Photographic support with titanium dioxide pigment polyolefin layer on a substrate

A photographic support consisting essentially of a substrate and a resin layer provided on the image forming side of the substrate, said resin layer comprising a specific titanium dioxide pigment and others. This photographic support is excellent in that it has a high brightness and a high apparent whiteness and stability of the apparent whiteness is good; printed image of high sharpness can be formed thereon: and occurrence of die lip stain at production is quite little and thus it has good surface property.

BACKGROUND OF THE INVENTION 
This invention relates to a photographic support consisting essentially of 
a substrate and a resin layer provided at least on the side of the 
substrate where images are to be formed (hereinafter referred to as 
"image-forming side"), said resin layer comprising a specific titanium 
dioxide pigment, etc. More particularly, this invention relates to a 
photographic support which has a high lightness and a high apparent 
whiteness, the apparent whiteness being highly stable, and has good 
surface property on which a highly sharp printed image can be formed and 
is quite a little in generation of die lip stain at production. 
A so-called resin-coated paper for photograph which comprises a substrate 
at least one side of which is coated with a resin composition comprising 
titanium dioxide pigment and a polyolefin resin has been known as 
photographic support. For example, U.S. Pat. No. 3,501,298 discloses a 
photographic support comprising a paper substrate, both sides of which are 
coated with a polyolefin resin. Since rapid development treatment has been 
employed, a polyethylene resin coated paper for photograph comprising a 
base paper for photographic paper, both sides of which are coated with a 
polyethylene resin has mainly been practically used as a support for 
photographic support, titanium dioxide pigment being usually contained in 
the resin on the image-forming side to give sharpness to images formed 
thereon. 
Hitherto, anatase type and rutile type titanium dioxide pigments have been 
known as those which are to be contained in the resin layer on the 
image-forming side of resin-coated paper for photograph. The following 
titanium dioxide pigments are also known:A titanium dioxide pigment, the 
surface of which is not subjected to coating treatment; a titanium dioxide 
pigment, the particles of which are subjected to coating treatment with an 
inorganic material such as hydrated aluminum oxide, hydrated silicon oxide 
or the like as disclosed in Japanese Patent Application Kokai Nos. 
52-35625 and 57-108849; and a titanium dioxide pigment, the particles of 
which are subjected to coating treatment with an organic material such as 
a polyhydric alcohol or a derivative thereof, a polyorganosiloxane or a 
derivative thereof, or the like as disclosed in Japanese Patent 
Application Kokai No. 52-35625, Japanese Patent Application Kokoku Nos. 
58-43734 and 61-26552 and the like. 
Furthermore, several resin-coated papers have been known as photographic 
supports when especially high sharpness of printed image is required. 
Examples thereof are as follows: (1) a resin-coated paper which contains a 
titanium dioxide pigment in the resin layer in a high concentration; (2) a 
resin-coated paper which contains a rutile type titanium dioxide pigment 
in the resin layer; (3) a resin-coated paper which contains titanium 
dioxide in the resin layer with addition of surfactants represented by a 
metal soap such as zinc stearate, calcium stearate, zinc palmitate and the 
like; and (4) a resin-coated paper which contains, in the resin layer, a 
so-called organic material-treated titanium dioxide pigment, the particles 
of which has been subjected to coating treatment with the organic material 
as mentioned above. 
However, the above photographic supports suffer from some severe problems 
in sharpness of image and other photographic properties and processability 
and thus are still not satisfactory. 
First, when concentration of titanium dioxide pigment in the resin layer of 
polyolefin resin-coated paper is increased as in the above (1), a 
photographic support which can provide printed image of high sharpness can 
be obtained, but severe problems often occur in photographic properties 
and productivity. That is, when a polyolefin resin composition, especially 
a polyethylene resin composition containing titanium dioxide pigment is 
melt-extruded into a film from a slit die and coated on a substrate, 
deposits or stains in the form of needles or iciles (hereinafter referred 
to as "die lip stain") tend to be formed on the tip of die lip in a short 
time. The die lip stain is very troublesome because it tends to grow 
larger with the lapse of time. If this die lip stain is formed at the 
melt-extrusion coating, streaks are formed in machine direction on the 
surface of the polyolefin resin-coated paper or streak-like flaws are 
generated due to nonuniform amount of coated resin. Furthermore, the die 
lip stain sometimes sticks to the substrate to form a foreign matter. 
Thus, the surface property of the polyolefin resin-coated paper is 
considerably damaged and such polyolefin resin-coated paper is unsuitable 
as photographic support which requires superior surface property and loses 
commercial value. Moreover, in order to completely remove the die lip 
stain once formed, production must be stopped to clean die lip or exchange 
die lip. Therefore, much labor and time are required and thus causes 
considerable reduction of productivity. 
Since titanium dioxide pigment contained in the resin layer of polyolefin 
resin-coated paper for photograph is subjected to severe requirements in 
its quality, mainly used is a so-called inorganic compound-treated 
titanium dioxide pigment, the particles of which are subjected to a 
coating treatment with inorganic compounds such as hydrated aluminum oxide 
and hydrated silicon oxide and a so-called untreated titanium dioxide 
pigment which is subjected to no surface treatment is scarcely used. 
However, when inorganic compound-treated titanium dioxide pigment is used, 
the larger the number of treatments of the titanium dioxide pigment with 
inorganic compound, the more the die lip stain formed. On the other hand, 
when untreated titanium dioxide pigment is used, the resin layer undergoes 
conspicuous deterioration by light and besides much discoloration with 
time, although die lip stain occurs less. 
In order to solve these problems, for example, Japanese Patent Application 
Kokai No. 57-108849 discloses a photographic support containing a titanium 
dioxide pigment, the surface of which is lightly treated with hydrated 
aluminum oxide. However, this photographic support also has the problems 
that some die lip stains occur when content of the titanium dioxide 
pigment in the polyolefin resin composition is considerably increased to 
obtain printed images of high sharpness. 
When a rutile type titanium dioxide pigment is used as titanium dioxide 
pigment contained in resin layer of polyolefin resin-coated paper as in 
the above (2), a photographic support which can provide printed images of 
fairly high sharpness can be obtained as compared with when anatase type 
titanium dioxide pigment is used. However, another serious problems on 
photographic properties occur. That is, the resin layer containing 
titanium dioxide pigment on the image-forming side of the photographic 
support tends to yellow due to the rutile type titanium dioxide and a 
printed image having vivid white ground cannot be obtained. 
The inventors have found that even if surfactants represented by metallic 
soaps such as zinc stearate, calcium stearate and zinc palmitate are added 
when titanium dioxide pigment is contained in resin layer of polyolefin 
resin-coated paper as in the above (3), sharpness of printed image on the 
resulting photographic polyolefin resin-coated paper cannot substantially 
be improved. 
Incorporation of titanium dioxide pigment into resin layer of polyolefin 
resin-coated paper is generally carried out in the following manner: That 
is, so-called masterbatch comprising the resin and the pigment contained 
in a high concentration in the resin is prepared by usual melt-kneading 
machines such as Banbury mixer, kneader and extruder for kneading and this 
masterbatch is diluted to desired concentration to obtain a polyolefin 
resin composition, which is coated on a substrate by melt-extrusion. 
Alternatively, a so-called compound comprising the resin and the pigment 
contained originally at a desired ratio in the resin is prepared and this 
compound is coated on a substrate by melt-extrusion. 
The main object of containing metallic soap in polyolefin resin-coated 
paper for photograph is to improve peelability of resin-coated Paper from 
cooling roll of melt extruder in coating resin on a substrate by 
melt-extrusion. 
