JPS63253354A - Photographic base - Google Patents

Abstract

PURPOSE:To obtain a photographic base generating no fog, spot, nor frilling during development by forming an adhesive layer comprising a specified copolymerizable compsn. on the surface of a metal capable of causing specular reflection or diffuse reflection of the second kind. CONSTITUTION:A copolymerizable compsn. consisting of diolefin, another polymerizable ethylenic unsatd. monomer and/or a monomer having at least one COOH group or PO3H group is incorporated into an adhesive layer. In this case, a copolymer compsn. contg. at least a kind of compd. expressed by formulas I and II is(are) used pref. for the adhesive layer singly or in the form of comonomer. In formulas I and II, A is an n-valent org. residue; n is an integer 2-10; R1 is H atom, (un)substituted alkyl, aryl, aralkyl, alkenyl. By this constitution, a photographic base generating no fog, nor spot during development, causing no defect such as frilling during drying after development, is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a photographic support that provides excellent images, and is particularly susceptible to film peeling, fogging, and spots during development processing. This invention relates to a photographic support that provides images with good reproducibility in hue, gradation, etc. and excellent sharpness.

(Prior art) TAC and PE, which are conventionally known as photographic supports,
Compared to transparent plates and films such as T or polycarbonate, paper 1 synthetic paper, baryta paper, films containing white pigments, plates, and metal plates such as aluminum plates with anodized surfaces, etc. By using a photographic support with a specular reflective or type 2 diffuse reflective surface, you can obtain photographs and recording media with excellent gradation reproducibility, hue reproducibility in the case of color photographs, and image sharpness. . For example, Japanese Patent Publication No. 47-2103 Hiroshi 6.

Patent application Sho t/-/1lrr00, gap A/-/4110
/ issue, space 4/-/41102, space 67-itrr
oJ issue, Showa t/-/l, rr01/- issue.

No. 47-/6IrOj, 1st year of Showa. /-1+'? 17
It is stated in issue 3 etc.

To provide specular reflectivity or 28th diffuse reflectance, natural mica, fish scales, and mineral substances such as minerals can be used, but in most cases aluminum, silver, gold, steel, chromium,
A metal such as nickel or platinum or an alloy thereof, and generally aluminum is preferably used. However, if a metal baser than metallic silver is used as a support for photographic or recording photosensitive materials that use silver halide photographic emulsions, fog and spots tend to occur during the development process. .

For this purpose, it is known to provide an adhesive layer of thermoplastic resin. However, film peeling is likely to occur during the development process and during drying after development, and when thermoplastic resin is used, it is thin, such as o, i or! There are difficulties in providing micrometer layers. Furthermore, over a long period of time after the development process, there is a risk that the specular surface or the 28th diffuse reflectance may deteriorate or unevenness may occur.

(Problems to be Solved by the Invention) An object of the present invention is to provide a photographic support that does not cause defects such as capri, spots, and film peeling during the development process, and also to An object of the present invention is to provide a photographic support having excellent storage stability.

Other objectives will be apparent from the description.

(Means for Solving the Problems) The above-mentioned objects of the present invention have been achieved by the following photographic support as a result of various studies.

(1) In a photographic support in which an adhesive layer of a laminated copolymer composition is provided on a gold i* surface with specular reflection property or type 2 diffuse reflection property, diolefins and other polymerizable A photographic support comprising a copolymerizable composition comprising an ethylenically unsaturated monomer and/or a monomer having at least one carboxylic acid or phosphoric acid group.

(2) In a photographic support provided with an adhesive layer of a laminated copolymer composition on a metal surface, A: butadiene monomer B: a monomer selected from itaconic acid, methacrylic acid, and acrylic acid. 7 types of monomers and C: sterene,
The copolymer of at least seven monomers selected from α-methylstyrene, methyl methacrylate and acrylonitrile contains 10 to 10% by weight of butadiene monomer and 9.9% by weight of B acid units. The photographic support according to (1)K above, containing 2 to 20% by weight.

(3) As a hardening agent for the layer or gelatin of the copolymer composition, active vinyl groups, epoxy groups, ethyleneimino groups, methanesulfonic acid ester groups, active ester groups, active carbodiimide groups, active sulfimide groups, isoxazole groups , or a compound having an isocyanate group, and at least one compound selected from the group of chromium alum and chromium acetate.

The adhesive layer according to the present invention has the following general formula (I) or XI.
) It is preferable to use a copolymer composition containing at least one compound represented by the following, either alone or as a monomer.

General formula (I) A +S O2CH=CH2)n General formula (If) (In the above general formulas (I) and (II), A represents an n-valent organic residue, and n represents an integer from λ to io .R
1 is a hydrogen atom or a substituted or unsubstituted alkyl group,
Represents an aryl group, an aralkyl group, an alkenyl group, or an alkenyl group. ) α In formula (m), R2 and R3 are a chlorine atom, -0M group (
MFi represents a hydrogen atom or a monovalent metal atom), a substituted or unsubstituted alkyl group, an alkoxy group, a substituted or unsubstituted amine group, -NI-I COIta (Ra is a hydrogen atom, an alkyl group, an aryl group, or represents an alkylthio group).

General Formula (fV) In the formula, R7 and rt8 represent a chlorine atom, a -0M group, a substituted or unsubstituted alkyl group, or an alkoxy group. Q, Q'
represents -0-1-3-, -Nl(-, L represents an alkylene group, and 9 represents an arylene group. 1.m represents 0 or l.
represents.

In the formula, R□1 and R12 are substituted or unsubstituted alkyl groups,
It represents an aryl group or an aralkyl group, and may be the same or different. R11 and R12 can be combined with each other to form a heterocycle with a phoneme atom. EL
ta is a substituent such as a hydrogen atom, a halogen atom, a carbamoyl group, a sulfo group, a sulfoxy group, a ureido group, an alkoxy group, a substituted or unsubstituted alkyl group, or a dialkyl-substituted amine group.

X- is an anion and is unnecessary when forming an inner salt.

In the formula, R11, R12, R13, and X- are general formula (IV)
Synonymous with .

In the formula, R1□, R12, R13 and R14 are an alkyl group, an aralkyl group, or an aryl group, and may be the same or different. Further, it may have a substituent.

f'Ltt, R1□, R13 and R14 may optionally be bonded at λ to form a ring. Y″″ represents an anion. Not required when forming an inner salt.

