JPH0375740A - Photographic printing paper base - Google Patents

Abstract

PURPOSE:To enhance adhesion and to give antistaticness by forming an undercoat layer containing a specified material on the surface of a polyolefin base. CONSTITUTION:The undercoat layer formed on the surface of the polyolefin base contains gelatin, a carboxylic-activated type hardening agent and a water- soluble polymer compound represented by formula I or II in which A is a vinyl monomer; B is H or a group of formula III of IV; when Z is 0, B is H, and when R is alkyl, B is H; M is H or a cation; R is a group of formula V or VI; R' is alkyl, aralkyl, aryl, a heterocyclic group or a nonmetal atomic group necessary to form a heterocyclic group together with R''; R'' is H, lower alkyl, or R'' may form said ring together with R'; each of R1 and R2 is H or lower alkyl; X is a group of formula VII or VIII; R3 is halogenoalkyl or the like; (m) is 40 - 60, (p) is 0 - 60, (q) is 0 - 50, (r) is 0 - 5, (x) is 0 - 70; (y) is 20 - 80, (z) is 0 - 80, m + p + q + r = 100, and x + y + z = 100.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a photographic paper having a surface which has been subjected to a subbing treatment, has improved adhesion to adhered substances, and has an antistatic property. Regarding the support. [Prior Art] In recent years, synthetic resin films have come to be used as photographic supports instead of ordinary paper because of their excellent water resistance, smoothness, etc. Therefore, it was applied to the support of photographic paper, but a photographic light-sensitive layer mainly composed of gelatin,
The adhesion to the anti-curl layer on the back side of the support was not sufficient and it was easy to peel off, resulting in an unsatisfactory result. For this reason, activation treatments such as corona discharge have been performed on the surface of the support prior to coating with a photographic light-sensitive layer, etc., but no satisfactory results have been obtained. Furthermore, when manufacturing photographic materials, it is extremely important to impart antistatic ability to the support; if this is insufficient, partial fogging, which is unfavorable for photographic properties, called static marks will occur. . Originally, photographic materials must have both adhesive properties and antistatic properties, but conventional treatments to improve adhesion and treatments to impart antistatic properties are different from each other, for example, by sufficiently imparting adhesive properties. If you try to add sufficient antistatic ability, the antistatic ability will decrease, and conversely, if you try to provide sufficient antistatic ability, the adhesion will decrease, so each processing effect tends to be reduced, making it difficult to obtain a satisfactory photographic material. The current situation is that this is not the case. [Problem to be Solved by the Invention 1] The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a photographic material having a surface with improved adhesiveness and antistatic ability. An object of the present invention is to provide a photographic paper support for use in printing. [Means for Solving the Problems] The above object of the present invention is to coat gelatin, a water-soluble polymer compound represented by the following general formula, and a carboxyl group-activated hardener on at least one surface of a substrate having a polyolefin resin surface. This is achieved by a photographic paper support characterized by being provided with a subbing layer containing at least one subbing layer. General formula (wherein A is a vinyl monomer, B is hydrogen, then B is hydrogen, and when R is an alkyl group, B is hydrogen, M is hydrogen or a cation (however, as shown in the above general formula) The cation substitution rate for all M contained in the water-soluble polymer compound is 10% or more.) R# R is 10-R' or -N-R' where R' is an alkyl group, aralkyl group, aryl group, heterocyclic residue, or a nonmetallic atom necessary to form a heterocyclic ring in cooperation with R'',
R" is hydrogen, a lower alkyl group, or a nonmetallic atom necessary to form a heterocyclic ring in cooperation with R', R1 and R2 are hydrogen or a lower primary alkyl group, X is hydrogen, -C-O-, or 1 -O-C+, R3 is a halogenoalkyl group or a halogenoalkyloxyalkyl group, m, p, q. r, x, y, z are values indicating the mol% of each monomer, - is 40 ~60, p is O~60゜q is O~50
1" is O~5, x is 0~70Sy is 20~801z is O
~80, l +p +q +r-100. x+y
・It is 2.100. >The present invention will be explained in more detail below. The specific water-soluble polymer compound used in the present invention is represented by the following general formula. General formula % Formula % (In the formula, A is a vinyl monomer, B is hydrogen, when B is hydrogen, and when R is an alkyl group, BG; L hydrogen, M is hydrogen or a cation, R is R# Tsui- 0-R' or -N-R' where R' is an alkyl group, an aralkyl group, an aryl group, a heterocyclic residue, or R
“Nonmetal atoms necessary to form a heterocyclic ring in cooperation with R
# is hydrogen, a lower alkyl group, or a nonmetallic atom necessary to form a heterocyclic ring in cooperation with R'; R1 and R2 are hydrogen or lower alk; R3 is a halogenoalkyl group or a halogenoalkyloxyalkyl group; , q, r, x
,y. 2 is a value indicating the mole% of each monomer, and Sono is 40 to 60% p is O to 60. Q is O~50, "is 0~5
, X is O~70. (2) is 20-80, Z is 0-80, g++p+q+r -100, x+y+z 100. > In the above general formula, vinyl monomers include, for example, styrene, styrene substituted with nido O group, fluorine, chlorine, bromine, chloromethyl group, lower alkyl group, etc., vinyl methyl ether, vinyl ethyl ether, vinyl chloroethyl ether, Unsaturated acids such as vinyl acetate, vinyl chloroacetate, vinyl propionate, acrylic acid, methacrylate or itaconic acid, alkyl acrylates or alkyls having 1 to 5 carbon atoms, unsubstituted or substituted with chlorine, phenyl, etc. Examples include methacrylate, phenyl acrylate or phenyl methacrylate, acrylonitrile, vinyl chloride, vinylidene chloride, ethylene, acrylamide, acrylamide substituted with an alkyl group having 1 to 5 carbon atoms, chlorine, phenyl group, etc., vinyl alcohol, glycidyl acrylate, acrolein, etc. ,
Preferably styrene, styrene having a substituent, vinyl acetate, vinyl methyl ether, alkyl acrylate,
Acrylonitrile, etc. In addition, the alkyl group of R' in the above formula has 1 carbon number.
