymer having a weight average molecular weight of 50,000 Mw or less in the adhesive layer of the present invention is 50% by weight.
The effects of the present invention can be obtained if the above is satisfied, but preferably 70
% By weight, more preferably 90% by weight or more.

In the polymer used in the present invention, the weight average molecular weight of 50,000 Mw or less is a value measured by a gel permeation chromatography (GPC method), specifically under the following conditions.

(GPC method) a) Column: Asahipak, GS-620 (manufactured by Asahi Chemical Industry Co., Ltd.) Two columns connected in series Temperature: 50 ° C. b) Eluent: 0.1 M KH ₂ PO ₄ and 0.1 M Na ₂
Equivalent mixed solution with HPO ₄ pH 6.8 Flow rate 1.0 ml
/ Min c) Sample: 0.2% eluent solution of gelatin Injection volume 100 μl d) Detection: UV absorption spectrophotometer (UV wavelength 230 n)
m) The calculation of the molecular weight is performed by preparing a calibration curve from the retention time and the molecular weight using albumin, ovalmin, mitochrome or the like whose molecular weight is known in advance under the above conditions,
The retention time of the sample gelatin solution is applied to a calibration curve to calculate the molecular weight. The weight average molecular weight is calculated from the ratio of the area for each molecular weight to the total area.

In the gelatin used in the present invention, at 20 ° C.
That the viscosity of a 10% aqueous solution is 0.2 Pa · s or less in the Pagii method
992) is 0.2 Pa · s or less. According to the above, the measurement concentration (10%) and the measurement temperature (2
0 ° C.), meaning that measurement was performed.

In the support of the present invention, the adhesive layer is preferably hardened with a hardener. As hardening agents, aldehyde-based and aziridine-based (for example, PB Report, 199
21, U.S. Pat. Nos. 2,950,197 and 2,96
Nos. 4,404, 2,983,611 and 3,27
1,175, JP-B-46-40898 and JP-A-50-91315).
Isoxazole-based (eg, US Pat. No. 3,331,331)
No. 609), epoxy type (for example, US Pat. No. 3,047,394, West German Patent No. 1,
085,663 and British Patent No. 1,033,518, and those described in JP-B-48-35495), vinyl sulfones (for example, PB Report 1)
9,920; West German Patent No. 1,100,942;
337,412, 2,545,722, 2,6
No. 35,518, No. 2,742,308, No. 2,74
No. 9,260 and British Patent Nos. 1,251,091 and Japanese Patent Publication Nos. 49-13563 and 48-1.
10996, furthermore, those described in the specifications of U.S. Pat. Nos. 3,539,644 and 3,491,911), and acryloyl (for example, JP-B-53-778 and U.S. Pat. 640,720), carbodiimide-based (eg, US Pat.
938,892, 4,043,818 and 4,
061,499), triazines (for example, West German Patent Nos. 2,410,973 and 2,
553,915 and U.S. Pat. No. 3,325,287, as well as those described in JP-A-51-2722), and oxazoline-based compounds (for example, JP-A-5-295).
No. 275), polymer type (for example, British Patent No. 822,061, US Pat. No. 3,623,87)
Nos. 8, 3,396,029 and 3,226,23
No. 4), JP-B Nos. 47-18578, 47
Nos. 18579 and 47-48896), isocyanates, polyamide-epichlorohydrin resins (for example, those described in JP-A-51-3619), compounds having a reactive halogen, and other maleimides And acetylene-based, methanesulfonate-based, and N-methylol-based hardeners.