General formula (■) R11-N-C=N-R12 In the formula,
R11 represents a substituted or unsubstituted alkyl group, cycloalkyl group, alkoxyalkyl group, or aralkyl group.

R□2 represents R11 and a substituted or unsubstituted alkylene group, and R14 and atS represent the same or different alkyl groups. R14 and nts can be combined to form a heterocycle. R16 represents a substituted or unsubstituted alkyl group.

X- represents an anion and is unnecessary when R16 forms an acid group to form an inner salt.

In the formula, R11 represents a substituted or unsubstituted alkyl group, aryl group, or aralkyl group. R12 and R13 are the same substituent such as a hydrogen atom, a halogen atom, an acylamido group, a nitro group, a carbamoyl group, a ureido group, an alkoxy group, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, an aralkyl group, etc. may also be different. R
12 and R13 can form a fused ring. X is a halogen atom, a sulfonyloxy group, -0P-(OR14)2 (however, R14 represents an alkyl group or an aryl group. When X is a sulfonyloxy group, X and R can be bonded) Y
- represents an extra ion and is unnecessary when forming an inner salt.

General formula (X) In the formula, R11 and R12 have the same meaning as general formula (IV), R13
represents a substituted or unsubstituted alkyl group, aryl group, or aralkyl group. X- is an anion.

In the formula, all is a substituted or unsubstituted alkyl group.

It can have a substituent representing an aryl group or an aralkyl group. Z represents a nonmetallic atomic group necessary to complete the nitrogen-containing heteroaromatic ring.

R12H water'? [child, halogen atom, carbamoyl group,
Substituents such as sulfo group, sulfoxy group, ureido group, alkoxy group, substituted or unsubstituted alkyl group, dialkyl-substituted amino group, etc., and X- represent an anion and are unnecessary when forming an inner salt.

The features of the present invention are that an extremely thin layer of 0.1 to 1 μm (the thinner the better) can be coated uniformly and stably in contact with the metal reflective layer on the surface of the support substrate; The layers must be able to be chemically shielded not only during aging of the raw sensitizer, but also during development processing and after image formation, and have good physical adhesion between the layers. It requires particularly severe chemical shielding properties and physical adhesion compared to a nine-layer undercoat based on a general film base, such as PET.

This is because the metal layer itself has a strong corrosion effect due to the silver halide emulsion and a dissolution effect due to the development processing solution. The undercoat layer made of the copolymer composition used in the present invention is an emulsion copolymer of diolefins and other polymerizable ethylenically unsaturated monomers, and the diolefins include, for example, butadiene, -monochloroprene, and isoprene. , neoprene, 2,3-dimethylbutadiene, etc. Other polymerizable ethylenically unsaturated monomers include, for example, methyl acrylate, methyl methacrylate, ethyl acrylate,
Ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, chloroethyl acrylate, chloroethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, glycidyl acrylate, glycidyl methacrylate, phenyl acrylate.

Phenyl methacrylate, benzyl acrylate, benzyl methacrylate, phenylethyl acrylate, phenylethyl methacrylate, chloromethyl acrylate, chloromethyl methacrylate, Hiro-chloromethyl acrylate, ≠-chlorobutyl methacrylate, N, N
-diethyl acrylic 1/-), N, N-syl methacrylate, sulfopropyl methacrylate, 2-ethoxyethyl acrylate, coethoxyethyl methacrylate, acrylamide, methacrylamide, N-
alkylacrylamide (however, the alkyl group is, for example, methyl, ethyl, propyl, butyl, amyl, hexyl), N,N-dialkyl acrylamide (however, the alkyl group is, for example, methyl, ethyl, propyl, butyl, amyl; two examples of alkyl groups are N-phenylacrylamide, N-benzylacrylamide, N-phenylethylacrylamide, which may be the same group or a different type of group.

N-methylolacrylamide, N-hydroxyethylacrylamide, N,N-dihydroxyethylacrylamide, N-oxycarbonylmethylacrylamide,
N-oxycarbonylethyl acrylamide, N-oxycarbonylphenyl acrylamide, acrylonitrile, methacrylatetril, α-chloroacrylonitrile, alkyl-α-chloroacryle-)1'c is furkyl-α-chloromethacrylate (however, the alkyl group is, for example, methyl, ethyl, propyl, butyl, benzyl,
cyclohexyl), acrolein, methacrolein, vinyl isocyanate, isopropylisocyanate, styrene, α-methylstyrene, p-chloromethylstyrene, m-chloromethylstyrene, α-chloromethylstyrene, vinyl methyl ether, vinyl ethyl ether,
Vinyl acetate, vinyl flopionate, vinyl chloroacetate,
Trichlorovinyl acetate, acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, methyl itaconic acid, monoester, ethyl itaconic acid monoester, maleic anhydride, alkyl maleic acid monoester (however, examples of alkyl include methyl, ethyl, flobyl, amyl, hexyl, pendel, octyl, benzyl), alkyl 7
At least one monomer such as malic acid, monoester (alkyl is the same as the alkyl of maleinoic acid monoester), crotonic acid, etc. is used. Emulsion copolymers of these diolefins and other polymerizable ethylenically unsaturated monomers are easily available as commercial products.
As a representative emulsion copolymer that is available, for example, one made by Nippon Zeon Co., Ltd.,
70X! , Hiker/! To/hiker/! A/, hiker/j7/, hiker/j62, no\squid/j77
, Niball Hiro rjo1 Niball LX-/10. Hiker LX20≠, Hiker LXj0! , Hiker J, X4L
07, Hiker LX≠//.

Hiker LX≠/j, Hiker LX≠/l, No1 Hiker 2107. Hikarko! /r: As manufactured by Shikinichi Yakuhin Co., Ltd., Crossuren 5A-20, Crossuren NA-10, Crossuren N8-/A, Crossuren 72M-3o, Crossuren NA-//, Crossuren/SA-koλ, Crossuren 5A
-23, Crosslen 5A-2≠, Crosslen λM-43
, Crossren 2M-4-3 people, Crossren λM-jA,
Crossren 2M-3r1 Rio S L/73 K j
(7; As manufactured by Asahi Dow Co., Ltd., Dow Latex RTO, S
61 B latex nuts, 3 SB latex φ loops; manufactured by Mitsui Toatsu Co., Ltd., Polylac AL-ta//, Polylac ML-401, Polylac ML-420, Polylac M
L-40/, Polylac ML-7ot.