-24 is preferred, and it may be any alkyl group such as a straight-chain alkyl group, a branched alkyl group, or a cycloalkyl group, and the alkyl group may have a substituent, and the substituent may include a hydroxy group, Desirable results can be obtained with hydroxycarbonyl 1 dicarbonyl groups, in particular halogenoalkyl groups or halogenoalkyloxyalkyl groups substituted with halogens such as fluorine. group or a halogenocycloalkyl group, and the number of halogens is preferably 1 to 37. This halogenoalkyl group and halogenoalkyloxyalkyl group and the halogenoalkyl group and halogenoalkyloxyalkyl group of R3 in the above formula are preferably represented by the following general formula [A
]. General formula [A] (wherein R4, Rs, Rs, R7, Ra are hydrogen or fluorine, R2 is O or 1, when R2 is 0, nl is Q1, when n2 is 1, nl is 2 or 3, R3 is an integer from 1 to 17, provided that nl + n3
is 1-17. However, if there are two or more R4s in the structural formula, they may be different groups, such as one being hydrogen and the other fluorine, and similarly, if there are multiple Rs, Rs, and R7 in the structural formula, Sometimes it may be a different group. ) Furthermore, when R' in the general formula is such a halogenoalkyl group or a halogenoalkyloxyalkyl group, preferably R in the general formula is 10-R.
'is. Furthermore, the aryl group such as phenyl group or aralkyl group such as benzyl group in R I may have a substituent, and examples of this substituent include halogens such as fluorine, chlorine, and bromine, lower alkyl groups, and hydroxyl groups.・Hydroxycarbonyl group ・Cationic oxycarbonyl group ・
Examples include nitrile groups and nitro groups. Also, R in the formula
The heterocyclic ring of ' or the heterocyclic ring formed by R' and R'' is a saturated or unsaturated heterocyclic ring containing oxygen, sulfur, or nitrogen, such as aziridine, virol, pyrrolidine, pyrazole, imidazole. - It is a heterocyclic ring selected from heterocyclic rings such as ikudacillin, triazole, piperidine, piperazine, oxazine, morpholine, thiazine, etc. In addition, the cation of M in the formula is, for example, ammonium ion, sodium ion, potassium ion. , cations such as lithium ions, and preferably the substitution rate of cations is about 10% or more for all M contained in the water-soluble polymer compound.The water-soluble polymer compound represented by the above general formula is They may be used alone or in combination of two or more, preferably those having an average molecular weight of about 500 to 500,000. Typical water-soluble polymer compounds used in the present invention include: Exemplary compounds (1) (a=45, p=3L Q=20) (2) (3) (-=55, p"2G+ q=20+ r=5
)(4) (5) (Otori=50* m=20s q=30) (Ron=50+
m=30s q=20)

[(m=40e m=30s q=25e r=5
) (10) (m=551 m=20s q=25) CFri 4 (m=50t m=20s Q=Q++Qx*
q+=20w ax=10) (CF,). (m=70. z=30) (ma) (8) (m=50+ p=3s, q==10+ r=
5 ) (CFx)t (m=50. m=20. Q=30) (,=4
Q, m=35s q=zo, m=5) (13) Hs (14) (m=1(L m=60s z=30) (m=10s
m=80s z=30) CF. (m=55s m=45) (F=F++Fts Fl=20゜lm=40゜m=40) (m=40゜m=40r m=20) CF. (m=50- m=50) (21) (m=40゜p=40v, ='20) (23) (m=40゜p 5G. q=10) (m=40゜F=F++F* e F+=20* y*=20* m=20) (19) (m=15゜■ CF. y-45v m=40) (y wealth 6G, m=40) and H2 ■ (CF*)* CF . (24) (25) (m=10e m=30t m=60) (26) (m=50°9=21 , =48) (27) (28) (m=40°p=8e q=47+ r =5) (29) (m=50゜p=1゜m=49) (m=50゜D=7 books m=43) (33) (CFx)g (m=55t p=L m=43) ■ (CF,)1 exposure (m-5(LD-7+ Q++mu= q +Q+=
33e q*=lo) (m=50* m=50) (30) (31) (m=50゜p=9゜q=3L r=5) (CFx)t (m=5(L p= 81) Q=42) (m=40゜(CFri4 p=60) (36) (m=40゜m=58゜r*2) (38) (-=45.Q+ 10Qt=Qkaiq,= ri o. CH. Mu = 5) (m, +ms = m, theory, = 40° phantom = 20° m = 40) (41) (45) (x = 45° yl 10 Ft = Book F + = 101 F *=40* z=5) (X=50°F+ +Ft=F snow F+ =30* ys=IL z=2) (Xl+X!=X snow wing, =16°x, =35°y=45.1 =4) (X-31゜y=eo, z←9) CH3 (CFdt CF. (X=27゜y=70y z=3) (CF,). (48) Su a (x=30. y= 70) (x=42°F=58) (s=55°p=2°q=43) (s=45°+1"51Q≦50) The molecular compound is synthesized by a known method. That is, it is well known that maleic anhydride copolymers are extremely common polymers, and these derivatives can also be synthesized using compatible alcohols or amines. It can be easily obtained by reacting with maleic anhydride copolymer, and it can also be obtained by copolymerizing purified product by reacting alcohol or amines compatible with maleic anhydride monomer with other vinyl monomers. In addition, acrylates such as halogenoalkyl and halogenoalkyloxyalkyl are described in Journal
of Polymer Science
fPolymer 5science, 15515~5
74 (1955)