However, as a result of the research conducted by the inventors, an utterly 
new fact has been found on the effect of metallic soap contained in 
resin-coated paper. That is, it has been found that when the metallic soap 
added in preparation of masterbatch or compound of titanium dioxide 
pigment is contained in the resin layer in an amount of less than 1.5% by 
weight based on the weight of titanium dioxide pigment and in an amount of 
less than 0.15% by weight based on the weight of resin layer, sharpness of 
printed image increases with increase in the content, but the peelability 
referred to above is inferior with such content and furthermore, when the 
metallic soap is contained in an amount of 1.5-7.5% by weight based on the 
weight of titanium dioxide pigment and in an amount of 0.15-0.75% by 
weight based on the weight of resin layer, the peelability is improved 
with increase in the content, but sharpness of printed image is 
considerably lowered and sometimes becomes lower than when no metallic 
soap is contained Furthermore, when metallic soap is contained in an 
amount of more than 7.5% by weight based on the weight of titanium dioxide 
pigment and in an amount of more than 0.75% by weight based on the weight 
of resin layer, sharpness of printed image gradually decreases with 
increase in the addition amount of the metallic soap and generation of 
oily smoke increases and processability at melt-extrusion coating of resin 
composition becomes much inferior. As explained above, even if a metallic 
soap is added at the time of incorporation of titanium dioxide pigment in 
resin layer of polyolefin resin-coated paper, there is the problem that 
photographic support which can afford high sharpness of printed image 
cannot be obtained. 
Furthermore, the inventors have found that even when a so-called organic 
compound-treated titanium dioxide pigment is used as the titanium dioxide 
pigment to be contained in resin layer of polyolefin resin-coated paper 
for photograph as in the above (4), sharpness of printed image is not 
improved. Moreover, when a metallic soap represented by zinc stearate in 
such an amount as can give sufficient peelability at preparation of 
resin-coated paper is added together with an organic compound-treated 
titanium dioxide pigment to resin layer of polyolefin resin-coated paper, 
sharpness of printed image on the resin-coated paper is nearly the same as 
or only slightly higher than when titanium dioxide pigment which has not 
been treated with organic compound is used. 
On the other hand, there have been known some techniques to improve 
whiteness of resin layer containing titanium dioxide pigment on the 
image-forming side of resin-coated type photographic supports. 
U.S. Pat. No. 3,501,298 discloses that a blue inorganic pigment such as 
ultramarine, cobalt blue or the like, a red inorganic pigment such as 
oxidized cobalt phosphate (e.g., Raspberry V-6260 manufactured by Ferro 
Colors Corp.), or a red organic pigment such as quinacridone red is 
contained in the resin layer in addition to the titanium dioxide pigment. 
It is also known to contain a fluorescent agent having 
bis(alkylsubstituted benzoxazolyl)thiophene structure which is represented 
by Uvitex OB (trademark for the product manufactured by Ciba Geigy) in 
resin layer. Japanese Patent Application Kokai No. 51-6531 discloses to 
contain a titanium dioxide pigment treated with hydrated alumina and a 
fluorescent agent in resin layer. Japanese Patent Application Kokai No. 
53-19021 discloses to contain a blue inorganic pigment such as ultramarine 
and a red inorganic pigment such as Daiichi Pink DP-1 or Daiichi Violet 
DV-1 (manufactured by Daiichi Kasei Co.). Further, Japanese Patent 
Application Kokoku 56-51336 discloses to contain a fluorescent agent 
having bis(alkyl-substituted benzoxazolyl)naphthalene structure in the 
resin layer. Japanese Patent Application Kokai No. 61-75341 discloses a 
technique to incorporate a quinacridone red organic pigment in resin 
layer. Moreover, U.S. Pat. No. 4,794,071 discloses to contain a mixture of 
bis(benzoxazolyl)stilbene fluorescent agents. 
However, the above enumerated techniques have the following defects. 
First, in the technique for improving apparent whiteness of resin layer by 
diminishing the tendency of yellowing of the resin layer caused by 
titanium dioxide pigment contained therein at a high concentration by 
containing an inorganic or organic coloring pigment or coloring dye in a 
resin layer on the image-forming side of resin-coated paper type 
photographic support, since color of resin layer is apparently whitened by 
coloration, brightness is lowered and vivid whiteness cannot be obtained. 
Secondly, it has also been found that when a polyolefin resin composition 
containing a fluorescent agent, especially a bis(benzoxazolyl)naphthalene 
type fluorescent agent or a bis(benzoxazolyl)stilbene type fluorescent 
agent and a titanium dioxide pigment, especially an inorganic 
compound-treated titanium dioxide pigment is melt-extruded into a film 
from a slit die and coated on a substrate, die lip stain occurs much and, 
especially when the resin composition additionally contains inorganic or 
organic color pigment or color dye, especially blue pigment or blue dye, 
die lip stain is especially conspicuous. Furthermore, as a result of 
investigation conducted by the inventors, it has been found that 
considerable die lip stain occurs when a polyolefin resin composition 
containing an inorganic or organic color pigment or color dye (especially 
inorganic color pigment) and a titanium dioxide pigment (especially 
inorganic compound-treated titanium dioxide pigment) is melt-extruded into 
a film from a slit die and coated on a substrate. 
Thirdly, when whiteness of resin layer is improved by containing in the 
resin layer a fluorescent agent of bis(benzoxazolyl)thiophene structure 
having a substituent as mentioned in U.S. Pat. No. 3,449,257 or a 
fluorescent agent of bis(benzoxazolyl)naphthalene structure having a lower 
alkyl group of 5 or less carbon atoms as mentioned in Japanese Patent 
Application Kokoku No. 56-51336, the fluorescent agent tends to bleed out 
of the resin layer and stability of color tone is inferior and besides, 
adhesion between resin layer and photographic emulsion layer is 
insufficient. In addition, a photographic support containing the above 
fluorescent agent is inferior in stability of whiteness and in weathering 
resistances such as so-called light resistance and discoloration in 
darkness and undergo yellowing with the lapse of time. Furthermore, 
photographic materials which comprise, as a support, a resin-coated paper 
containing in the resin layer a fluorescent brightening agent of 
bis(benzoxazolyl)thiophene structure having a substituent, a 
representative of which is Uvitex OB are deteriorated in whiteness and 
rather are considerably yellowed as compared with conventional 
photographic materials when treated with an acidic hardening fixer. 
SUMMARY OF THE INVENTION 
The object of this invention is to provide a photographic support which are 
superior in that it has high brightness and high apparent whiteness which 
is stable, it has good surface property on which a highly sharp printed 
image can be formed and besides die lip stain occurs little in production 
of the support. 
The inventors have conducted an intensive research in an attempt to attain 
the above object. As a result, it has been found that the above object can 
be attained by a photographic support which consists essentially of a 
substrate and a resin layer provided at least on the image-forming side of 
the substrate, said resin layer comprising a specific titanium dioxide 
pigment and the like. 
According to this invention, there is provided a photographic support 
consisting essentially of a substrate and a resin layer provided at least 
on the side of the substrate where images are to be formed, said resin 
layer comprising (A) a polyolefin resin or a polyolefin resin mixture, (B) 
a rutile type titanium dioxide pigment and (C) a fluorescent agent, said 
titanium dioxide pigment having been subjected to at least one treatment 
selected from the group consisting of (1) a surface treatment with 
aluminum-containing hydrated metal oxides to coat the titanium dioxide 
pigment with an aluminum-containing metal composition in an amount of more 
than 0.2% by weight, but less than 1.5% by weight in terms of anhydrous 
metal oxide based on the weight of the titanium dioxide pigment and with a 
silicon composition in an amount of 0 inclusive--0.4 inclusive % by weight 
in terms of anhydrous silicon dioxide based on the weight of the titanium 
dioxide pigment and (2) an inside treatment with an aluminum compound to 
contain, in the titanium dioxide pigment, an aluminum composition in an 
amount of more than 0.2% by weight, but less than 1.5% by weight in terms 
of anhydrous aluminum oxide based on the weight of the titanium dioxide 
pigment, said polyolefin resin having a melt index of more than 4.0, but 
less than 9.5, said polyolefin resin mixture having a weighted-mean melt 
index of more than 4.0, but less than 9.5, and said fluorescent agent 
being a bis-(benzoxazolyl)naphthalene type fluorescent agent having a 
substituent or a bis(benzoxazolyl)stilbene type fluorescent agent having a 
substituent (referred to as "first invention" hereinafter). 