Polylac ML-101, Polylac ML-j77, Polylac ML-24≠, Polylac 5L-20≠; As manufactured by Sumitomo Naugatac, Nidorex 2t/6, Naugatex, 27j2E, Naugatex λ00/, Naugatex J-ta O data, Nocatex 27/
44.5N-3o4c; Binder 4rti, Binder LF-J as manufactured by Dainichisei Kako; NK binder SM-λooR as manufactured by Nakamura Chemical; Coholex +100/, Corporex ÷7 as manufactured by Nippon Gas Chemical Co., Ltd.
031; Wool cement 3 manufactured by Kyoritsu Kagaku Sangyo Co., Ltd.
C. Wool cement 3C8: manufactured by Kaisei Kagaku Co., Ltd., such as Portex GU; etc., all of which are effective. The emulsion copolymer used in the present invention contains diolefins by weight of
Preferably, the copolymerization composition contains hydroxyl groups, formyl groups, activated vinyl groups, epoxy groups, methanesulfonic acid ester groups, active ester groups, isoxazole groups, carboxyl groups, amide groups, Polymerizable ethylene having at least seven mono-reactive (active or easily reactive) functional groups, such as an alkoxy group, an incyanate group, an ethyleneimino group, or a group having at least one of these groups at the end. Those containing about 0.2 to 30 grams of unsaturated monomer by weight are preferred.

In particular, as a copolymer composition that satisfies the above-mentioned characteristics and is easy to synthesize stably at low cost, a butadiene copolymer, which has been used in practical use for PET undercoat layers, is particularly preferred. The butadiene copolymer used in the present invention is capable of harmonizing the ethylenic inertness of component C such as styrene, α-methylstyrene, methyl methacrylate, and acrylonitrile to the butadiene monomer (A) and reducing the blocking phenomenon. can. This also makes it possible to alleviate the wrinkles and folding characteristics of the metal reflective layer. The feature of the present invention is that 0
．． A copolymer mixed with an appropriate amount of ethylenically unsaturated acid monomer in an amount of 7 to 20% by weight is used. If the amount of this acid is too large, the shielding properties between the highly hydrophilic metal reflective layer of the adhesive layer and the photosensitive layer will deteriorate, making it difficult to prevent fog spots.

In addition, if it is not used, the adhesion between the metal reflective layer and the adhesive layer cannot be maintained. When a metal reflective layer, for example aluminum, is used, the very surface thereof is an oxide.

The aluminum atom and the oxygen atom are covalently bonded to the carboxyl group, which is particularly advantageous for the purpose of the present invention in that it provides adhesion between the metal reflective layer and the adhesive layer.

The next feature of the present invention is the combined use of an adhesive. The adhesive according to the invention is similar to the hardening agent of hydrophilic colloids such as gelatin.

Adhesives are compounds that partially react with unsaturated bonds present in the copolymer composition, carboxy groups present in the copolymer, or are immobilized in the copolymer composition by hydrophobic affinity and active for curing. Functional groups can remain. Of course, the present invention also includes compositions obtained by synthesizing copolymers with monomers having functional groups active for curing. Also, an undercoat layer or an adhesive layer made of a copolymer composition (for example,
o.

When a layer containing a hydrophilic colloid such as gelatin is provided on top of a layer containing a hydrophilic colloid such as gelatin, the two layers are formed by a cross-linking reaction with the hydrophilic colloid such as gelatin. Improve the adhesion between. For this purpose, it is preferable to use no curing agent in the hydrophilic colloid layer or to use a lower concentration of active groups for curing the subcoat #) NiI.

The adhesive used in the present invention will be explained.

Hydrophilic colloids used in the present invention include, for example, gelatin,
Synthesis of proteins such as gelatin derivatives, polysaccharides such as polyvinyl alcohol, cellulose derivatives, starch, natural substances such as gum arabic, water-soluble polyvinyl compounds such as dextrin, flurane, polyhinyl alcohol, polyvinylpyrrolidone, and acrylamide polymers. A polymeric substance or the like is used. In particular, proteins such as gelatin and gelatin derivatives, polyvinyl alcohol, and derivatives thereof are used. Compounds having functional groups used for hardening hydrophilic colloids, especially gelatin, are used. In particular, compounds having an active vinyl group, an epoxy group, an ethyleneimino group, a methanesulfonic acid ester group, an active ester group, a carbodiimide group, an active carboimide group, an active sulfoimide group, an inoxazole group, or an isocyanate group, particularly preferably at least moss or higher. It is a compound with

Specifically, adhesives that can be used in the present invention include divinylsulfone N, N'-xfrenbis(
vinylsulfonylacetamide), 113-bis(vinylsulfonyl)-11pronol), methylenebismaleimide,! -acetelyl.

3-diacryloyl-hexahydro-8-) riazine,
i, 3. z-t+)acryloyl-hexahydro-S-
Triazine, /, J, j-)rivinylsulfonyl-hexahydro-s-tazine, etc., as well as U.S. Patent No. J, t
J! , No. 7/r, No. 3°232.71J, British Patent No. Tata Hiro, Rari, etc.

λ, 4! --dichloro-4-hydroxy-8-) riazi sodium salt, λ, ≠-dichloro t-methoxy 8
-)Ryazine, λ, 4cm dichloro-(≠-sulfoanilino)-8-)Ryazine sodium salt, co,≠-
dichloro-,4-(2-sulfoethylamino)-8-)
riazine, N-N'-bis(cochloroethylcarbamyl)piperazine, and others, US Patent No. 3. λrl,
No. 77j, No. 2,732.303, British Patent No. 27
No. 1,723, same No. 1. Active halogen compounds such as those described in No./67.207.

Bis(J,j-epoxyprobyl)methylpropylammonium p-1 luenesulfonate, l,
λ′, 3′-epoxyzorobyloxy)butane, /,
3. ! -) diglycidyl isocyanurate, /, 3-diglycidyl-! -(r-acetoxy-β-oxypropyl)isocyanurate, et al., U.S. Patent No. 72!
, Kota No. 2, 7λj, 2ri No. 3, Kota No. 3,0ri i, 137 and the like.