Of the above hardeners, the one preferably used is 1,2-bis (vinylsulfonylacetamide)
Ethane (BVSAE), bis (vinylsulfonyl) methane (BVSM), bis (vinylsulfonylmethyl) ether (BVSME) and bis (vinylsulfonylethyl)
Ether (BVSEE), 1,3-bis (vinylsulfonyl) propane (BVSP), 1,3-bis (vinylsulfonyl) -2-hydroxypropane (BVSHP),
1,1-bis (vinylsulfonyl) ethylbenzene sodium sulfate, 1,1,1-tris (vinylsulfonyl) ethane (TVSE), tetrakis (vinylsulfonyl) methane, tris (acrylamide) hexahydro-
s-triazine, acrolein-methacrylic acid copolymer, glycidyl ether, acrylamide, dialdehyde, blocked dialdehyde, α-diketone, active ester, sulfonic acid ester, active halogen compound, s-
Triazines, diazines, epoxides, formaldehyde, formaldehyde condensation products, acid anhydrides, aziridine, activated olefins, blocked active olefins, halogen-substituted aldehyde acids, vinyl sulfones having other hardening functional groups, polymer hardeners, polymers It is an aldehyde, a polymer vinyl sulfone, a polymer blocked vinyl sulfone or a polymer active halogen.

In the support of the present invention, the method for providing the adhesive layer is not particularly limited, but is preferably provided by coating. As a coating method, a conventionally known method such as curtain coating or slide bead coating can be used.

In the support of the present invention, if the amount of the adhesive layer applied to the substrate is in the range of 5 to 100 mg / m ² , the effects of the present invention can be exhibited effectively.

In the support of the present invention, the substrate is preferably subjected to an energy treatment such as an atmospheric pressure plasma treatment, a vacuum plasma treatment, a corona discharge treatment, and an ultraviolet treatment so as to further enhance the adhesiveness. For these energy treatments, generally known methods can be used. Among the energy treatments, the atmospheric pressure plasma treatment is most preferable from the viewpoint of uniformity, stability, productivity and cost of the treatment.

Atmospheric pressure plasma treatment is performed by discharging a gas with a pair of electrodes facing each other while introducing a gas under an atmospheric pressure or a pressure close to the atmospheric pressure, and continuously transporting the substrate between the electrodes. This is to perform an in-gas discharge plasma treatment. The introduced gas can be divided into an inert gas such as argon gas, helium gas, neon gas, xenon gas, and krypton gas which does not react by plasma discharge, and a reaction gas which reacts by plasma discharge.
The surface property can be changed by the reaction gas causing some reaction and binding to the substrate surface.

As the reaction gas, one that makes the substrate hydrophilic is effective for improving the adhesiveness. As such a reaction gas, a gas that can impart a polar functional group such as an amino group, a carboxyl group, a hydroxyl group, or a carbonyl group to the surface of the substrate is preferable. Nitrogen, oxygen, carbon dioxide, hydrogen, water vapor (H ₂ O)
Alternatively, ammonia gas can be used. Among them, nitrogen, oxygen, carbon dioxide, hydrogen, or steam is easy to use for handling.

When plasma discharge is performed at or near atmospheric pressure, stable discharge can be generated by mixing an inert gas such as helium or argon at 60% by pressure or more. 50% by pressure of inert gas at this time
It is preferable that the above be an argon gas.

It is preferable to increase the ratio of the reaction gas as much as possible and employ high power conditions in order to increase the processing speed. However, if the electric field intensity is too high, the substrate will be damaged. However, in atmospheric pressure plasma processing, by generating plasma with a pulsed electric field,
Inert gas is not necessarily required, and the reaction gas concentration can be increased. This makes it possible to greatly increase the reaction rate.

In order to form a pulsed electric field, it is necessary to apply the voltage intermittently to the electrodes. The pulse waveform at this time is, for example, the one shown in FIG. Also, Japanese Patent Application Laid-Open
The pulse waveforms shown in FIGS. 1A to 1D of JP-A No. 0-130851 may be used.

In FIG. 1 of the present invention, the vertical axis represents pulse voltage, and the horizontal axis represents time. The frequency of the pulse electric field is 1 to 1
A range of 00 kHz is preferred.

The time during which one pulse electric field is applied is 1 to
Preferably, it is 1000 μs. The time during which one pulse electric field is applied is the time during which a pulse having one pulse waveform in FIG. 1 is applied.