It can be easily synthesized by the monomer and polymer synthesis method described in No. 357, M1Bilnig. In the present invention, the amount of the water-soluble polymer compound used is 10 to 80G+1! II/f is preferable, and 30 to 4G08111/v'' is particularly preferable.Next, the hardening agent that acts by activating the carboxyl group will be explained in detail.The carboxyl group in the present invention A hardener that acts by activation (hereinafter referred to as a carboxyl group-activated hardener) refers to a hardener that reacts with a carboxyl group in a binder.Carboxyl group-activated U-type t' in the present invention Examples of the !I! agent include compounds represented by the following general formulas [H-I] to [Rho methyl group, ethyl group, benzyl group, phenethyl group, 2-ethylhexyl group, etc.), or an aryl group (e.g. phenyl group, naphthyl group, etc.), and it is also preferable that they bond with each other to form a heterocycle with a nitrogen atom. Examples of the group ring include a pyrrolidine ring, a piperazine ring, a morpholine ring, etc. R3 is a substituent, such as -NR4R5 (R4 and R5 are synonymous with R1 and R2), a halogen atom, a carbamoyl group,
Represents a sulfo group, ureido group, alkoxy group, alkyl group, etc. R3 includes those having an Il substituent, and examples of the substituent include a halogen atom, an alkyl group, a carbamoyl group, a sulfo group, a sulfooxy group, and a ureido group. m represents O to 5, and when Peng≧2, a plurality of R3s may be the same or different from each other. xe represents an anion, and preferable examples include halide ion, sulfate ion, sulfonate ion, CIO
+ e, BF4 e, PF6 etK, etc. l represents O or 1, n represents O~2, and when forming an inner salt, n is O. ] General formula H-I [] R1-N-C-N-R2 [wherein R115 and R2 are a cycloalkyl group (e.g. cyclohexyl group) or an alkyl group (e.g. methyl group, ethyl group, 2-ethylhexyl group) groups), alkoxyalkyl groups such as methoxyethyl groups, benzyl groups, aralkyl groups such as phenethyl groups, -R3-N-R5 and IBR6
(XCI)w represents a group. Here, R3 is an alkylene group (e.g., ethylene group, propylene! IJ trimethylene group, etc.), R4R5 and R6
represents an alkyl group (e.g., methyl group, ethyl group, etc.), and when two of R4-R6 are combined to form a heterocycle (e.g., pyrrolidine ring, piperazine ring, morpholine ring, etc.) with a nitrogen atom, or a substituted Including cases where it has a group. Preferred examples of the substituent include carbamoyl groups such as diethylcarbamoyl and piperidinocarbonyl, and sulfo groups. The term represents O or 1, xe represents an anion, halide ion, sulfonate ion, sulfate ion, C
IO+ e, BF4 e. PFse and the like are preferred. It also forms an inner salt □
If - is 0. ] General formula [H-1[[] [wherein R1 is an alkyl group (e.g., methyl group, ethyl group, butyl group, as well as an aralkyl group such as benzyl group, phenethyl group) or an aryl group (e.g.) T-nyl group ,
Naphthyl group, etc.). These groups further include those having a substituent, and examples of the substituent include a carbamoyl group, a sulf7moyl group, and a sulfo group. R2 and R3 represent a hydrogen atom or a substituent such as a halogen atom, an acylamido group, a nitro group, a carbamoyl group, a ureido group, an alkoxy group, an alkenyl group, an alkenyl group, an aryl group, an aralkyl 1&, etc., and R2 and R3 represent It is also preferable to bond to form a condensed ring together with a pyridinium ring skeleton. X represents a group that can be eliminated when the compound represented by the general formula [H-II reacts with a nucleophile. Preferred examples include a halogen atom, a sulfonyloxy group, a sulfoalkyl group, 10, and 41 (R4 represents an alkyl group or an aryl group) represented by P(OR'')2. X is sulfonyloxy When it does not represent a group, it is also preferable that X and R1 are bonded. Ye represents an anion, such as a halide ion, sulfonate ion, sulfate ion, C104e, BF order +9.P
Fse and the like are preferred. - represents O or 1, and m is O when forming an inner salt. To the general formula [H-IVI 6 [wherein, the definitions of R1 and R2 are exactly the same as the definitions of R1 and R2 in the general formula [H-II], and R3 is an alkyl group (e.g. methyl group, ethyl group, butyl group) In addition to the above, it also represents an aralkyl group such as a benzyl group or a phenethyl group), or an aryl group (such as a phenyl group or a naphthyl group). xe is an anion, halide ion, sulfonate ion, HM ion, Cj
! 04e, 8F4e, PFse, etc. are preferred.] General formula [Rho V]
The definitions of R1 and R2 in -II are exactly the same, and R1 and R3 may further form a ring. xl represents a group that forms 1l1211L when reacted with a nucleophile, and is preferably a halogen atom, a sulfonyloxy group (
Preferably, alkylsulfonyl group (4), arylsulfonyloxy), 1-pyridium group, imidyl group (J!