According to this invention, there is furthermore provided a photographic 
support consisting essentially of a substrate and a resin layer provided 
at least on the side of the substrate where images are to be formed, said 
resin layer comprising (A) a polyolefin resin or a polyolefin resin 
mixture, (B) a rutile type titanium dioxide pigment, (C) a fluorescent 
agent, and at least one member selected the group consisting of (D) a 
color pigment and a color dye, said titanium dioxide pigment having a 
number-average diameter of 0.110-0.150 .mu.m and having been subjected to 
at least one treatment selected from the group consisting of (1) a surface 
treatment with aluminum-containing hydrated metal oxides to coat the 
titanium dioxide pigment with (a) an aluminum-containing metal composition 
in an amount of more than 0.2% by weight, but less than 1.8% by weight in 
terms of anhydrous metal oxide based on the weight of the titanium dioxide 
pigment and (b) a silicon composition in an amount of 0 inclusine--0.4 
inclusine % by weight in terms of anhydrous silicon dioxide based on the 
weight of the titanium dioxide pigment and (2) an inside treatment with an 
aluminum compound to contain, in the titanium dioxide pigment, an aluminum 
composition in an amount of more than 0.2% by weight, but less than 1.8% 
by weight in terms of anhydrous aluminum oxide based on the weight of the 
titanium dioxide pigment, and said fluorescent agent being a 
bis(benzoxazolyl)naphthalene type fluorescent agent having a substituent 
or a bis(benzoxazolyl)stilbene type fluorescent agent having a substituent 
(referred to as "second invention" hereinafter). 
According to this invention, there is additionally provided a photographic 
support consisting essentially a substrate and a resin layer provided at 
least on the side of the substrate where images are to be formed, said 
resin layer comprising (A) a polyolefin resin or a polyolefin resin 
mixture, (B) a titanium dioxide pigment, (C) an antioxidant, said titanium 
dioxide pigment having a number-average diameter of 0.110-0.150 .mu.m and 
having at least one compound selected from the group consisting of a 
magnesium compound, a calcium compound and a barium compound supported on 
the surface thereof in amount of 0.004-0.1% by weight in terms of metal 
based on the weight of the titanium dioxide pigment (referred to as "third 
invention" hereinafter). 
DETAILED DESCRIPTION OF THE INVENTION 
In this invention, a resin layer is provided at least on the image-forming 
side of a substrate. 
In the first invention, the resin layer contains, as essential components, 
(A) a polyolefin resin or a mixture of polyolefin resins, (B) a titanium 
dioxide pigment and (C) a fluorescent agent. 
In the second invention, the resin layer contains, as essential components, 
(A) a polyolefin resin or a mixture of polyolefin resins, (B) a titanium 
dioxide pigment, (C) a fluorescent agent and (D) a color pigment and/or a 
color dye. 
In the third invention, the resin layer contains, as essential components, 
(A) a polyolefin resin or a mixture of polyolefin resins, (B) a titanium 
dioxide pigment and (C) an antioxidant. 
The first invention is explained. 
The titanium dioxide pigment used in the first invention has rutile 
structure. This titanium dioxide pigment is (1) one which has been 
subjected to a surface treatment with an aluminum-containing hydrated 
metal oxide to coat the surface of titanium dioxide with an 
aluminum-containing metal composition in an amount of more than 0.2% by 
weight, but less than 1.5% by weight in terms of anhydrous metal oxide 
based on the weight of the titanium dioxide pigment and with a silicon 
composition in an amount of 0-0.4% by weight in terms of anhydrous silicon 
dioxide based on the weight of the titanium dioxide pigment and/or (2) one 
which has been subjected to an inside treatment with an aluminum compound 
to contain an aluminum composition in an amount of more than 0.2% by 
weight, but less than 1.5% by weight in terms of anhydrous aluminum oxide 
based on the weight of the titanium dioxide pigment. 
Particle diameter of the titanium dioxide pigment used in the first 
invention is not critical, but is preferably about 0.04-0.5 .mu.m and more 
preferably about 0.08-0.2 .mu.m (considering sharpness of print image) in 
number-average diameter measured in a certain direction by electron 
microscope. 
Representative methods for preparation of rutile type titanium dioxide 
pigment used in the first invention include sulfuric acid method and 
chlorine method. 
The sulfuric acid method comprises the following steps: 
Raw titanium dioxide.fwdarw.digestion.extraction.fwdarw.allowing to 
stand.crystallization.fwdarw.filtration. 
concentration.fwdarw.hydrolysis.fwdarw.washing.fwdarw.calcination.fwdarw.g 
rinding.dressing of grain.fwdarw.wet grinding.classification.fwdarw.surface 
treatment.fwdarw.washing.drying.fwdarw.finishing grinding.fwdarw.titanium 
dioxide pigment 
In case of the sulfuric acid method, usually ferric sulfate is crystallized 
from a solution of ilmenite in sulfuric acid and is removed to obtain an 
aqueous titanyl sulfate solution, which is hydrolyzed to obtain a hydrated 
titanium dioxide. This hydrated titanium dioxide is calcined to improve 
properties as pigment. The hydrolysis of aqueous titanyl sulfate solution 
can be carried out by so-called self seed method which comprises adding 
titanyl sulfate solution to warm water to precipitate hydrated titanium 
dioxide, which is used as a seed or so-called external seed method which 
comprises adding to titanyl sulfate solution a hydroxide of titanium 
prepared by hydrolyzing titanyl sulfate or titanium tetrachloride as a 
seed. The calcination is carried out at 800.degree.-1100.degree. C., 
namely, at a calcination temperature higher than that for preparation of 
titanium dioxide of anatase structure or in the presence of a compound 
containing metals such as sodium, potassium and zinc to accelerate 
formation of rutile structure at calcination. The term "rutile type 
titanium dioxide" used in the present invention means a titanium dioxide 
pigment in which 90% by weight or more, preferably 95% by weight or more 
of the crystal structure has been converted to rutile structure. 
According to the chlorine method, titanium dioxide particles are formed by 
vapor phase calcination decomposition of titanium tetrachloride at high 
temperature and in oxygen atmosphere and generally those of rutile 
structure are obtained. 
The chlorine method comprises the following steps. 
Highly purified titanium dioxide or synthetic rutile type titanium 
oxide.fwdarw.chlorination.fwdarw.separation 
condensation.fwdarw.purification.fwdarw.preheating.fwdarw.calcination.deco 
mposition.fwdarw.separation.fwdarw.grinding.dressing of grain.fwdarw.wet 
grinding.classification.fwdarw.surface 
treatment.fwdarw.washing.drying.fwdarw.finishing grinding.fwdarw.titanium 
dioxide pigment 
The product obtained by calcination or vapor phase calcination 
decomposition is referred to as "titanium dioxide clinker" hereinafter. 
The titanium dioxide clinker is dry-ground by a centrifugal roller mill 
such as Raymond mill or a fluid energy mill such as air mill. The ground 
product is suspended in water to make a titanium dioxide slurry. This 
slurry is wet-ground in a wet ball mill or a vibration mill and is 
wet-classified by centrifugal separation using a continuous horizontal 
centrifugal separator and/or by passing through a vibration double deck 
screen (U.S. standard screen: 325 meshes) to obtain a titanium dioxide 
slurry called "fines" substantially free from coarse particles of titanium 
dioxide. In case of surface treating titanium dioxide, the surface of the 
fines from which coarse particles have been removed and are still in the 
form of slurry is coated with an aluminum-containing hydrated metal 
compound. After the surface treatment, the slurry is subjected to 
filtration and washing with water using a filter press and is further 
ground finely in an impact grinder and/or a fluid energy mill to obtain a 
titanium dioxide pigment. 
The rutile type titanium dioxide pigment used in the first invention 
include one which has been subjected to a surface treatment with a 
specific amount of an aluminum-containing hydrated metal oxide or one 
which has been subjected to an inside treatment with a specific amount of 
an aluminum compound or one which has been subjected to both the surface 
treatment and the inside treatment. Especially, when titanium dioxide 
pigment is produced by sulfuric acid method, one which has been subjected 
to the surface treatment with a specific amount of an aluminum-containing 
hydrated metal oxide is preferred from the point of designing of titanium 
dioxide pigment. 