The magnitude of the voltage applied to the electrode is preferably in the range where the electric field strength is 1 to 100 kV / cm. The processing speed increases as the electric field intensity increases, but the same applies to the damage to the substrate if it is too high.

Hereinafter, a specific atmospheric pressure plasma processing apparatus will be described with reference to FIG. 2, but the atmospheric pressure plasma processing of the present invention is not limited to this.

In FIG. 2, a processing chamber 2 for continuously plasma-treating a long support 1 that is continuously conveyed under atmospheric pressure or a pressure close thereto is provided with an inlet 2 of the support 1.
A is constituted by a partitioned processing chamber having A. The same applies to the exit side.

In the processing chamber 2, a plurality of cylindrical electrodes 3 are provided on both sides of the support 1. As shown in the drawing, the juxtaposition method may be such that the juxtaposition is made, but the juxtaposition method may be adopted. The electrode interval L is represented by the distance between the lowermost end of the upper electrode of the support 1 and the uppermost end of the lower electrode. The spacing between the electrodes may or may not be uniform.

The cylindrical electrode has a conductive metal disposed inside.
It has a double-tube structure with a dielectric disposed outside.Generally, conductive materials are provided by spraying, vapor-depositing, coating, etc. on conductive materials such as silver, gold, copper, stainless steel, and aluminum. However, it is also possible to provide a conductive layer on the solid dielectric by plating, vapor deposition, coating, thermal spraying or the like.

As the solid dielectric, it is also preferable to use a sintered ceramic obtained by sintering a highly airtight and high heat resistant ceramic. Examples of the material of the sintered ceramic include alumina-based, zirconia-based, silicon nitride-based, and silicon carbide-based ceramics. The thickness of the sintered ceramic is preferably 0.5 mm or more and 5 mm or less. The volume resistivity is preferably 10 ⁸ Ω · cm or more.

When an alumina-based sintered ceramic is used as the sintered ceramic, it is preferable to use an alumina-based sintered ceramic having a purity of 99.6% or more from the viewpoint of increasing the durability of the electrode. Regarding the alumina-based sintered ceramics having a purity of 99.6% or more, the invention (Japanese Patent Application No. 9-369413) previously proposed by the present applicant can be referred to.

In the method of manufacturing an electrode using this sintered ceramic, a highly durable ceramic is sintered to produce a sintered ceramic, and the sintered ceramic is plated, vapor-deposited, sprayed or coated to form a metal. A conductive part is attached.

As a solid dielectric, Japanese Patent Application No. Hei 10-3
The low temperature glass lining described in 00984 can also be used.

Further, a metal tube or a rod can be inserted into the ceramic pipe.

The metal electrode may be entirely covered with the solid dielectric or may be only partially covered.

The gap L between the electrodes is preferably in the range of 0.3 to 10 mm, more preferably in the range of 3 to 7 mm.

A high-frequency power supply 5 is connected to the entire upper electrode, and the entire lower electrode is provided with a ground 6, so that an electric field can be applied between the respective electrode groups.

Reference numerals 20, 21, and 22 denote transport rolls.

In the illustrated example, a preliminary chamber 10 is provided adjacent to the processing chamber 2 at the entrance side of the support. Although not shown on the outlet side of the support, a spare chamber is provided adjacent to the processing chamber 2. Further, these partitions are performed by the nip rolls 7, but are not limited thereto.

In the case of providing a spare chamber, an embodiment may be provided one by one on the entrance side of the support 1, but is not limited to this, or two or more on the entrance side and two or more on the exit side It may be.