! (e.g. phthalimidyloxy, succinimidyloxy, glutarimidyloxy), azolyloxy groups,
Examples include ammonio group. Examples of the anion represented by Yle include halogen ion, sulfonate ion, sulfate ion, CIO*e, BF4e, PFse
, phosphonate ion, and phosphate ion. ]
General formula [H-Vll R' -C-N-R2 1 [wherein R1 and R2 are an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, or -NR
3R (R3 and R4 represent an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an aromatic heterocyclic group,
(including those in which R3 and R4 are combined to form a ring). ×1 is the same as the definition of ×1 in the general formula [HV]. ]General formula H-■] [In the formula, R1, R2 and R3, R4 and R5R6 are the same as the definition of RI R2 in the general formula [+-1-11] ×1 and YleG;
L general formula [H-V] 1cj5Gt6Y+ Same as the definition of 8. ] General formula [H-■] [In the formula, R1 represents an aryl group, 2 represents a nonmetallic atomic group necessary to form an aromatic heterocycle, and the ring formed by R1 and 2 has Ij/111 Including things. Ye represents an anion, Tsuru represents 0 or 1, and Sono represents O when forming an inner salt. ] As the carboxyl group-activated hardener preferably used in the present invention, for example, a methanesulfonic acid ester type hardener represented by the following general formula [H-rX] and a molecule of the following general formula [H-Xl] Examples include so-called ethyleneimine type hardeners having two or more ethyleneimino groups. Further, these methanesulfonic acid ester type hardeners and ethyleneimine type hardeners are synthesized by known methods. General formula [H-rX] CHa 8020-R-O8O2CHa [wherein R is -(CH2)2- - (CH2)a --(CH2)
Gin-, -(C2Hto-〇-C2H4)-. -(CH2CmiCCH2)- or CH3-(CH2-C-CH2)-. ]O2 Among these, it is particularly preferable that R is -(CH2)3-. General formula [H-Xl [wherein A is -8O2--502NH--CO--CO
O--CONH- -C8NH--PON (CH2)2NH-, etc., and R is an alkylene group, an arylene group, -8i R
+ R2-PRa R4--P (NC284)2
-1 nitrogen-containing heterocyclic group, etc., and these groups may have a substituent. (R1 and R2 are alkoxy groups, and R3 is a hydrogen atom, an alkoxy group, a substituent such as -N (CH2)2-, etc.) Also, -A-R-A- may form a ring. i, m,
Each n represents an integer. ] The carboxyl group-activated hardener used in the present invention has the general formula [H-1
In addition to the compounds represented by formulas 1 to 1 to H-Xl, JP-A-50-38540, JP-A-52-93470,
JP-A-56-43353, JP-A-58-113929
Also preferred are the compounds described in US Pat. No. 3,321,313. Specific examples of the compounds used in the present invention are classified below, but the present invention is limited to the general formula [H-I
Exemplary compounds represented by
No. 1-59625, JP-A-6L-9641J! , JP-A-62-262854 and JP-A-62-264044
@) -1-1 -1-2 -1-3 -I-4 H-1-5 H-1-11 -r-12 -1-6 -1-13 1(-1-7 - 1-8 -1-9 -1-15 -1-10 Exemplary compound-n-5 represented by the general formula [H-If] (These compounds and their synthesis methods are described in JP-A No. 1-126125 and For details, refer to JP-A No. 52-48311.) -11-1 -ff-6 -n-2 -11-7 tC -1f-3 -u-4 Exemplary compound H-111- represented by the general formula [Rho ■] 5 (These compounds and their synthesis methods are detailed in JP-A-51-4-4140, JP-B-57-46538, and JP-B-58-50669.) H-1 [[-1 -11-2 General formula Exemplary compounds represented by [H-rV] (These compounds and their synthesis methods are detailed in JP-A-52-54427.) -11-3 -IV-1 -IV-2 -m-4 H- 111'-3 Exemplary compound-V-4 represented by the general formula [Rho v1 (These compounds and their synthesis methods are detailed in JP-A-1 225148 and JP-A No. 61-240236.) -V-1 -V-5 I -V-6 -V-2 -V-7 -V-3 -V-8 H-?9 H-V!-1 -W-2 -V-10 )1-■-3 - V-11 -Vf-4 -V-12 -Vl-5 Exemplary compounds represented by the general formula [H-Vll (These compounds and their synthesis methods are described in JP-A-62-68866 and JP-A-62-68867) 〉 Exemplary compound H-■-1 represented by the general formula [H-■] (These compounds and their synthesis method are detailed in JP-A-1-128241.) -2 H-■-2 H-■-3 -Vf-3 Exemplary compounds represented by the general formula [H-■] (These compounds and their synthesis methods are detailed in JP-A-2-234152@) Mountain H-%1-4 Exemplary compound represented by general formula [H-Xl -X-1 -X-2 -X-3 -X-4 -X-5 -X-6 General formula [represented by H-III] Exemplary compound H-I!-
1 CH, So! 0-(CH2)ffi-OS02CH2-
ff-2 CHaSOtO(CH2)3 0SOzCHs-IK-
3 CH3So□O(CHz)+-OS 02CH3-IK
-4 CH3SOzO-(C*H40CzH4) O8O*
CHs-ff-5 CH3SO□0-(CH,CmiCCHt) 0SOz
CHsCHsSOtO-(CHt-C-CHt)-0S
OzCH2-X-7 -X-8 -X-9 -X-10 -X-11 -X-12 H-X-13 H-X-21 -X-22 -X-19 CH. -X-20 Compound described in JP-A No. 50-38540 -0-1 -0-2 -0-3 Compound H-0-4 described in Danwi Surisu Special Report @52-93470 -0-5 - 0-6 -0-7 -0-8 -0-14 -0-15 -0-16 -0-17 Compound described in JP-A-58-113929 -0-9 -0-10 U.S. Patent ff13,321 Compound-0 described in No. 313
-11 -0-12 -0-13 The amount of carboxyl group-activated hardener used in the present invention can be arbitrarily selected depending on the purpose, but ranges from 3 x 10-5 mol to 15 x 10 mol per 1 g of binder. Preferably, it is used in proportions ranging up to 'molar. The binder herein refers to gelatin and the water-soluble polymer compound described above. Further, the carboxyl group-activated hardener and other hardeners can be used in any ratio, but if the carboxyl group-activated hardener is 1, the other hardeners are 0.