The surface-treated rutile type titanium dioxide pigment used in the first 
invention is prepared by subjecting titanium dioxide to wet grinding and 
classification and then to a surface treatment with a aluminum-containing 
hydrated metal oxide to coat the surface of titanium dioxide with an 
aluminum-containing metal composition in an amount of more than 0.2% by 
weight, but less than 1.5% by weight in terms of anhydrous metal oxide 
based on the weight of the titanium dioxide pigment and a silicon 
composition in an amount of 0-0.4% by weight in terms of anhydrous silicon 
dioxide based on the weight of the titanium dioxide pigment. If amount of 
the metal composition is 0.2% by weight or less, not only weathering 
resistance of resin layer of resin-coated paper in which the titanium 
dioxide pigment is contained is deteriorated, but also fine foreign 
matters or fine particles called microgrit may occur much. If amount of 
the metal composition is 1.5% by weight or more, die lip stain occurs much 
and further, microgrit appears much. Amount of the metal composition is 
preferably 0.4-1.25% by weight, more preferably 0.5-1.0 % by weight in 
terms of anhydrous metal oxide based on the weight of titanium dioxide. 
The aluminum-containing hydrated metal oxide is preferably a hydrated 
aluminum oxide. Amount of the silicon composition is 0-0.4% by weight, 
preferably 0-0.2% by weight in terms of anhydrous silicon dioxide. Other 
hydrated metal oxides such as hydrated titanium oxide and the like can be 
used so that titanium dioxide is coated with other metal components such 
as titanium and the like in a total amount of 0-1.5% by weight in terms of 
anhydrous metal oxide. It is also possible to carry out the surface 
treatment with a hydrated aluminum silicon oxide so as to coat the 
titanium dioxide with a silicon component in an amount of 0-0.4% by weight 
in terms of anhydrous silicon dioxide. 
The surface treatment of titanium dioxide particles with a hydrated metal 
oxide can be carried out by the following method: That is, titanium 
dioxide slurry is subjected to wet grinding and classification and then is 
adjusted to pH of preferably 5 or more, more preferably or more, further 
preferably about 7. Thereafter, to the slurry is added a water-soluble 
aluminum slit and, if necessary, other slightly soluble metal (e.g., 
slightly soluble silicon compound) and subsequently pH of the slurry is 
varied to precipitate a slightly soluble hydrated aluminum oxide and, if 
necessary, other slightly soluble hydrated metal oxide on the surface of 
titanium dioxide pigment. For example, explanation will be made with 
reference to a representative method of carrying out surface treatment 
using a reaction tank provided with a stirrer. That is, a solution of 
water-soluble alkali compounds such as sodium hydroxide or potassium 
hydroxide is added to the titanium dioxide slurry after subjected to wet 
grinding and classification to adjust pH of the slurry to 7.0.+-.1.0. To 
the pH-adjusted titanium dioxide slurry is added an aluminate such as an 
alkali metal salt of aluminic acid and, if necessary, additionally, an 
aqueous solution of a water-soluble alkaline compound such as sodium 
hydroxide or potassium hydroxide to reduce pH of the slurry to show 
alkalinity and besides, a mineral acid such as sulfuric acid or 
hydrochloric acid or an aqueous solution of a salt which reacts as an acid 
is added to the slurry to precipitate hydrated aluminum oxide on the 
surface of titanium dioxide particles. Thus, the surface treatment is 
accomplished. The pH of the titanium dioxide slurry after subjected to 
surface treatment is usually within the range of 7.0.+-.1.0. Sodium 
aluminate is especially useful among the alkali metal salts of aluminic 
acid. Besides the aluminates, other inorganic compounds may also be used 
for the surface treatment. In this case, this inorganic compound can be 
added at optional stage of before, during or after the addition of 
aluminate, but advantageously before addition of aluminate. As the 
inorganic compounds used for surface treatment in addition to aluminate, 
there may be used various compounds, for example, silicon compounds such 
as alkali metal salts of silicic acid and silicon tetrachloride, titanium 
compounds such as titanium tetrachloride, other metal compounds such as 
those of zirconium, zinc, magnesium and manganese and phosphorus 
compounds. 
The inside-treated rutile type titanium dioxide pigment used in the first 
invention is produced by subjecting to inside treatment with an aluminum 
compound to contain, in the titanium dioxide pigment, an aluminum 
composition in an amount of more than 0.2% by weight, but less than 1.5% 
by weight in terms of aluminum oxide based on the weight of the titanium 
dioxide pigment. If amount of the aluminum composition is 0.2% by weight 
or less, weathering resistance of the resin layer of photographic supports 
which contains the titanium dioxide is deteriorated. If amount of the 
aluminum composition is 1.5% by weight or more, die lip stain occurs much 
and microgrit also appears much. The amount of the aluminum composition is 
preferably 0.4-1.25% by weight in terms of aluminum oxide based on the 
weight of the titanium dioxide pigment. As aluminum compounds used for 
inside treatment of titanium dioxide pigment, mention may be made of 
aluminum compounds such as aluminum chloride, aluminum sulfate, aluminum 
hydroxide, and sodium aluminate, and preferably aluminum chloride and 
aluminum sulfate when the titanium dioxide pigment is produced by sulfuric 
acid method. When the titanium dioxide pigment is produced by chlorine 
method, aluminum chloride is preferred. Inside treatment of the titanium 
dioxide pigment with aluminum compound is carried out by adding aluminum 
compound to titanium composition before calcination step when the titanium 
dioxide pigment is produced by sulfuric acid method. Preferably, after 
hydrolysis, the resulting hydrated titanium oxide composition was washed 
and concentrated by a filter and the like and is put in a mixer such as a 
kneader and well mixed with addition of aluminum compound or the hydrated 
titanium oxide composition is redispersed in water in a mixing tank with a 
stirrer and well mixed with aluminum compound and thereafter the 
composition is subjected to calcination. In case of Chlorine method, 
titanium tetrachloride and oxygen and aluminum compound, preferably 
aluminum chloride are fed to the calcination decomposition step using an 
apparatus disclosed, for example, in U.S. Pat. No. 3,121,641. 
In view of the effective prevention of the microgrit of the photographic 
support containing the titanium dioxide pigment, the rutile type titanium 
dioxide pigment used in the first invention is preferably washed with 
water after the surface treatment or after the wet grinding and 
classification when the surface treatment is not carried out, until the 
suspension electric conductivity of the titanium dioxide pigment defined 
below becomes 60 .mu. /cm or less. 
In a 100-ml-volume beaker is placed a rotator for a magnetic stirrer 
(manufactured by Universal Co., Ltd., treated with Teflon, having a length 
of 45 mm and a diameter of 8 mm) and 100 ml of distilled water (at 
21.5.degree. C.) is poured into the beaker, and then 10.0 g of the 
titanium dioxide pigment is added thereto. After that, the beaker is 
placed on the stage of a magnetic stirrer (manufactured by Yamato Kagaku 
K.K., type MH-61). In the liquid in the beaker is fixed a conductivity 
cell [manufactured by Toa Denpa Kogyo K.K., type CG-200lPL (.theta.=0.1)] 
attached to an electric conductivity meter (manufactured by Toa Denpa 
Kogyo K.K., model CM-5B) out of touch with the rotator so as to trace the 
value of the electric conductivity with the lapse of time. After fixing 
the cell, the magnetic stirrer is started so that the rotator is rotated 
at 420 rpm, in order to stirr the composition in the beaker and the 
composition into a suspension of the titanium dioxide pigment. The 
suspension of the titanium dioxide pigment is stirred for 16 minutes 
keeping the temperature of the dispersion at 21.5 .+-.0.5.degree. C.. 16 
Minutes after the start of stirring, the suspension electric conductivity 
of the titanium dioxide pigment at a liquid temperature of 21.degree. C. 
is measured with stirring. From the electric conductivity measured above, 
the electric conductivity at 25.degree. C. is calculated. The electric 
conductivity thus obtained is defined as the suspension electric 
conductivity of the titanium dioxide pigment in this specification. 
The rutile type titanium dioxide pigment advantageously used in the first 
invention, the suspension electric conductivity of which is 60 .mu. /cm or 
more is prepared as follows After the surface treatment, the original 
composition of the titanium dioxide pigment is filtered by a filter press, 
and subsequently the titanium dioxide cake in the filter press is washed 
with flowing water until the suspension electric conductivity of the 
titanium dioxide pigment becomes 60 .mu. /cm or less. 