In any of the embodiments, the pressure in the processing chamber needs to be higher than the pressure in the preliminary chamber adjacent to the processing chamber, and preferably higher than 0.3 mmAq. By providing a pressure difference between the pressure chamber and the preparatory chamber, mixing of external air is prevented, the effective use of the reaction gas becomes possible, and the processing effect is further improved. When two or more preparatory chambers are provided on the inlet side and two or more preparatory chambers on the outlet side adjacent to the processing chamber, the pressure difference between the preparatory chamber and the adjacent preparatory chamber becomes smaller than the preparatory chamber closer to the processing chamber. Is preferably set high, and more preferably 0.03 mmAq or more. By providing a pressure difference between the plurality of spare chambers in this way, the incorporation of external air is more effectively prevented, and the effective use of the reaction gas becomes possible.
The processing effect is further improved.

The preliminary chamber preferably contains at least one component of the processing gas from the viewpoint of efficient use of the reaction gas and improvement of the surface treatment effect.

It is necessary that the processing chamber, the preparatory chamber, and the rooms of the preparatory chambers be partitioned, and the partitioning means is preferably provided with a nip roll as shown in the figure.

Although such a nip roll has a function of closing or partitioning while being in contact with the support, the means for providing a differential pressure as in the present invention effectively functions because the rooms cannot be completely partitioned. .

Further, the partition means may be a mode in which a predetermined gap is maintained with respect to the support and the partition is not in contact with the support. As such an embodiment, an air curtain system (not shown) or the like can be employed. In the case where no spare chamber is provided, a partition may be provided between the processing chamber and the outside.

Further, it is preferable that the pressure in the processing chamber 2 is higher than the external pressure.

By setting the air pressure in the processing chamber 2 higher than the external pressure, a stable processing can be performed because the gas from the outside does not enter the processing chamber 2.

In the present invention, more stable and uniform processing can be performed by the mode in which the pressure in the processing chamber 2 is higher than the external pressure by 0.03 mmAq or more.

In the present invention, prior to introducing a gas into the processing chamber 2, it is preferable to use a mixed gas in which an inert gas and a reactive gas are mixed in advance. Also, it is sufficient that the atmosphere between the electrodes in the processing chamber 2 has the above-described ratio of the reaction gas.

By using such a cylindrical electrode, it becomes easier to introduce a gas between the electrodes, so that the contact efficiency between the reaction gas and the electrode is increased, and as a result, the processing effect is also improved. In addition, the structure is simple, the compatibility is excellent, and the processing can be performed at low cost. Also, excellent effects are exhibited in high-speed transport of the support.

Although the electrode used in the above-described embodiment is a cylindrical electrode, it is also preferable to use a roll electrode or a gas flow type curved surface electrode.

By subjecting the substrate to the plasma treatment including the atmospheric pressure plasma treatment and the vacuum plasma treatment described above, the surface energy of the substrate surface after the plasma treatment is 3 mN / m in the non-polar component as compared with before the plasma treatment. It is preferable that the amount decreases or the polarity component increases by 10 mN / m or more.

The surface energy of the solid is
From the contact angles of two types of liquids, water (polar solvent) and show methane (non-polar solvent), the following You
ng and Fowkes equation.

[0099]

(Equation 1)

The surface tension, non-polar components and polar components of water and show methane are as shown in Table 1 below.

[0101]

[Table 1]

The values of the surface energy of the substrate are calculated by substituting the contact angle between the substrate and water or methane and the values shown in Table 1 above into the above equation.

In the above equation, γ _S , γ _L , γ _SL and θ are as shown in FIG.

Γ _S is the surface energy of the substrate (= γ _S
^d + ^γ _S ^p), the gamma _S ^d and gamma _S ^p is a non-polar component of the surface energy of each substrate (d) and polar component (p).

The support of the present invention may be a photographic material represented by a silver halide photographic material, a magnetic recording medium, or the like.
Although it can be applied to various products, it is preferably applied to a photographic material.

[0106]

The present invention will now be described by way of examples, which should not be construed as limiting the invention.

Example 1 Atmospheric-pressure plasma treatment was carried out using the apparatus shown in FIG. 2 while continuously transporting a long substrate under the following conditions, and immediately thereafter, without winding the substrate,
A gelatin coating solution was applied online using a wire bar coating device (application of an adhesive layer), and dried to obtain a sample. An adhesion test was performed on each sample.