2, μ, monotriethylene-8-) riazine, /, 6-
Hexamethylene-N, N'-bisethylene urea, bis-β-ethyleneiminoethylthioether, and others, U.S. Pat. No. 3,0/7,210, No. 2. yr3. tt
Ethyleneimine compounds as described in item i etc.

1,-2-di(methanesulfonoxy)ethane, /, 4
cm di(methanesulfonoxy)butane, l.

! - Di(methanesulfoneoxy)pentane-like chimethanesulfonic acid ester compounds.

dicyclohexylcarbodiimide, /-cyclohexyl-J-(J-)dimethylaminopropyl)carbodiimide-p-)luenesulfonate, l-ethyl-3-(J
-dimethylaminopropyl) carbodiimide-based compounds such as carbodiimide hydrochloride. Ko,! -dimethylisoxazole perchlorate, 2-ether-! -Phenyl isoxazole-3'-sulfone), j,j'-(par-2-2-2)-hisisoxazole, and other compounds.

Inorganic compounds such as chromium alum, chromium acetate, and zirconium sulfate.

N-carboethoxycoyne propoxyl.

-1-dihydroquinoline, N-(/-morpholinocarboxy)-μm dehydrated condensed peptide reagents such as methylpyridinium chloride, N,N'-aziboyldioxydisuccinimide, N,N'-tere7taloyldioxydisac Active ester compounds such as 7-imide.

Toluene-2,4cm diisocyanate, A-hexamethylene diisocyanate, etc. U.S. Patent No. 3.1
03. In7-anates such as those described in Kou No. 37 and the like can be mentioned. C,E.

Kenneth Mees and T, H, James @ T
theory of the photog
rapic pross.

The Macmillan Co., Ltd.
, Y, ) / 2 years (first edition)! Description on page 2 and 2, Special public official Akihiro 7-2≠2! ri number, gap ≠ tar 13 yo 63
No., Makai JA-Hirozeta No., Makai 77-J No. 202, JP-A No. 02J, etc.

Special public show≠7-j/j/ issue, gap zi-ii≠lλO issue,
Special application 1977-2 ≠ trt, 1977-46/ri 6, 1974/-r 1 rot, JP 1972-46/ri 1 rot
R issue, special public show jt-/λt issue 33, open! t-32
Japanese Patent Publication Showa ZO-3RZP, such as the T Tata issue and the 7/3 issue of the 1973 patent.

No., Opening Jλ -Ta 3 ≠ 70, Mae -Open JJ -Sea 33, No. 3, the same Akira JR - // JP2, US Patent J, J2 /,
Compounds described in No. 3/J etc. are used.

In the present invention, the following compounds are particularly useful.

General formula (1') A 4 S O2CH=CH2)n General formula (II) In the above general formulas (1) and (It), A represents an n-valent organic residue, and n is an integer of λ to 10. represent. R represents a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, aralkyl group, alkenyl group or alkynyl group.

Here, the image-forming reaction system means a region where an image-forming reaction occurs. Specifically, layers belonging to both the photosensitive element and the dye-fixing element can be mentioned. If there are λ or more layers, any one of them may be used.

The organic residue represented by A is preferably a substituted or unsubstituted alkylene group (e.g., methylene group, ethylene group, propylene group, H -CH2-CH-CH2-, etc.), an arylene group (e.g., t
p-phenylene group, m-phenylene group, ÷CH2+,
C0NH+CH2+, NHCO+CH2+,.

J -CH2-0-moCH2)-i0CH2-, +CH2←
=0 child CH2ji.

Feng l +CH2←S+CH2+.

1 + CH2 ← S O2 + CH2+: , (Here, i Fi is an integer of / - / 2, and j is O ~ 1
Represents an integer of 2. ) etc.

Among these, 1% is substituted or unsubstituted alkylene group.

-CH20÷CHz) i0CH2-1 ÷CH2+t CONH4CH2+jNHCO+ CH
2+H etc. are preferred.

The alkyl group represented by R is a methyl group.

Ethyl group, propyl group, etc.; Aryl group: phenyl group, naphthyl group, etc.; Aralkyl group: benzyl group, etc.; Alkenyl group: vinyl group, zorobenyl group, etc.; Alkynyl group: ethynyl group, propynyl group, etc. ; can be mentioned. Examples of the substituent in this case include a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, an acyl group, an acylamino group, an alkylthio group, an arylthio group, a carbamoyl group, and a sulfamoyl group.

Particularly preferred as R is a hydrogen atom.

General formula (III) J In general formula (III), R2 and R3 are chlorine atoms, -0
M group (M represents a hydrogen atom or a monovalent metal atom (R4, R
5 each represents a hydrogen atom, an alkyl group, or an aryl group. ), NHCORs (Ra represents a hydrogen atom, an alkyl group, an aryl group, or an alkylthio group.)
represents. However, neither R2 nor R3 is a chlorine atom.

General formula (F/) In general formula (fV), R7 and R8 are chlorine atoms, -0M
Group (M represents a hydrogen atom or a monovalent metal atom) represents an alkyl group or an alkoxy group. Q, Q' is 10-1-S-
1-NH-, and L represents alkyl 1', a run group or an arylene group. ! , m represents O or l.

In general formula (nl), either of the substituents represented by R2 and R3 is preferably a chlorine atom. R2, R
When the substituent represented by 3 is 10M, M is preferably a sodium atom or a potassium atom. R2
, when the substituent represented by R3 is an alkyl group or an alkoxy group, it is preferably a methyl group, ethyl group, butyl group, methoxy group, ethoxy group, butoxy group, etc.

-NHCOCR3 etc. are used for -NHCORa.

When the substituents represented by R7 and R8 in general formula (IV) are an alkyl group or an alkoxy group, it is preferably a methyl group, ethyl group, butyl group, methoxy group, ethoxy group, butoxy group, etc.

When R7 and R8 are 10M, M is preferably a sodium atom or a potassium atom. L is 10 H2-1(CH2)2 - The hardening agent represented by the general formula (I[) is 4! Kosho 4c7-1/! / issue, same $7-3JJ
IrO No., US Patent J, A Hiro! , 7 Hiro 3, Tokukai Akihiro?
-/Octopus No. 20, same! /-7r71r1, 72-4
01. LZ issue, same! λ-/211130, same j2-1
No. 30326 and No. 1t-101/-J, and any of them can be used.