The range from 01 to 1 is preferred. Gelatins used in the undercoat layer in the present invention include lime-treated gelatin, acid-treated gelatin, and Bull. Soc, Sci, Phot, Japan,
In addition to enzyme-treated gelatin as described in No. 16, p. , maleimide compounds, polyalkylene oxides, engineered boxy compounds, etc.). In the present invention, the coating amount of the undercoat layer is 0.05M, because if it is too small, sufficient antistatic effect will not be obtained, and if it is too large, the film adhesion will deteriorate and the sharpness of the image will be impaired.
It is preferably in the range of f to l/f, particularly 0.1 to o, 5 g/f. Furthermore, various additives can be added to the undercoat layer as necessary. For example, a matting agent such as amorphous silica may be added. The amount of the matting agent added is preferably 1% to 20% by weight, particularly preferably 2% to 12%, based on the weight of the binder. Next, the substrate having a polyolefin resin surface in the present invention will be described in detail. Examples of the polyolefin resin include homopolymers or copolymers of ethylene, propylene, butene, isoprene, pentene, methylpentene, etc., but are not limited thereto. In addition, as a substrate for providing polyolefin resin,
Examples include polyester, polypropylene, paper, etc., which are commonly used as supports, but polypropylene is preferred. In the present invention, it is sufficient that the polyolefin resin is exposed on the surface, so it is not only possible to use a substrate coated with a polyolefin resin, but also a substrate that is made of a polyolefin resin without a coating layer, for example, a substrate made of a -layer. Also included. The substrate having a polyolefin resin surface in the present invention is made from so-called synthetic paper or natural pulp, which is made by mixing polypropylene with fillers and additives, melt-kneading the mixture in an extruder, and extruding it through a die/slit to form a film. Examples include so-called laminate paper, which is made of high-quality paper coated with polyethylene, and a composite film, which is made of polyester coated with polyethylene containing titanium oxide. In the present invention, it is preferable to provide a polyethylene layer on at least one surface of the substrate having a polyolefin resin surface. In the present invention, polypropylene resin is used as the main raw material,
It is preferable that an inorganic filler is added to this, and a polyethylene layer is provided on the base of an opaque resin film produced by a two-wheel stretched film molding method. The film thickness of the substrate having a polyolefin resin surface used in the present invention is preferably 50 to 250 μm. An undercoat containing at least gelatin, a specific water-soluble polymer compound represented by the above-mentioned general formula, and a carboxyl group-activated hardening agent is applied to at least one surface of the substrate having the polyolefin resin obtained as described above. The coating liquid is applied by various known methods. For example, a roll coating method, a gravure roll method, a spray coating method, an air knife coating method, a bar code method, an impregnation method, a curtain coating method, etc. can be applied alone or in combination. . At least one light-sensitive silver halide photographic emulsion layer is coated on the photographic paper support of the present invention formed as described above. In this case, a surface activation treatment such as corona discharge can be performed, if necessary, prior to coating the photosensitive silver halide photographic emulsion layer. Hydrophilic colloids used in the present invention include, for example, proteins such as gelatin, albumin, and kabiin; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyvinyl alcohol partial acetals, polyN-vinyl biOlidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Preferably, gelatin is used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull Society Science Photography Japan <Bull
, 5OC5Sci, Phot, Japan),
No., p. 16.30 (1966) Oxygen-treated gelatin as described in 2 may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used, and gelatin derivatives, gelatin and other highly concentrated gelatin may also be used. It also includes graft polymers with molecules. In the present invention, any of various conventional silver halide emulsions can be used as the silver halide emulsion used in at least one silver halide emulsion layer provided above the undercoat layer. Examples include emulsions for black and white photographic paper, direct positive emulsions for black and white, negative emulsions for ordinary color photographic paper, internal latent image type direct positive emulsions for color, and reversal emulsions. When an internal latent image type silver halide photographic light-sensitive material is used, the light-sensitive material is provided with a silver halide emulsion layer containing internal latent image type silver halide. As the emulsion for forming the emulsion layer, various conventionally known internal latent image type silver halide emulsions can be used. For example, the converted silver halide emulsion described in U.S. Pat. No. 2,592,250, Japanese Patent Publication No. 58-14
Laminated structure type silver halide emulsions described in Publication No. 12 etc., Japanese Patent Publication No. 52-34213 and Japanese Patent Publication No. 6G-55
Core/with chemically sensitized particle interior described in Publication No. 821 etc.