<Treatment Conditions> Treatment chamber: 0.2 m ³ capacity, 420 mm width Substrate: 400 mm width, 90 μm PEN film Treatment gas: 100% pressure of inert gas introduced is argon gas, reaction with inert gas The inert gas ratio is Ar: N
₂ = 50: 1 Frequency: 10 kHz Gap between electrodes: 5 mm Supporting material transport speed: 50 m / min Processing time: 0.5 sec Output: 22 kW / m ² The surface energy of the substrate by the atmospheric pressure plasma processing is the value before the processing. The non-polar component decreased by 3 mN / m and the polar component increased by 10 mN / m.

<Coating Conditions> A wire bar coating device was used.
The coating film thickness and the coating solution concentration were adjusted so that the amount of the adhesive layer applied was 10 mg / m ² .

<Liquid condition> The weight average molecular weight of gelatin was selected from 30,000 to 100,000 as shown in Table 2, and 0.1% of dichloro-s-triazine was used as a hardening agent.
An amount of 3 mg / m ² was added.

<Adhesion Test> For each of the obtained samples, p
After being immersed in a developer at a temperature of 42 ° C. for 10 minutes at H12, cuts were made in a grid at intervals of 2 mm, rubber gloves were attached, and the operation of firmly rubbing off by hand was performed. Table 2 shows the results.

[0112]

[Table 2]

◎: Not peeled off at all △: Partially peeled off ×: Completely peeled off (Example 2) Only the liquid conditions were as shown in Table 3 below, and the other conditions were the same as in Example 1. An experiment was performed. The results are shown in Table 3.

[0114]

[Table 3]

Example 3 An experiment was performed under the same conditions as in Examples 1 and 2 except for the processing gas conditions and the applied voltage conditions.

<Treatment Conditions> Treated gas: Nitrogen gas and hydrogen gas mixed at a ratio of N ₂ : H ₂ = 50: 2 Frequency: 20 kHz (rise and fall times are 100 n)
(Pulse voltage of sec) Applied voltage 12 kV Gap between electrodes: 5 mm Output: 25 kW / m ² The results were exactly the same as those in Examples 1 and 2.

[0117]

According to the present invention, a support capable of securing strong adhesiveness can be obtained by the support of the present invention.
A method for manufacturing a support stably, at low cost, and excellent in productivity was provided.

[Brief description of the drawings]

FIG. 1 shows a pulse waveform applied to an electrode applicable to an atmospheric pressure plasma discharge process in the present invention.

FIG. 2 is a schematic diagram showing a processing apparatus applicable to atmospheric pressure plasma processing in the present invention.

FIG. 3 is a diagram showing a relationship between a contact angle between a substrate and a liquid and a component of surface energy.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Support body 2 Processing chamber 3 Electrode 5 Power supply 6 Earth 7 and 8 Nip roll 10, 11, 12 Preparatory chamber 20, 21, 22 Transport roll L Electrode spacing

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 167/02 C09J 167/02 189/00 189/00 G03C 1/91 G03C 1/91 F-term (Reference) 2H023 FB01 FB02 FB05 4J004 AA04 AA08 AA10 AA15 CA06 CC02 CD08 FA10 4J040 BA161 DB002 DD021 DD062 DF011 DJ012 EB012 ED041 HB02 HB17 HB20 HB22 HB44 HC11 HC22 HC25 HD11 HD13 HD16 JB10 KA16 LA06

Claims (19)