The conditions for washing with water such as washing time, the amount of 
the water used, the pressure of the water and the like can be determined 
as follows: The titanium dioxide washed with water under a series of 
combinations of acid-washing conditions is dried and subsequently ground 
to prepare the titanium dioxide pigment. The suspension electric 
conductivity of the titanium dioxide pigment thus obtained is measured to 
find combinations of the acid-washing condition, under which the 
suspension electric conductivity of the titanium dioxide pigment becomes 
60 .mu. /cm or less. 
After the surface treatment, the reaction mixture containing the titanium 
dioxide can be washed with water as such or in the form of the suspension 
obtained by suspending the titanium dioxide cake again in the bath of the 
filter press. As the water, stored water or flowing water which slowly 
displaces the supernatant can be used. Washing with water may be carried 
out simultaneously with washing with water in the filterpress or 
separately. The suspension electric conductivity of the titanium dioxide 
pigment used in this invention is preferably 55 .mu. /cm or less, more 
preferably 50 .mu. /cm or less in view of further prevention of the 
microgrit. 
In view of more effective prevention of the microgrit and obtained higher 
sharpness of the printed image of the resin-coated paper for photograph 
containing the rutile type titanium dioxide pigment used in the first 
invention, it is advantageous that the titanium dioxide cake is washed 
with water and dried and then the dry titanium dioxide is finely ground in 
a fluid energy mill to produce the titanium dioxide pigment. As the fluid 
energy mill, a steam mill such as a micronizer is preferably used; 
however, an air mill may be used in combination. It is especially 
preferable that grinding of the first step is carried out in an impact 
grinder such as hammer mill and then, as grinding of the second step, fine 
grinding is carried out in the fluid energy mill. 
The rutile type titanium dioxide pigment used in the first invention may 
be, if necessary, treated with various organic compounds such as 
triethanolamine, trimethylolpropane, a metal salt of a fatty acid, 
polyorganosiloxane and the like. 
In the first invention, the resin layer contains, as an essential 
component, a polyolefin resin or a polyolefin resin mixture comprising two 
or more polyolefin resins. Melt Index (hereinafter referred to as "MI") of 
the polyolefin resin is more than 4.0, but less than 9.5. Weighted-mean 
melt index of the polyolefin resin mixture is more than 4.0, but less than 
9.5. 
MI of polyolefin resin is measured at 190.degree. C. under a load of 2.16 
kgf in accordance with JIS K 7210 before being mixed with other 
components. 
Weighted-mean MI of polyolefin resin mixture is calculated from MI of 
respective polyolefin resins constituting the mixture measured under the 
above conditions before being mixed. In this case, MI of respective 
polyolefin resins may be 4.0 or less or 9.5 or more. When weighted-mean MI 
of the polyolefin resin mixture is more than 4.0 but less than 9.5, the 
object of this invention can be accomplished. 
When resin layer contains the single polyolefin resin, if MI of the 
polyolefin resin is 4.0 or less, die lip stain cannot be prevented at 
production of photographic support and if it is 9.5 or more, not only 
considerable neck-in occurs, but also thickness of resin layer is 
ununiform and surface property of photographic support is deteriorated. 
When resin layer contains the polyolefin resin mixture, if weighted-mean 
MI of the polyolefin mixture is 4.0 or less, formation of die lip stain 
cannot be prevented at production of photographic support and if it is 9.5 
or more, not only considerable neck-in occurs at production of 
photographic support, but also thickness of resin layer is ununiform and 
surface property of photographic support is deteriorated. 
MI of the polyolefin resin and weighted-mean MI of the polyolefin resin 
mixture are preferably 5-8. 
In the first invention, resin layer on the image-forming side may have a 
multi-layer structure. For example, the resin layer may have an outer 
layer comprising a polyolefin resin mixture having a weighted-mean MI of 
more than 4.0, but less than 9.5 and an inner layer comprising a 
polyolefin resin having a weighted-mean MI of 2-10. 
As examples of the polyolefin resin and the polyolefin resins constituting 
the polyolefin resin mixture used in the first invention, mention may be 
made of homopolymers such as polyethylene, polypropylene, polybutene, 
polypentene and the like; copolymers comprising two or more 
.alpha.-olefins such as ethylenepropylene copolymer and ethylene-butylene 
copolymer. From the points of economy and melt-extrusion coatability, 
preferred are polyethylene type resins such as, for example, low-density 
polyethylenes; medium-density polyethylenes; high-density polyethylenes; 
straight-chain low-density polyethylenes; copolymers of ethylene with 
.alpha.-olefins such as propylene and butylene; and carboxy-modified 
polyethylene. The polyolefin resin and polyolefin resins constituting the 
polyolefin resin mixture may have various densities, molecular weights and 
molecular weight distributions, and preferably they have a density of 
0.90-0.97 and a molecular weight of 20,000-250,000. 
For containing the rutile type titanium dioxide pigment used in the first 
invention in resin composition for making photographic support, the 
following two methods are usually employed: That is, titanium dioxide 
pigment is previously contained in polyolefin resin at a certain 
concentration to make a so-called masterbatch and this masterbatch is 
diluted to the desired concentration with a diluent resin and this is used 
as resin composition. Alternatively, a so-called compound is prepared 
which comprises a polyolefin resin containing titanium dioxide pigment at 
the desired concentration and this compound is used as resin composition. 
For preparation of these masterbatches and compounds, a Banbury mixer, a 
kneader, a kneading extruder, a twin-roll mill, a triple-roll mill and the 
like are usually employed. Among them, Banbury mixer and kneading extruder 
are advantageously used. These may be used in combination of two or more. 
In order to improve peelability in making resin-coated paper for 
photograph, it is preferred to add a metal salt of fatty acids to 
masterbatch or compound of titanium dioxide pigment during preparation 
thereof and thus to contain the metal salt in the resin layer of 
resin-coated paper for photograph. These metal salts of fatty acids 
include, for example, zinc stearate, calcium stearate, aluminum stearate, 
magnesium stearate, zirconium octylate, sodium palmiate, calcium palmitate 
and sodium laurate. Amount of these metal salts to be added is preferably 
0.1-50% by weight based on the weight of titanium dioxide pigment and 
0.01-5% by weight based on the weight of resin composition containing 
titanium dioxide pigment. 
When content of rutile type titanium dioxide in the resin layer in the 
first invention is 7% by weight or less based on the weight of resin, 
sharpness of printed image formed is insufficient and when it is 35% by 
weight or more, flowability decreases and extrusion property is 
deteriorated or occurrence of die lip stain is Conspicuous. The content is 
especially preferably 9-35% by weight. 
Examples of the substituent-containing bis(benzoxazolyl)naphthalene 
fluorescent agent or substituent-containing bis(benzoxazolyl)stilbene 
fluorescent agent used in the first invention are as shown by the 
following formulas. The naphthalene type fluorescent agents are preferably 
those which have a substituent of 6 or more carbon atoms in view of 
prevention of breeding-out. 
##STR1## 
For containing the fluorescent agent in polyolefin resin composition, the 
fluorescent agent is added in preparing a masterbatch or compound of 
titanium dioxide pigment to make masterbatch or compound comprising 
titanium dioxide pigment, fluorescent agent, polyolefin resin and 
dispersant such as metal salt of fatty acid, thereby to contain the 
fluorescent agent in the resin composition. 
It is also possible to contain the fluorescent agent in the resin 
composition by preparing fluorescent masterbatch by dispersing in the main 
polyolefin resin the fluorescent agent preliminarily mixed with a low 
molecular weight polyolefin which has lower softening point than the main 
polyolefin resin and is solid at room temperature or/and a dispersant such 
as metal salt of fatty acid. Content of the fluorescent agent in the resin 
composition is 0.3-25 mg/m.sup.2 from the points of whiteness, 
anti-breeding out and occurrence of die lip stain. If it is less than 0.3 
mg/m.sup.2, apparent whiteness is considerably insufficient and if it is 
more than 25 mg/m.sup.2, tendency to form die lip stain is conspicuous. 
The range of 0.5-10 mg/m.sup.2 is especially preferred. 