Examples include shell type silver halide, core/shell type emulsion described in Japanese Patent Publication No. 6-55820. The emulsion can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye. Silver halide emulsions also contain antifoggants, stabilizers,
A hardening agent etc. can be added. As the binder for the emulsion, hydrophilic colloids such as those mentioned above may be used, but it is advantageous to use gelatin. The strength of silver halide emulsion layers and other hydrophilic colloid layers can be increased by using a hardening agent. Examples of such hardening agents include aldehyde-based, aziridine-based, isoxazole-based, epoxy-based, and vinyl-based hardeners. Sulfone type, acryloyl type, carbodiimide type, triazine type, polymer type,
In addition, maleimide-based, acetylene-based, and methanesulfonic acid ester-based hardening agents can be used alone or in combination. In addition, plasticizers, dispersions of water-insoluble or poorly soluble synthetic polymers (latex), coating aids,
Antistatic agents, formalin scavenger-1, optical brighteners, matting agents, lubricants, image stabilizers, surfactants, color fog preventive agents, development accelerators, development retardants, bleach accelerators, etc. may be included. You can also do it. Particularly useful methods for coating the light-sensitive silver halide photographic emulsion layer are extrusion coating and curtain coating, which allow two or more layers to be coated simultaneously. Further, the coating speed can be arbitrarily selected, but from the viewpoint of productivity, a speed of 50 a/min or more is preferable. [Example] Hereinafter, it will be explained in more detail using Examples. Example 1 Production of 1 to 5 Melt index (Ml) 80 parts of polypropylene of 1G/10 minutes, Calcium carbonate 19 with an average particle size of 1.5 μm
．． A mixture of 9 parts and 0.1 part of 2,6-di-tert-butyl-para-cresol (hereinafter abbreviated as BHT) was melt-kneaded in an extruder, extruded into a sheet, and then cooled. The obtained sheet was heated to 140° C. and then stretched 4 times in the machine direction to obtain a film. (AI) Next, MI 10! II/10 min boria 0 pyrene 68
．． 9 parts, BHTo, 1 part, 15 parts of fine talc powder with an average particle size of 2.0 μm, 15 parts of rutile-type titanium oxide with a particle size of 0.3 μm
After melting and kneading a mixture of 1.0 parts and 1.0 parts of fatty acid metal salt in an extruder and extruding it into a sheet, it was immediately laminated on both sides of the film A layer and cooled while being nipped with rolls to form a three-layer structure sheet. I got it. This three-layer film sheet was heated to 160° C. and then stretched about 10 times in the transverse direction to obtain a film with a thickness of 110 μm. The thickness of each layer of the obtained film was 60 μm for A layer, 25 μm for front and back Bll, and 25 μm for each layer.
Met. This will be referred to as support 1. After corona discharge treatment on one side of the support 1, using a melt extruder, low density polyethylene (density 0.918° MIg,
A resin composition consisting of 30 parts of a masterbatch in which 80% by weight of titanium oxide was kneaded into 51J) and 70 parts of low density polyethylene was coated with a resin layer of 5μ, and this was used as support 2. Next, paper with a basis weight of 75 g/f is run at 80+a/min, and after corona discharge treatment on the back side in the first zone, low density polyethylene (density 0.918° MI5) 50
Part, high density polyethylene (density 0.965, MI7) 5
A resin composition consisting of 0 parts was applied by melt extrusion at a coating amount of 16 g/V to form a resin layer with a matte surface. After corona discharge treatment on the cover surface in the second zone, 80 parts of a master batch of 80% by weight of titanium oxide kneaded into low density polyethylene (density 0.918. M I 8.5) was prepared using a melt extruder. Density polyethylene (density 0.918.
A resin composition consisting of 45 parts of M I 5.0) and 25 parts of high-density polyethylene (density 0.965. M T7.0) was applied by melt extrusion coating at 1160/f to form a resin layer with a semi-gloss surface. A polyethylene-coated paper having a thickness of 110 μm was obtained, which was used as Support 3. 20 parts by weight of anatase-type titanium oxide with an average particle size of 0.35μ and 80 parts by weight of polyethylene terephthalate with an intrinsic viscosity of 0.80 were mixed and extruded using two co-rotating screws (1).
The mixture was melt-kneaded using a 20M53/60 (manufactured by Automatic Co., Ltd.) and then pelletized. This pellet was vacuum dried at 180°C for 6 hours, then melted in an extruder and extruded from a slit die onto a rapidly cooling rotary drum to form an amorphous sheet with a film thickness of 420μ, and then heated at 95°C in the longitudinal direction for 2.6 Stretched twice, then 110°C in the transverse direction
The film was stretched 3.0 times, then heat-set at 210°C, and then cooled to obtain a white opaque film support with a thickness of 75 μm, which was used as Support 4 (for comparison). After corona discharge treatment on one side of the polyethylene terephthalate film, using a melt extruder, low density polyethylene (density o, 918.M I
30 parts of a masterbatch in which 80% by weight of titanium oxide is kneaded into 8.5(1), 70 parts of low-density polyethylene
The resin composition was coated with a resin layer of 30 μm, and this was used as a support 5. After performing corona discharge treatment on the surface of the obtained support,
A subbing layer having the composition shown in Table 1 was provided. Next, follow the steps shown below to create an internal latent image type red-sensitive emulsion! ! i (First layer) A 20% inert gelatin solution was maintained at 50° C., and the following solutions A and B were simultaneously added and poured over 3 minutes while stirring. 1
After 0 minutes, Solution C was added by injection over 3 minutes. After aging for 40 minutes, the solution after removing excess salt by precipitation and washing with water and solution E were added, and AOCj! Silver chlorobromide consisting of 95 mol % and 5 mol % of Ao Br was laminated on the surface. Excess water-soluble salts were removed again by the precipitation washing method, and a small amount of gelatin was added and dispersed. Thereafter, in this silver halide emulsion, the following sensitizing dye [C], 2,5-dioctylhydride 0quinone protected and dispersed with dibutyl phthalate, and the following cyankabu, lar (C-
1), a liquid containing 4-hydroxy-6-methyl-1,3,
3a, 7-chitrazaindene, 1-phenyl-5-mercaptotetrazole, gelatin, and the following coating aid (S
-1) Add an appropriate amount. The amount of silver coated was set to 0.4Q/f.