The hardening agent represented by the general formula (III) is
It is described in Japanese Patent Application Laid-Open No. 7-02114A and can be used from among them.

General formula (V) In the formula, Hll and R12 are an alkyl group having 10 carbon atoms (e.g. methyl group, ethyl group, 2-ethylhexyl group, etc.), an aryl group having 6 to 1j carbon atoms (e.g. phenyl group, naphthyl group) ), or an aralkyl group having 7 to lj carbon atoms (for example, a benzyl group).

phenethyl group, etc.), and may be the same or different from each other. It is also preferable that R11 and R12 bond to each other to form a heterocycle with the nitrogen atom.

An example of forming a ring is a pyrrolidine ring.

Examples include piperazine ring and morpholine ring.

R3 is a hydrogen atom, a halogen atom, a carbamoyl group, a sulfo group, a sulfoxy group, a ureido group, an alkoxy group having 1 to IQ carbon atoms, an alkyl group having 1 to 10 carbon atoms, a carbon number -
Substituents such as ~-〇 dialkyl-substituted amino groups are included. R13 is an alkoxy group.

When the group is an alkyl group, dialkylamino group, or N-alkylcarbamoyl group, these groups may be further substituted. The basics are given. Xe generates anions and becomes a counter ion for the N-carbamoylpyridinium salt. When a sulfo group or a sulfoxy group is included in the substituent of R13, an inner salt may be formed and Xe may not be present. Preferred examples of anions include halide ions, sulfate ions, sky
t=Nateio:y, (j04e, BF4e, PF6"
etc. can be mentioned.

A detailed description of the carbamoylammonium salt hardener represented by the general formula (V) can be found in Japanese Patent Publication No. 16-1
No. 2113, No. JR-72A9P.

Tokukai Sho sitter j/Rihiro! Same issue! 62 from /-! For details, refer to publications such as No. 61-ta A4c/.

General formula (M) R11, R12, R13 Oyohi Xe definition bar General formula (V
) and these compounds are detailed in Belgian Patent No. r2jm.

General formula (■) R11, R12, 1t13 and R14 have carbon numbers/~-
20 alkyl groups (e.g. methyl group, ethyl group, butyl group, coetherhexyl group, dodecyl group), aralkyl group having 6 to 20 carbon atoms (e.g. benzyl group, phenethyl group, 3-pyridimethyl group, etc.), or carbon number! ~CoO is an aryl group (eg, phenyl group, naphthyl group, pyridyl group, etc.).

They may be the same or different. Also R11,
R12, R13 and R14 may have a substituent,
Examples of the substituent include a halogen atom, a carbon a/-carbon alkoxy group, an aryloxy group having z to 20 carbon atoms, and an N,N-disubstituted carbamoyl group.

It is also preferred that any one of Hll, R12, R13 and R14 be bonded to form a ring.

Examples of R11 and R12, or R13 and R14 bonding together to form a ring with a nitrogen atom include a pyrrolidine ring, a piperazine ring, a hydroazepine ring, a morpholine ring, and the like.

Examples of R11 and R13, or R12 and 114 bonding together to form a ring with two nitrogen atoms and the carbon atoms sandwiched between them include an imidacilline ring, a tetrahydropyrimidine ring, a tetrahydrodiazepine ring, etc. There are cases where it is formed.

X represents a group that can be eliminated when the compound represented by the general formula (■) reacts with a nucleophile, and preferable examples thereof include a halogen atom, a sulfonyloxy group, and a l-pyridinyramyl group. Ye rains anions, halide ions, sulfonate ions, sulfate ions,
cJ04e.

e e BF4. PF6 and the like are preferred. When Ye rains sulfonate ions, X, R11, R12゜R
13 or R14 to form an inner salt.

Regarding the amidinium salt hardener expressed by the general formula (■), please refer to JP-A-10-1999-λλ! There is a detailed description in the number l≠.

General formula (■) R11-N=C=N-R12 In the formula, R11 is an alkyl group having carbon number/-10 (for example, methyl group, ethyl group, 2-ethylhexyl group, etc.), carbon number! ~t cycloalkyl group (e.g. cyclohexyl group, etc.), C3-10 alkoxyalkyl group (e.g. methoxyethyl group etc.), or C7-it aralkyl group (e.g. benzyl group, phenethyl group etc.). vinegar.

R12 may be any of the groups defined for R11. R
13 represents an alkylene group having 2 to 3 carbon atoms (eg, ethylene group, propylene group, trimethylene group, etc.). R
14 and R15 each represent an alkyl group (eg, methyl group, ethyl group, etc.) having carbon number/-A, which may be the same or different.

It is also preferred that R14 and R15 combine to form a heterocycle (eg, a pyrrolidine ring, a piperazine ring, one morpholine ring, etc.) together with a nitrogen atom. R16 is carbon number/-4
Substituted alkyl groups (eg, methyl, ether, butyl, etc.) are preferable. Preferred examples of the substituent include substituted or unsubstituted carbamoyl groups and sulfo groups. Xe rains anions,
・Logenide ion, sulfonate ion, sulfate ion, (1704e, BF4e, PFae, etc.) are preferable.If R16 is substituted with a sulfo group, an inner salt is formed and Xe is not present. It's okay.

These carbodiimide hardeners are described in Japanese Patent Application Laid-open No. 11
-/2612! For details, see the same issue, jλ-μg31/.

General formula (IX) In the formula, R11 is an alkyl group having a carbon number of /-70 (for example, a methyl group, an ethyl group, a butyl group, etc.), an aryl group having a carbon number of t to /j (for example, a phenyl group, a naphthyl group, etc.), Or carbon number 7~/! Aralkyl groups (e.g. benzyl group, phenethyl group, etc.). These groups may be substituted, and examples of the substituent include carbamoyl group, sulfamoyl group, and sulfo group. R12, R
13 represents substituents such as a hydrogen atom, a halogen atom, an acylamido group, a nitro group, a carbamoyl group, a ureido group, an alkoxy group, an alkyl group, an alkenyl group, an aryl group, and an aralkyl group, and each substituent may be the same or different. Also good. It is also preferred that R12 and R13 combine to form a condensed ring together with the pyridinium ring skeleton.