[Claims] 1. The method according to claim 1, wherein the weight average molecular weight is 50,000 on the substrate.
A support having an adhesive layer containing a polymer of 0 Mw or less. 2. A support having, on a substrate, an adhesive layer containing gelatin whose viscosity of a 10% aqueous solution of gelatin alone at 20 ° C. is 0.2 Pa · s or less. 3. The support according to claim 1, wherein the substrate has been subjected to an energy treatment. 4. The support according to claim 3, wherein the energy treatment is a plasma treatment. 5. The support according to claim 4, wherein the plasma processing is an atmospheric pressure plasma processing. 6. The support according to claim 5, wherein the gas used for the atmospheric pressure plasma treatment is a mixed gas of an inert gas and a reaction gas. 7. The support according to claim 6, wherein the inert gas contains 50% by pressure or more of argon gas. 8. The support according to claim 6, wherein the reaction gas is nitrogen, oxygen, carbon dioxide, or hydrogen. 9. The surface energy of the substrate subjected to the plasma treatment is lower than that of the substrate before the plasma treatment by 3
5. The method according to claim 4, wherein the value is reduced by mN / m or more.
9. The support according to any one of 8 above. 10. The surface energy of the plasma-treated substrate has a polar component of 1 compared to that before the plasma treatment.
5. An increase of 0 mN / m or more.
The support according to any one of claims 1 to 8. 11. The support according to claim 1, wherein the polymer is gelatin, polyvinyl alcohol (PVA), an acrylic resin, or a polyester resin. 12. The adhesion amount of the adhesive layer is 5 to 100 m.
Support according to any one of claims 1 to 11, characterized in that a g / m ^2. 13. The adhesive layer comprises 1,2-bis (vinylsulfonylacetamide) ethane (BVSAE), bis (vinylsulfonyl) methane (BVSM), bis (vinylsulfonylmethyl) ether (BVSME) and bis (vinylsulfonyl). Ethyl) ether (BVSEE),
1,3-bis (vinylsulfonyl) propane (BVS
P), 1,3-bis (vinylsulfonyl) -2-hydroxypropane (BVSHP), 1,1-bis (vinylsulfonyl) ethylbenzene sodium sulfate, 1,1,
1-tris (vinylsulfonyl) ethane (TVSE),
Tetrakis (vinylsulfonyl) methane, tris (acrylamide) hexahydro-s-triazine, acrolein-methacrylic acid copolymer, glycidyl ether, acrylamide, dialdehyde, blocked dialdehyde, α-diketone, active ester, sulfonic ester, active halogen Compound, s-triazine, diazine,
Epoxides, formaldehyde, formaldehyde condensation products, acid anhydrides, aziridine, activated olefins, blocked activated olefins, halogen-substituted aldehyde acids, vinyl sulfones having other hardening functional groups, polymer hardeners, polymer aldehydes, polymer vinyls The support according to any one of claims 1 to 12, wherein the support is hardened with a hardener selected from the group consisting of sulfone, polymer blocked vinyl sulfone, and polymer active halogen. 14. The support according to claim 1, wherein the substrate is a polyester substrate. 15. The support according to claim 1, wherein the support is a support for a photographic light-sensitive material. 16. A method for producing a support, comprising: subjecting a substrate to a plasma treatment; and providing an adhesive layer containing a polymer having a weight average molecular weight of 50,000 Mw or less on the substrate subjected to the plasma treatment. A method for producing a support, comprising: 17. A method for producing a support, wherein a plasma treatment is performed on the substrate, and the viscosity of a 10% aqueous solution of gelatin alone at 20 ° C. is 0.2 Pa · s or less at 20 ° C. Providing an adhesive layer containing gelatin as described in (1). 18. The plasma processing is an atmospheric pressure plasma processing, wherein a gas used for the atmospheric pressure plasma processing is:
17. A mixed gas of an inert gas and a reaction gas, wherein the inert gas contains 50% by weight or more of argon gas, and the reaction gas is nitrogen, oxygen, carbon dioxide, or hydrogen. Or a method for producing a support according to item 17. 19. The plasma processing is an atmospheric pressure plasma processing, wherein a gas used in the atmospheric pressure plasma processing contains a reaction gas at 40% by pressure or more, and the atmospheric pressure plasma processing is performed by a pulsed electric field. The method for producing a support according to claim 16, wherein the method is performed by generating plasma.