In the first invention, it is preferred to contain inorganic or organic 
blue pigment or blue dye in resin layer to further improve apparent 
whiteness by synergistic effect of the pigment or dye and the fluorescent 
agent. Examples of the inorganic blue pigments and dyes are cobalt blue, 
Prussian blue and ultramarine and examples of organic blue pigments and 
dyes are cerulean blue, Phthalocyanine Blue and Chromophthal Blue A3R. 
Amount of the pigment or dye to be added to resin layer is preferably 
0.025-0.5% by weight, more preferably 0.05-0.2% by weight for inorganic 
blue pigment and is preferably 0.001-0.1% by weight, more preferably 
0.0025-0.05% by weight for organic blue compound. If the amount is too 
small, sufficient coloring effect cannot be obtained and if it is too 
large, not only brightness decreases, but also die lip stain is very 
conspicuous. 
Furthermore, it is advantageous to contain inorganic or organic magenta 
pigment or dye in the resin layer. Examples of these pigment and dye are 
cobalt violet, fast violet, manganese purple and quinacridone red. Amount 
of these pigment and dye added to resin layer is preferably 0.025-1.0% by 
weight, more preferably 0.1-0.4% by weight for inorganic magenta pigment 
and is preferably 0.001-0.03% by weight, more preferably 0.002-0.015% by 
weight for organic magenta pigment. 
It is preferred to contain an antioxidant in the resin layer in order to 
more effectively prevent die lip stain in production of resin-coated 
paper. As the antioxidant, there may be used various antioxidants such as 
phenol type, amine type and phosphate type as far as no troubles are 
caused when used in resin composition for photograph, but especially 
preferred are hindered phenol type antioxidants because they have no 
adverse effect on photographic emulsion layer and die lip stain can be 
more effectively inhibited. 
As these advantageous hindred phenol type anti-oxidants, mention may be 
made of, for example, 
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 
tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)]methane, 
octadecyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate, 
2,2',2"-tris[3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethylisocyanur 
ate, 1,3,5-tris(4-tertbutyl-3-hydroxy-2,6-di-methylbenzyl)isocyanurate, 
tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphite, 
4,4'-thiobis-(6-tert-butyl-o-cresol), 
2,2'-thiobis-(6-tertbutyl-4-methylphenol), 
tris-(2-methyl-4-hydroxy-5-tertbutylphenyl)butane, 
2,2'-methylene-bis-(4-methyl-6-tertbutylphenol), 
4,4'-methylene-bis-(2,6-di-tert-butylphenol), 
4,4'-butylidenebis-(3-methyl-6-tert-butylphenol), 
2,6-ditert-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, 
and 2,6-di-tert-4-n-butylphenol. These antioxidants may be used in 
combination of two or more depending on properties of them. 
Content of the antioxidant in resin composition is 5-1000 ppm, preferably 
10-500 ppm, more preferably 20-300 ppm in weight ratio. If it is less than 
5 ppm or more than 1000 ppm, die lip stain readily occurs. In case of more 
than 1000 ppm, adhesion between base paper and resin layer is inferior. 
For containing antioxidant in resin composition, there may be used a 
so-called compound comprising a polyolefin resin used in which antioxidant 
has been contained. Alternatively, there may be used a proper amount of 
resin in which antioxidant is contained at a relatively high concentration 
or antioxidant may be added during preparation of resin composition by a 
kneader. Further, these methods may be suitably combined depending on kind 
and content of the antioxidant. 
The resin layer contains (A) a polyolefin resin or a polyolefin resin 
mixture, (B) a rutile type titanium dioxide pigment and (C) a fluorescent 
agent as essential components and preferably further contains the 
above-mentioned inorganic or organic blue pigments or blue dyes, metal 
salts of fatty acids, antioxidants and inorganic or organic magenta 
pigments or magenta dyes. When resin layer has multi-layer structure, any 
layers may contain the above titanium dioxide pigment, fluorescent agent, 
color pigment or color dye, metal salt of fatty acid and antioxidant. 
Furthermore, in the first invention, the resin layer provided on the 
image-forming side of photographic support and, if necessary, the resin 
layer provided on back side may further contain various additives, in 
proper combination, such as white pigments (e.g., other titanium dioxide, 
zinc oxide, talc, and calcium carbonate), fatty acid amides (e.g., stearic 
acid amide and arachic acid amide), organosilicone compounds (e.g., 
polyorganosiloxane), ultraviolet absorbers [e.g., Tinuvin 320, Tinuvin 
326, Tinuvin 328 (trade names for ultraviolet absorbers of Ciba-Geigy)] in 
addition to the above titanium dioxide pigment, fluorescent agent, color 
pigment or color dye, metal salt of fatty acid and antioxidant. 
The photographic support of this invention is produced by a so-called 
extrusion coating method, in which the molten polyolefin resin is casted 
on the running substrate such as paper, synthetic paper or a film to coat 
usually both sides of the substrate with the resin. In order to form a 
resin layer having a multilayer structure, preferably used is a so-called 
tandem extrusion system, in which the inner resin layer and the outermost 
resin layer on the right side of the photographic support are 
successively, preferably continuously, formed by extrusion coating or 
so-called coextrusion coating system in which the outermost resin layer 
and the inner resin layer are simultaneously formed by extrusion coating. 
Before the substrate is coated with the polyolefin resin, the substrate is 
preferably subjected to an activating treatment such as a corona discharge 
treatment, a flame treatment or the like. The emulsion-layer side of the 
photographic support has a glossy surface, a finely roughened or matte 
surface to such an extent that it does not affect the gloss of the surface 
of the photographic paper obtained therefrom disclosed in Japanese Patent 
Application Kokai No. 55-26507 a silky surface or the like. Usually, the 
back side of the photographic support has a dull surface. The right side 
or, if necessary, both sides of the photographic support may be subjected 
to an activating treatment such as a corona discharge treatment, a flame 
treatment or the like. The photographic support may be further subjected 
to an undercoating treatment as disclosed in Japanese Patent Application 
Kokai No. 61-84643 after the activating treatment. The thickness of the 
resin layer on the right or back side is not critical; however, in 
general, it is preferably 10-50 .mu.m. 
The substrate used in this invention includes a natural pulp paper mainly 
composed of a natural pulp; a synthetic fiber-containing paper composed of 
natural pulp and a synthetic fiber; a synthetic fiber paper mainly 
composed of a synthetic fiber; a so-called synthetic paper produced by 
making a film composed of a synthetic resin such as polystyrene, 
polypropylene or the like into a paper form; and a film composed of 
cellulose acetate, poly(ethylene terephthalate), a polycarbonate or the 
like. As the substrate for a polyolefin resin-coated paper, the natural 
pulp paper (hereinafter referred to as the base paper) is advantageously 
used in view of the objects of this invention of providing economically a 
photographic support excellent in that high sharpness of the printed image 
can be obtained, the microgrit or die lip strings does not substantially 
appears, and hence, has excellent surface property. 
As a pulp composing the base paper used in this invention, advantageously 
used is a natural pulp appropriately selected as disclosed in Japanese 
Patent Application Kokai Nos. 58-37642, 60-67490, 60-69649, 61-35442 and 
the like. However, if necessary synthetic pulp or synthetic fiber may be 
used along with the natural pulp. As the natural pulp, preferably used is 
a wood pulp such as softwood pulp, hardwood pulp or a mixture thereof, 
which has been subjected to usual bleaching with chlorine, hypochloride, 
chlorine dioxide or the like; alkali extraction or alkali treatment; 
oxidation bleaching with hydrogenperoxide, oxygen or the like; or a 
combination of these treatments. Moreover, various pulps may be used such 
as kraft pulp, sulfite pulp, soda pulp and the like. 
Into the base paper used in this invention may be incorporated various 
sizing agents, high molecular weight compounds or additives in the 
preparation of a paper slurry. 
The sizing agents for the base paper preferably used in this invention 
include metal salts of fatty acids, fatty acids, alkylketene dimers, 
alkenyl- or alkylsuccinic anhydrides, epoxized amides of higher fatty 
acids as disclosed in Japanese Patent Application Kokai No. 54-147211 and 
organic fluoro compounds as disclosed in Japanese Patent Application Kokai 
No. 56-109343. 