X represents a group that can be eliminated when the compound represented by the general formula (■) reacts with a nucleophile, and preferred examples include a halogen atom, a sulfonyloxy group, or a 10P (
The group represented by OR')2 (R14 represents an alkyl group or an aryl group) can be opened. When X represents a sulfonyloxy group, it is also preferable that X and R11 are bonded.

Ye rains anions,...rogenide ions, sulfonate ions, sulfate ions, α04e, BF4,
PF6e and the like are preferred. Further, when R1 is substituted with a sulfo group, an inner salt is formed and Ye may not be present.

Regarding these pyridinium Shioya hardeners, please refer to Tokko Akira
Detailed descriptions can be found in r-rot Tata issue, JP-A-37-44≠74cO, and J7-≠6yo-31.

General formula (X) In the formula, R11 and R12 are defined as 1 in general formula (V)
11. The definition of R12 is exactly the same, and R13 is an alkyl group having carbon number/-10 (e.g. methyl group, ethyl group,
(butyl group, etc.), an atomyl group (e.g. phenyl group, naphthyl group, etc.) having 6 to 1 carbon atoms, or a carbon number 7 to /j
Aralkyl groups (e.g. benzyl group, phenethyl group, etc.). Xe is an anion, halide ion, sulfonate ion, sulfate ion, α04e, B
F4e.

PF6e and the like are preferred.

The pyridinium salt hardener represented by the general formula (X) is described in detail in JP-A-2-4≠≠27.

General Formula (XI) In the formula, R11 is an alkyl group having 7 to 10 carbon atoms (eg, methyl group, ethyl group, λ-ethylhexyl group, etc.), 6 to 1 carbon atoms! aryl group (for example, phenyl group, naphthyl group, etc.) or aralkyl group having 7 to /j carbon atoms (for example, benzyl group, phenethyl group, etc.), and may be substituted or unsubstituted. Examples of substituents include halogen atoms, carbamoyl groups, sulfo groups, sulfoxy groups, ureido groups, alkoxy groups with carbon numbers/-10, alkyl groups with 7 to 10 carbon atoms, and dialkyl-substituted amine groups with λ to 20 carbon atoms. There is.

Z represents a nonmetallic atom group necessary to complete the nitrogen-containing heteroaromatic ring, and preferable examples thereof include a pyridine ring, a pyrimidine ring, a pyrazole ring, an imidazole ring, an oxazole ring, and a benzo-condensed ring thereof.

R12 is a hydrogen atom, a halogen atom, a carbamoyl group, a sulfo group, a sulfooxy group, and more!・Ido group, number of carbon atoms 1 to 1
Substituents such as an alkoxy group having 0 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and a dialkyl-substituted amine group having 2 to 20 carbon atoms are included. When R12 is an alkoxy group, an alkyl group, a dialkylamino group, an N-alkylcarbamoyl group,
These groups may be further substituted, and examples of substituents include halogen atoms, carbamoyl groups, sulfo groups, sulfoxy groups, and ureido groups.

Xe rains down ions. When R11, R12 or their substituents contain a sulfo group or a sulfooxy group,
Xe may not be present, forming an inner salt. Preferred examples of anions include halide ions, sulfate ions, sulfonate ions, cto4, BF4
, PF6e, etc.

Specific compounds are shown in the description on pages 76 to 4/3 of the application specification of Japanese Patent Application No. 4/1979 By 7/3.

Two to three specific examples of the compound represented by the general formula (1) are listed below.

/) CH2=CH-8O2CH2SO2CH=CH2J
) CH2=CH3O2CH2CONH-(CH2)
Specific examples of the compound represented by the general formula (■) (2-NHCOCH2SO2C)KvH2 are listed below.

Specific examples of the compound represented by the general formula (III) are listed below.

/) 2) J) Specific examples of the compound represented by general formula (IV) are listed below.

l) Specific examples of the compound represented by the general formula (V) are listed below.

Number 1 Specific examples of the compound represented by the general formula (M) are listed below.

Specific examples of the compound represented by the general formula (■) are listed below.

Specific examples of the compound represented by the general formula (■) are listed below.

Specific examples of the compound represented by the general formula (IX) are listed below.

l)　　　　　　　　　λ) Specific examples of the compound represented by general formula (XI) are shown below.

Specific examples of the compound represented by general formula (XI) are shown below.

The main difference is that the undercoat layer or adhesive layer made of the copolymer composition according to the present invention is provided on the upper surface of the gold thinning layer having specular reflection property or type 2 diffuse reflection property.
A coating film can be formed using the method shown in t-ii≠/20, same-cho j4cm94LO2r, and same-cho ff84I-ter/////I.

When an undercoat layer made of the copolymer composition (in the form of aqueous latex) according to the present invention is applied to the top surface of the thin metal layer and dried, the higher the drying temperature, the better the adhesion between the thin metal layer surface and the undercoat layer. ,
Becomes strong. The drying temperature is 100C or higher, preferably 14CO'C or higher.

A support according to the present invention having a specularly reflective or type 2 diffusely reflective surface can be prepared by providing a thin layer of material on the support substrate that provides specularly reflective properties when the surface is sufficiently smooth. It will be done. For example, Japanese Patent Application Publication No. 67-210344, Japanese Patent Application No. 4
The methods described in No./-141100, Makai al-itrroi, Makai 4/-24I-tat73, etc. are used. Preferably, the metal is F, Pennfurt (F, Be
Metals such as silver, aluminum, gold, copper, chromium, nickel, platinum, etc., and their alloys, as described in J, Opt, Soc, Amer, Vol. 32/74L~, p. r. For example, aluminum/magnesium, sinchu, etc. Natural mica also provides specular reflection even with the metal powders and inorganic substances mentioned above.

A layer filled with scale powder or the like may also be used.

The substrate of the support may be conventionally used as a support such as plastic film, paper, Ichino ζ-1 synthetic paper for RC, metal plate, etc., or polycarbonate, polystyrene, polyacrylate, polycarbonate, etc., which have excellent dimensional stability. These are polymer and copolymer plates of methacrylate and PET.

Paper and RC paper are particularly preferred. The support of the present invention can be obtained easily and at a low cost level by laminating the pre-textured aluminum foil of the present invention using a polyethylene layer of RC-Eper in combination with low density polyethylene.

Polycarbonate, polystyrene, polyimide resin, and ceramic materials, which have particularly excellent dimensional stability and physical strength, are used for the disk-like recording medium described in Japanese Patent Application No. 2173/1973.