[1] (s - i) First intermediate 1i (No. 211> 2,5-dioctylhydroquinone dispersed in dioctyl phthalate, ultraviolet absorber Tinuvin 328 (manufactured by Ciba Geigy), coating aid (S-1) A gelatin solution containing Tinuvin 328 was prepared and coated to give a coating weight of 10.15 Mt'. Green-sensitive emulsion layer (third layer) Silver halide grains were prepared in the same manner as the red-sensitive emulsion. This was sensitized as described below. Pigment [■], dibutyl phthalate
A liquid containing Tect-dispersed 2,5-dioctylhydroquinone and the following magenta coupler (M-1), 4-hydroxy-6-methyl-1,3,3a, 7-chitrazaindene, 1-phenyl-5-mercaptotetrazole,
Furthermore, appropriate amounts of gelatin and coating aid (S-2) are added. The amount of coated silver was 0.40/V. [11 Second intermediate layer H (41st!) Same formulation as the first intermediate layer with a coating amount of 0.2
It was set as Q/f. Yellow filter layer (No. 57!> 2,5-dioctyl dispersed in yellow colloidal silver and dibutyl phthalate made by liquefaction under alkaline pouring reducing agent (weak reducing agent removed by noodle water washing method after neutralization) Add the hydroquinone liquid, the above coating aid (S-2) and the following W! film agent (H-1) (add immediately before coating),
Coating amount a 0.1 (1/rSGel coating full G, 91
) /l'. (H-1) (S-2) C, H-CH2-Coo-CH, -0H-(CH,), -CH3
Third Intermediate Wi (Sixth Layer) A gelatin solution containing a coating aid (S-1) was prepared, and the gelatin coating amount was set to 0.5Q/v'. Blue emulsion! ! (No. 711> The following emulsion was used here. In other words, the following solutions A and B were simultaneously added to a 1.5% inert gelatin solution while stirring at 60°C and injected over a period of 15 minutes. 15 minutes After that, the solution was injected over 2 minutes, and the 1 min diameter hypo was 3 so/A.
The amount equivalent to Q was added and further aged for 40 minutes. Sampling and compositional analysis revealed AoCffi 4 mol%, AgSr.
It was salt-rich silver iodide consisting of 96 mol% and Aa 12 mol%. After removing excess salt by the precipitation water washing method, the solution and E solution were added to give 97 mol% of AoCIt and AgB.
After laminating a surface layer of r3-E1%, excess salt was removed by a precipitation washing method, and gelatin for dispersion was added to prepare a product. Next, a solution containing the following sensitizing dye [■], the following yellow coupler (Y-1) dispersed with dioctyl phthalate, 2-
Contains mercaptobenzothiazole, 4-hydroxy-6-methyl-1,3,38,7-titrazaindene, gelatin, the following coating aid (S-3) and hardener (H-3) (added immediately before coating) Using liquid, coated silver amount 0.5 Q/f
It was applied so that [1111 Fourth intermediate layer (811th) Tinuvin 328 was coated in the same manner as the first intermediate layer so that the coating amount was 0.3 mm/f. However, just before application, use a hardener (
H-3) was added. Reservoir layer (9th layer) Colloidal silica, coating aid (S-3), hardener (H-
A gelatin solution containing 2) and (H-3) (added immediately before coating) was used to coat the gelatin at a rate of 11.Oa/V.A red-sensitive emulsion was applied to surface-treated polyethylene laminate paper. Nine layers up to the protective layer were coated and dried using a simultaneous coating method. (H-2) OsNa (H-3) Each of these samples was incubated so that the hardness of the emulsion layer was appropriate, and then processed. A film attachment test, a static mark test, a handling test, and a sunlight exposure test were conducted. Each test was conducted as follows: <Processed film attachment test> After immersion in a developer solution at 38°C for 2 minutes, the emulsion was The layer was scratched in a grid pattern with an iron nail and rubbed with a finger to observe the degree of peeling.The state where the grid pattern remained completely was rated O, and the state where more film remained was ◎ , the state in which the corners of the lattice have been removed is indicated as Δ, and the state in which the grid is completely peeled off is indicated as ×. Static mark test〉 Each sample was cut into a length of 891111 x 1 m and placed in a dark room at 25°C and relative humidity of 30%. The sample was wrapped in a loop around three rubber rolls, rotated without slipping between the sample and the roll, and then developed to examine the occurrence of static marks due to peeling and charging. Sunlight exposure test after treatment Wedge exposure treatment A sunlight exposure test was conducted by exposing the sample to sunlight for 60 days. Cases in which the 1itil image layer and the support were peeled off at the edges were marked as ×,
The case where it did not peel off was rated O. The above results are shown in Tables 2 to 5. Table-2 (Process 1!! Discipline test results) Table-3 (Static mark test results Table-4 (post-treatment sunlight 1111 exposure test wA) Table-2, Table-3
As is clear from the above, the sample of the present invention satisfied both the treated film test and the static mark test at the same time. As is clear from Table 4, Support 2.3.5 provided with a polyethylene layer was found to have excellent light resistance. Next, using the undercoat III No. 9, the support was
A handling test was conducted using five types of samples with different sizes from 11 to 5, and a copy sheet of the AO size map was prepared. A comparison was made regarding ease of creasing and tearing strength. Table 5 (Handling test results) These results show that polypropylene synthetic paper is resistant to folding and tearing, is tough against various types of handling, and is suitable for large-sized prints such as maps. Ta. As is clear from the above results, it has been found that an excellent photographic material with a treated film can be obtained by providing the undercoat layer according to the present invention on a substrate having a polyolefin surface. In particular, the carboxyl group activated type Tall1 of the undercoat layer
It has been found that even better film adhesion can be obtained by using a methanesulfonic acid ester type hardener or an ethyleneimine type hardener. Among substrates with a polyolefin surface, opaque resin films made from polypropylene resin as the main raw material and inorganic fillers added thereto by a two-wheel stretched film forming method, so-called synthetic paper, have excellent water resistance and smoothness. ,
In addition to printability, it has flexibility, double-cutting properties, tensile strength, tear initiation resistance, etc., so it was found to be suitable for use in maps, large-sized photographs such as posters, photo stickers, etc. In particular, when a thin polyethylene layer was provided on the surface of the so-called synthetic paper, the image forming layer did not peel off even after being exposed to sunlight, and the paper had excellent light resistance. Example 2 Water-soluble polymer compound (1) was placed on the support 2 of Example 1.