The sizing agent suitable for the base paper used in this invention 
includes metal salts of fatty acids and fatty acids in such a form that 
they can be fixed to pulp using a water-soluble aluminum salt such as 
aluminum chloride, sulfite alumina, poly(aluminum chloride) or the like; 
alkylketene dimers in such a form that they can be fixed with or without 
the water-soluble aluminum salt and a combination of the alkylketene dimer 
and an epoxized amide of a higher fatty acid. The metal salts of higher 
fatty acids and the fatty acids are preferably those having 12-22 carbon 
atoms and they are preferably added in an amount of 0.5-4.0% by weight 
based on the bone-dry weight of the pulp. The proportion of the solid 
weight of the water-soluble aluminum salt optionally added to the weight 
of the sizing agent is preferably 1/20-4/1, more preferably 1/10-1/1. The 
alkyl group of the alkylketene dimers has preferably 8-30 carbon atoms, 
more preferably 12-18 Carbon atoms. Usually, alkylketene dimers are on the 
market in the form of the emulsion, and a specific example is Aquapel 
360XC (a trade name of Dic Hercules Chemicals. Inc.). They are added 
preferably in an amount of 0.2-4.0% by weight based on the bone-dry weight 
of the pulp. 
The high molecular weight compound advantageously added to the base paper 
used in this invention in preparing a paper slurry includes a cationic 
wet-strength-reinforcing agent or a cationic, anionic or amphoteric 
strength-reinforcing agent. The cationic wet-strength-reinforcing agent is 
preferably polyamine-polyamide-epichlorohydrin resin and it is added in an 
amount of preferably 0.05-4.0% by weight, more preferably 0.15-1.5% by 
weight, based on the dry weight of the pulp. Specific examples of the 
cationic wet-strength-reinforcing agent are kymene 557H, kymene S-25, 
Epinox P-130 (these are trade names of Dic Hercules Chemicals. Inc.) and 
the like. 
The cationic, anionic and amphoteric strength-reinforcing agents include 
cationized starch as disclosed in Japanese Patent Application Kokoku 
60-17103; cationic poly(vinyl alcohol) as disclosed in Japanese Patent 
Application No. 62-49699; cationic polyacrylamide as disclosed in Japanese 
Patent Application Kokai Nos. 57-185432 and 57-197539; anionic 
polyacrylamide as disclosed in Japanese Patent Application Kokoku Nos. 
62-23119 and 62-31118; amphoteric polyacrylamide as disclosed in Japanese 
Patent Application Kokoku No. 61-37613 and Japanese Patent Application 
Kokai No. 59-31949; vegetable galactomannan as disclosed in Japanese 
Patent Application Kokai No. 59-125731; and the like. They are added in an 
amount of preferably 0.05-8% by weight, more preferably 0.15-4% by weight, 
based on the dry weight of the pulp. 
To the base paper used in this invention may be added various additives in 
the preparation of the paper slurry. There may be added, in proper 
combination a filler such as Clay, kaolin, potassium carbonate, barium 
sulfate, magnesium silicate, titanium dioxide or the like; a pH modifier 
such as sodium hydroxide, sodium carbonate or the like; a coloring 
pigment, a coloring dye or a fluorescent whitening agent as disclosed in 
Japanese Patent Application Kokai No. 54-147033 and Japanese Patent 
Application Nos. 62-37555 and 63-96516. 
To the base paper used in this invention may be added various water-soluble 
polymers, antistatic agents, latices, emulsions, pigments, pH modifiers 
and the like by spraying or tab size pressing. The water-soluble polymer 
includes starchy polymers as disclosed in Japanese Patent Application No. 
63-96516, poly(vinyl alcohol)-type polymers, gelatinic polymers, 
polyacrylamide-type polymers, cellulosic polymers and the like. The 
antistatic agent includes alkali metal salts such as sodium chloride, 
potassium chloride and the like; alkaline earth metal salts such as 
calcium chloride, barium chloride and the like; colloidal metal oxides 
such as colloidal silica and the like; organic antistatic agents as 
disclosed in Japanese Patent Application Kokai No. 58-82242; and the like. 
The latices and emulsions include petroleum resin emulsion and latices of 
styrene/acrylic acid/acrylic acid ester terpolymer, styrene/acrylic 
acid/butadiene terpolymer, ethylene/vinyl alcohol copolymer, 
styrene/maleic acid/acrylic acid ester terpolymer and the like. The 
pigment includes clay, kaolin, talc, barium sulfate, titanium dioxide and 
the like. The pH modifier includes hydrochloric acid, phosphoric acid, 
citric acid, sodium hydroxide, sodium carbonate and the like. These 
additives are advantageously used in appropriate combination with the 
coloring pigment, coloring dye or fluorescent agent mentioned above. 
In order to make the base paper used in invention, there may be used a 
conventionally used paper machine such as Fourdrinier machine, a cylinder 
machine or the like; however, it is advantageous to adopt an appropriate 
method for making paper as disclosed in Japanese Patent Application Kokai 
Nos. 58-37642, 61-260240 and 61-284762. Though the thickness of the base 
paper is not critical, the base paper is preferably treated by an calender 
after the base paper is made as shown in Japanese Patent Application Kokai 
Nos. 58-37642 and 60-126397. The basis weight of the base paper is 
preferably 40-250 g/m.sup.2. 
For the purpose of the prevention of electrification, curling or the like, 
various backcoats layers may additionally be applied to the photographic 
support of this invention. The backcoat layers may contain in appropriate 
combination an inorganic anti-statistic agent, an organic antistatistic 
agent, a hydrophilic binder, a latex, a hardening agent a pigment, a 
surfactant and the like as disclosed in Japanese Patent Application Kokoku 
Nos. 52-18020, 57-9059, 57-53940, 58-56859; Japanese Patent Application 
Kokai Nos. 59-214849 and 58-184144; and the like. 
After various photograph-constituting layers are formed by coating, the 
photographic support obtained in this invention can be applied to various 
uses such as a color photographic paper, a monochromic photographic paper, 
a phototype-setting photographic paper, a copy photographic paper, a 
reversal photographic material, a negative and positive photographic 
material for silver salt dispersion transfer, a printing material and the 
like. The photographic support may have an emulsion layer containing 
silver chloride, silver bromide, silver chlorobromide, silver iodobromide, 
silver chloroiodobromide or the like. The photographic emulsion layer 
containing a silver halide may contain a color coupler to form a silver 
halid constituting layer having a multilayer structure. The emulsion layer 
may contain a physycal developing nucleus to form a receiving layer for 
silver salt dispersion transfer. As a binder of these 
photographic-containing layers, there may be used a hydrophilic polymer 
such as poly(vinyl pyrrolidone), poly(vinyl alcohol) a sulfuric acid ester 
of a polysaccharide or the like in addition to a conventional gelatin. The 
photographic-constituting layer may contain various additives. For 
example, there may be contained, in appropriate combination, an optical 
sensitizing dye such as a cyanine dye, a merocyanine dye or the like; a 
chemical sensitizer such as a water-soluble gold compound, a sulfur 
compound of the like; an antifoggant or a stabilizer such as a 
hydroxytriazolopyrimidine compound, a mercaptoheterocyclic compound or the 
like; a hardening agent such as formaldehyde, a vinylsulfone compound, an 
aziridine compound or the like; an auxiliary agent for coating such as a 
salt of benzene-sulfonic acid, a salt of sulfosuccinic acid or the like; 
and anti-contaminant such as a dialkylhydroqyuinone compound of the like; 
other components such as a fluoresent whitening agent, a dye for improving 
the sharpness, an antistatic agent, a pH modifier, a fogging agent, or a 
water-soluble iridium or rhodium compound in the production or dispersion 
of a silver halide. 