The support of the present invention can be widely used as a reflective support for photography. A silver halide emulsion layer for black and white printing paper may be provided on the support via an undercoat layer if necessary, and a protective layer may be provided thereon. Similarly, a color photographic paper photosensitive material can be prepared by providing one or more light-sensitive silver halide emulsion layers, each having a different spectral sensitivity and each containing a different color coating, as used for ordinary color photographic paper. I can do it. It is also possible to produce color reversal photosensitive materials, direct positive color photographic papers, and direct positive color copy materials using a light fogging method. In addition, red-, green-, and blue-sensitivity silver halide emulsions containing silver halide grains having different spectral sensitivities and dyes used in the silver dye brite (SDB) method were deposited on this support. It is also possible to make SDB-type printed photosensitive materials by using this method. In addition, reflective disk plates and disks using silver halide are also available.
It can also be applied to film and recording materials. For more details, please refer to the patent application No. Sho t/-1411102, Makaij/-/
No. 61103, 47-/6110 No. 4/-
16110! It can be widely applied and used in photosensitive materials such as those described in Japanese Patent Application No. 67-2, No. 273, Kaikaifu/-21-27, Reference, and Makai No. 4/-27!172.

It can also be used as a material for forming color images by providing a mordant layer on the support of the present invention and diffusing and transferring the color-developing dye. It can also be used as a material for forming a silver diffusion transfer type silver image by providing a physical development nucleus in the lower layer on the support of the present invention. Also, Tokko Akira! Tar No. 3737 and JP-A-1989-
It is also possible to provide an adsorption layer ADL of a substance that inhibits development or desilvering action such as No. 61230, for example, an iodide ion, bromide ion, a heterocyclic compound having a mercapto group, or a heterocyclic compound that has the possibility of forming imino silver. can.

Further, a photographic support of the present invention is disclosed in U.S. Pat.

100.426, JP-A-40-/J34A'fi-9, JP-A-1999/J34A'fi-9, J-ter λ/U→3, Tokugansho, IGO-7-70, etc. It can also be applied to dye-fixing materials (image-receiving materials).

(Example of the invention) Next, examples will be shown, but the invention is not limited thereto.

Example 7 Metal aluminum was roughly rolled, and then two sheets of metal aluminum were overlapped and rolled around the center rolling roller by rolling the upper and lower two adjacent rolling rollers.
An aluminum foil having a thickness of oμ was obtained. Next, this was annealed. Surprisingly, this adjoining surface had a type 2 diffuse reflection property.

An emulsion polymer composition obtained by emulsion polymerization of monomers having the following composition was applied as an adhesive layer onto the λ-th type diffuse reflective surface of soft aluminum having a thickness of ioμ.

The dry weight of this adhesive layer was 0. Apply y/m2.

This was dried at 7≠o'C for io minutes. On top of this, gelatin was applied as an undercoat in a dry amount of 0.2 f/rrL2, and dried at 14 CO 0 C for 10 minutes. Butyl titanate was applied to the surface opposite to this adhesive layer in o, ty/milk 2.

The above-mentioned undercoated aluminum foil has a basis weight of Jtoy/
Bonded to m2 base paper using fused low-density polyethylene. Also, high-density polyethylene was melt-laminated on the opposite side of the aluminum lamination.

A silver halide emulsion was coated on the undercoated aluminum surface of the support prepared as described above in accordance with the Example published in the 1997 A/-1 Troi issue to obtain a color photographic paper.

Silver halide emulsion (1) used in the present invention was prepared as follows.

(L liquid) (coliquid) Sulfuric acid (/N)! Ginseng (3 liquids) The following silver halide solvent (1%) JCC〇H.

(Liquid) (!Liquid) (Liquid) (Liquid 7) (Liquid 1) was heated to jA °C, and (Liquid 2) and (Liquid 3) were added. Thereafter, (liquid 4c) and (liquid !) were added simultaneously for 30 minutes. Furthermore, io minute diameter (liquid) and (7
solution) was simultaneously added over a period of λθ minutes. Addition! The particle size and temperature were lowered to desilver. Add water and dispersed gelatin, adjust pH to 6.2, average particle size 0. 'A! μm, coefficient of variation (standard deviation divided by average particle size: s/d
)0. A monodisperse cubic silver chlorobromide emulsion having a silver bromide concentration of 70 mol was obtained. Add sodium thiosulfate to this emulsion,
Optimal chemical sensitization was performed.

Next, silver halide emulsions (2) (3) with different silver chloride contents
) (4), the above da liquid, the KBr, Naa amount and φ liquid of the liquid! Similar preparations were made by changing the addition time of the liquid as shown in Table 1.

Table 1゛ Average grain size of silver halide emulsions (1) to (4).

The coefficient of variation and halogen composition are shown in Table 2.

Layers 7 to 7 shown in Table 3 were layered on each support to obtain a color photosensitive material.

1st layer: Silver halide emulsion (4) with blue-sensitive sensitizing dye (a
) to A g X 1 mol”jrb7.oXto −
Spectral sensitization was performed by adding el. In addition, yellow coupler (
d) and the color image stabilizer (e) were mixed and dissolved in the solvent (f), dispersed, and added in a predetermined amount. This was applied as the first layer.

Third layer: Silver halide emulsion (3) with green-sensitive sensitizing dye (d
) to A g X / % 4! , (1)X/
Spectral sensitization was carried out by adding 0-'% Le. Furthermore, magenta coupler (h) and color image stabilizer (i) were mixed and dissolved in solvent (j), dispersed, and added in predetermined amounts. This was applied as the third layer.

3rd layer: Silver halide emulsion (2) K red-sensitive sensitizing dye (
C) was spectrally sensitized by adding #)t, oXto-' mol per 1 mol of Agx. Furthermore, cyan coupler (,1) and color image stabilizer (0) were mixed and dissolved in solvent (f)K, dispersed, and a predetermined amount was added. Apply this and do the first layer, binding.

The λth layer, the 3rd layer, the 7th layer, and the 7th layer were treated in the same manner. 1st layer, 2nd layer, 3rd layer, j layer,
Samples AI to AA and a comparative sample were obtained by coating the first layer and the seventh layer. (See Table V) The above sample was prepared in 1. zrz≠
Using a light source at zero, gradation exposure for sensitometry was performed through a three-color analysis filter of blue, green, and red, or image exposure for enlargement printing was performed through a negative film.