Undercoating was performed by changing the ratio of gelatin and gelatin as shown in Table 6, and using H-IX-2 as a carboxyl group-activated hardening agent so that the solid coating amount of the undercoat layer was 0.2Q/f. formed a layer. Next, in the same manner as in Example 1, an emulsion layer was formed on the formed undercoat layer to prepare Samples 1 to 9. After incubating each sample so that the hardness of the emulsion layer was appropriate, a treatment film test was conducted. The results are shown in Table-6. Incubation was carried out as shown in Table 6 (Water-soluble polymer compound/gelatin) ratio and treated membrane results-7. Then,
Samples 1 to 9 were prepared by forming emulsion layers in the same manner as in Example 1. After incubating each sample again so that the degree of hardness of the emulsion layer was appropriate, a treatment film test was conducted. The results are shown in Table-7. As is clear from Table 7 (hardening agent/binder) ratio and aging coating of undercoated product with treated film-6, the ratio of water-soluble polymer compound to gelatin is in the range of 0.1 to 5.0. was found to be preferable. Example 3 The solid coating amount of the undercoat layer was 0 on the support 2 of Example 1.
．． 2 (1/i'), the water-soluble polymer compound <1
) as a solid content, 66 parts of gelatin, and the carboxyl group-activated hardener Rho IX-2 were varied as shown in Table 7 to prepare an undercoat layer. If the hardening agent is too small, the film adhesion will be poor, and if it is too large, the film adhesion will tend to deteriorate over time when incubation is performed after undercoating. Considering these factors, the hardening agent application amount is 3. x 10'mole/g binder~15X
A range of 10-5a+ole/a binder was found to be preferred. [Effects of the Invention] According to the present invention, it was possible to provide a photographic paper support which has been subjected to undercoating treatment and has a surface that has improved adhesion to adhered substances and is endowed with antistatic ability. . Procedural amendment (0 button August 10, 1990 1, Indication of the case 1999 Patent Application No. 212654 2, Name of the invention Photographic paper support 3, Person making the amendment Relationship to the case Patent applicant Address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (
127) Konica Corporation Representative Director Takasumi Yoneyama 4, Agent 102 Address Kudan-Rosaka Building, 4-1-1 Kudankita, Chiyoda-ku, Tokyo Telephone 263-9524 Fax 263-9526

Claims (5)

[Claims] (1) A subbing layer containing at least gelatin, a water-soluble polymer compound represented by the following general formula, and a carboxyl group-activated hardener is provided on at least one surface of the substrate having a polyolefin resin surface. Photographic paper support. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A is vinyl monomer, B is hydrogen, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, where when Z=O, B is hydrogen, and when R is an alkyl group, B is hydrogen, and M is hydrogen or a cation (however, the water-soluble The substitution rate of cations is 10% or more for all M contained in the polymeric compound.) R is -O-R' or ▲ Numerical formula, chemical formula, table, etc. ▼ Here R' is an alkyl group , an aralkyl group, an aryl group, a heterocyclic residue, or a nonmetal atom necessary to form a heterocyclic ring in collaboration with R'', R'' is hydrogen, a lower alkyl group, or a heterocyclic residue in collaboration with R'. Nonmetal atoms necessary to form R_1 and R_2 are hydrogen or lower alkyl groups, X is ▲ formula,
There are chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, R_3 is a halogenoalkyl group or a halogenoalkyloxyalkyl group, m, p, q, r, x, y, z are each monomer m is 40 to 60 and p is 0 to 60.
, q is 0-50, r is 0-5, x is 0-70, y is 20
~80, z is 0 to 80, m+p+q+r=100
, x+y+z=100. ) (2) The photographic material according to claim 1, wherein the substrate is an opaque resin film manufactured by a biaxially stretched film molding method using polypropylene resin as a main raw material and adding an inorganic filler thereto. Photographic paper support. (3) The photographic paper support according to claim 1 or 2, wherein the substrate has a polyethylene layer provided on at least one surface thereof. (4) The ratio of the water-soluble polymer compound to gelatin is 0.1
The photographic paper support according to claim 1, characterized in that it has a molecular weight of 5.0 to 5.0. (5) The content of the carboxyl group-activated hardener is 3 x 10^-^5 mol to 15 x 10^-^ in 1 g of binder.
The photographic paper support according to claim 1, characterized in that the amount thereof is 5 mol. (6) The photographic paper support according to claim 1 or 5, wherein the carboxyl group-activated hardener is a methanesulfonic acid ester type hardener or an ethyleneimine type hardener.