Thereafter, a photographic image was obtained through the steps of color development, bleach-fixing, and rinsing.

Development Prescription A Bleach and fix for 3 to 0 C for j seconds Prescription A J! r0C≠! Second rinse Prescription A 2r~3s0ci min 30 seconds Color developer A Water 10
0 ■ Diethylenetriaminepentaacetic acid /, 0g Sodium sulfite 0.2gN, N-
Diethylhydroxylamine ≠, 2g potassium bromide
0.6g sodium chloride
/ , jg triethanolamine
r,og potassium carbonate
JOgN-ethyl-N-(β-methanesulfonamidoethylamino)-3-methyl-≠-aminoaniline sulfate Hiroshi, jg≠-diaminostilbene-based fluorescent brightener (Sumitomo Chemical ■Whitex4') 2 Add .0g water and make 10OOCCKOH
pH 10,21 Bleach fixer formulation A Ammonium thiosulfate (wt%) /j Q door l Na 2803 / j
gNH4(Fe(III)(EDTA):l
j j gEDTA-2Na
ag glacial acetic acid
If, j/g water is added to the total amount
toootnl (pHt, Hiroshi) Rinse liquid formulation A EDTA-,2Na-λH2Q O,4
Add cg water and make the total amount tooomt
(pH 7, Hiromu) Note that when the photographic images were observed with the naked eye, the saturation of the magenta and yellow images was extremely excellent, and the sharpness had been improved to the point of being outrageous. In the comparative sample, the film was peeled off and no image could be observed.

(a) Blue-sensitive sensitizing dye (b) Green-sensitive sensitizing dye (C) Red-sensitive sensitizing dye (d) Yellow coupler (e) Color image stabilizer (f) Solvent (g) Color mixing inhibitor (h) Magenta Coupler (i) Color image stabilizer (j) Solvent Example-2 On the surface of a polycarbonate sheet (thickness/70μ),
Aluminum was vacuum deposited at io' Torr. The thickness of the deposited film was about 1000 nm. Its surface was specular. Next, approximately 1% by weight of chromium acanthus was added to the monomer composition 3 described in Example 1, based on the copolymer, to obtain an emulsion polymer. This was applied in an amount equivalent to o, 1P/rn2 and dried to form an adhesive layer. Following this, gelatin was applied and dried to form an undercoat layer. This thickness is approximately 0. /μ.

On top of this, a silver halide photosensitive layer and a protective layer were provided on the ultrafine grain high contrast silver iodobromide gelatin emulsion according to the example of Japanese Patent Application No. 4/-2μ2173 to obtain an ozotic disk recording plate.

9. A pulse signal of 400 fl Sec was applied through an acousto-optic modulation element using a He-Ne laser beam to provide signal exposure.9. Using the MQ type black and white developer shown in the example -
It was developed for 200 Cjr, fixed, washed with water, and dried. We were able to obtain a laser disk plate with high physical strength without any peeling. On the other hand, a comparative sample of a laser disk plate using only chrome alum was prepared and developed in the same manner.

The film peeled off and images could not be obtained.

Example-3 In Example-2, a patent application was made for the chrome alum in 1974/-
The following compounds (1) and (2) described in /J 713 were used, and l-hydroxy-
3,! - Disc recording plates were obtained using similar compounds (1) and (3) in place of dichlorotriazine sodium salt.

In the same manner as in Example 1, exposure, development, and fixing treatments were carried out, followed by passing through a stabilizing bath, to obtain a laser disk plate with easy film peeling and excellent image sharpness.

Compound (1) Compound (2) Compound (3) Comparative Example The emulsion polymer shown in the Example was not applied, but gelatin was applied directly to the aluminum surface, and the rest was carried out in exactly the same manner as in the Example. I got a print.

Adhesion was evaluated using the following test method.

Adhesion test method 1) Adhesion test when drying before processing After drying the photographic emulsion, attach Tottohmylar tape A3/) to the polyester adhesive tape and peel it off instantly.

2) Adhesion test when processing is wet In a wet state, after development, fixing, and washing with water, make a square-like scratch on the emulsion surface of the sample with an iron brush, and rub it 10 times with a rubber bearing a load of 3 to 9.

3) Adhesion test when drying after processing After development, fixation, washing with water, and drying, make scratches on the emulsion surface of the sample in the shape of iron moth eyes and apply knit-Mylar tape &J/2j0(:!r!%) After standing for 2≠ hours under RH conditions, the tape is instantly peeled off.

In the tests 1) to 3) above, those in which the emulsion layer does not peel off at all are graded A, those with slight peeling are graded B, and those with peeling but at the upper and lower limits of practical use are grade 0, which poses a practical problem. Items that peel to a certain degree are classified as D grade.

Table 1 shows the results of adhesion tests of the photographic color paper obtained as described above, when drying before the development process, when wet during the process, and after drying after the process described in Examples/≠.

As is clear from the results in Table 1, the adhesive layer of the copolymer composition used in the present invention improves the adhesion, and the addition of a curing agent further improves the adhesion. I know that there is.

Claims (3)

[Claims] (1) In a photographic support in which an adhesive layer of a laminated copolymer composition is provided on a metal surface with specular reflection property or type 2 diffuse reflection property, diolefins and other polymerizable ethylene-based A photographic support comprising a copolymerizable composition comprising an unsaturated monomer and/or a monomer having at least one carboxylic acid or phosphoric acid group. (2) In a photographic support provided with an adhesive layer of a laminated copolymer composition on a metal surface, A: butadiene monomer B: a monomer selected from itaconic acid, methacrylic acid, and acrylic acid. Both one type of monomer and C: styrene,
The copolymer consisting of at least one monomer selected from α-methylstyrene, methyl methacrylate and acrylonitrile contains 10 to 90% by weight of butadiene monomer A and 0.0% by weight of acid units of B. A photographic support according to claim 1 containing 2 to 20% by weight. (3) As a hardening agent for the layer or gelatin of the copolymer composition, active vinyl groups, epoxy groups, ethyleneimino groups, methanesulfonic acid ester groups, active ester groups, active carbodiimide groups, active sulfimide groups, isoxazole groups , or a compound having an isocyanate group, and at least one compound selected from the group of chromium alum and chromium acetate.