The photographic material containing a silver halide obtained from the 
photographic support of this invention is subjected to treatments such as 
exposure, development, termination, fixing, bleach, stabilization and the 
like as shown in "Photosensitive Materials for Photography and Handling 
Thereof" by Goro Miyamoto, published by Kyoritsu Shuppan Co., Ltd., 
Photographic Techniques Course Vol. 2, depending upon the photographic 
material thereof. Especially, the multilayer silver halide photographic 
material which is applied to a single bath bleaching-fixing treatment 
after the coloring development may also be applied to a treatment with a 
color development solution of any main ingredient such as CD-III, CD-IV 
(these two compounds are products of Kodak Co., Ltd.), Droxychrom (a trade 
name of May & Bayker Co., Ltd.) or the like. The development solution 
comprising the main ingredient may contain a development accelerator such 
as benzyl alcohol, a thallium salt, phenidone or the like. However, the 
photographic material may also be treated with a development solution 
which contains substantially no benzyl alcohol. A useful one-bath 
bleaching-fixing solution is a solution of a metal salt of 
aminopolycarboxylic acid (e.g. a ferric salt of ethylenediaminetetraacetic 
acid, propylenediaminetetraacetic acid, etc.). The useful fixing agent is 
sodium thiosulfate, ammonium thiosulfate or the like. The one-bath 
bleaching-fixing solution may contain various additives. For example, 
there may be contained in combination of desilver accelerator (e.g. 
mercaptocarboxylic acid as disclosed in U.S. Pat. No. 3,512,979, a 
mercaptoheterocyclic compound as disclosed in Belgian Patent No. 682,426, 
etc.), an anti-contaminant, a pH modifier, a pH buffer, a hardening agent 
(e.g. magnesium sulfate, aluminum sulfate, potassium alum, etc.), a 
surfactant and the like. The one-batch bleaching-fixing solution may be 
used at various pH values though the useful pH range is 6.0-8.0. 
Next, the second invention will be explained. 
In the second invention, the titanium dioxide pigment may have rutile 
structure, anatase structure or mixed crystal structure composition rutile 
structure and anatase structure. Furthermore, titanium dioxide pigments 
having any of these structures may be used in combination. In order to 
obtain photographic support which can provide printed image of especially 
high sharpness, the titanium dioxide pigment preferably has rutile 
structure, the titanium dioxide pigment is produced by methods such as 
sulfuric acid method and chlorine method. 
In the second invention, titanium dioxide pigment has a number-average 
diameter of 0.110-0.150 .mu.m. The "number-average diameter" used in this 
invention means number-average value calculated from particle diameter 
obtained by measuring diameter of 1000 titanium dioxide pigment particles 
in a certain direction by an electron microscope. If the number-average 
diameter is less than 0.110 .mu.m, much die lip stain occurs when 
polyolefin resin composition containing the titanium dioxide pigment is 
coated on a substrate and besides, printed image having a sufficient 
sharpness cannot be obtained. If it is more than 0.150 .mu.m, also image 
of sufficient sharpness cannot be obtained. Titanium dioxide pigment used 
in the second invention preferably has a number-average diameter of 
0.115-0.135 .mu.m in order that die lip stain occurs little in production 
of photographic support and printed image of high sharpness can be 
obtained. The titanium dioxide pigment of 0.110-0.150 .mu.m in 
number-average diameter can be produced under predetermined production 
conditions. That is, production conditions for obtaining the titanium 
dioxide pigment, especially, calcination conditions such as calcination 
temperature, calcination time, and mid and amount of inorganic compounds 
to be present in calcination (for example, various inorganic compounds 
disclosed in Japanese Patent Application Kokoku No. 48-18718 or 
combination thereof) can be determined by measuring number-average 
diameter of titanium dioxide pigment produced under a series of 
combination of test conditions. In this case, representative calcination 
conditions under which number-average diameter increases are higher 
calcination temperature, longer calcination time and smaller amount of 
inorganic compounds to be present in calcination and representative 
conditions under which number-average diameter decreases are lower 
calcination temperature, shorter calcination time and larger amount of 
inorganic compounds to be present in calcination. Especially preferred 
calcination conditions for titanium dioxide pigment used in the second 
invention are combined conditions of 800.degree.-1100.degree. C. in 
calcination temperature, 15 minutes--5 hours in calcination time and 
0.2-5% by weight in amount of inorganic compound to be present in terms of 
inorganic oxide and based on the weight of titanium dioxide. 
In the second invention, the titanium dioxide pigment is (1) one which has 
been subjected to a surface treatment with an aluminum-containing hydrated 
metal oxide to be coated with an aluminum-containing metal composition in 
an amount of more than 0.2% by weight, but less than 1.8% by weight in 
terms of anhydrous metal oxide based on the weight of the titanium dioxide 
pigment and with a silicon composition in an amount of 0-0.4% by weight in 
terms of anhydrous silicon dioxide based on the weight of the titanium 
dioxide pigment and/or (2) one which has been subjected to an inside 
treatment with an aluminum compound to contain, in the titanium dioxide 
pigment, an aluminum composition in an amount of more than 0.2% by weight, 
but less than 1.8% by weight in terms of anhydrous aluminum oxide based on 
the weight of the titanium dioxide pigment. The titanium dioxide may be 
subjected to both the surface treatment and the inside treatment. When the 
titanium dioxide pigment is produced by sulfuric acid method, it is 
preferably subjected to a surface treatment with a specific amount of 
aluminum-containing hydrated metal oxide in view of designing of titanium 
dioxide pigment. 
The surface-treated titanium dioxide pigment used in the second invention 
is produced by wet grinding and classifying titanium dioxide and then 
subjecting it to surface treatment with an aluminum-containing hydrated 
metal oxide to coat the surface of the titanium dioxide with an 
aluminum-containing metal composition in an amount of more than 0.2% by 
weight in terms of anhydrous metal oxide based on the weight of the 
titanium dioxide pigment and with a silicon composition in an amount of 
0-0.4% by weight in terms of anhydrous silicon dioxide based on the weight 
of the titanium dioxide pigment. If amount of the metal composition is 
0.2% by weight or less, resin layer of resin-coated paper type 
photographic support containing the titanium dioxide pigment is inferior 
in weathering resistance. On the other hand, if it is 1.8% by weight or 
more, die lip stain occurs much. The amount of metal composition is 
preferably 0.35-1.5% by weight, more preferably 0.5-1.0% by weight in 
terms of anhydrous metal oxide based on the weight of the titanium oxide 
pigment. The aluminum-containing hydrated metal oxide is preferably 
hydrated aluminum oxide. Amount of the silicon composition is 0-0.4% by 
weight, preferably 0-0.2% by weight in terms of anhydrous silicon dioxide. 
Furthermore, other hydrated metal oxides such as hydrated titanium oxide 
and the like may also be used so as to coat the surface of titanium 
dioxide with other metal components such as titanium and the like in a 
total amount of 0-1.8% by weight in terms of anhydrous metal oxide. 
Alternatively, the surface treatment may be carried out with hydrated 
aluminum silicon oxide to coat the titanium dioxide 
pigment with silicon component in an amount of 0-0.4% by weight in terms of 
anhydrous silicon dioxide. 
The surface treatment of titanium dioxide can be carried out using the same 
materials and methods as referred to in the surface treatment of titanium 
dioxide in the first invention. 
The inside-treated titanium dioxide pigment used in the second invention is 
produced by subjecting the titanium dioxide to inside treatment with an 
aluminum compound to contain therein an aluminum composition in an amount 
of more than 0.2% by weight, but less than 1.8% by weight in terms of 
aluminum oxide based on the weight of the titanium dioxide pigment. If 
amount of the aluminum composition is 0.2% by weight or less, resin layer 
of resin-coated paper containing the titanium dioxide pigment is inferior 
in weathering resistance. If it is 1.8% by weight or more, considerable 
die lip stain occurs and microgrit appears much. Preferred amount of the 
aluminum composition is 0.35-1.5% by weight in terms of aluminum oxide 
based on the weight of titanium dioxide pigment. 
The inside treatment of titanium dioxide can be carried out using the same 
materials and methods as referred to in the inside treatment of titanium 
dioxide in the first invention. 
If necessary, the titanium dioxide pigment used in the second invention may 
be subjected to treatment with various organic materials such as 
triethanolamine, trimethylolpropane, metal salts of fatty acids, and 
organopolysiloxanes. 
As methods, apparatuses and materials used for producing the titanium 
dioxide pigment used in the second invention, there may be used those 
which are used for producing titanium dioxide pigment used in the first 
invention. 
As polyolefin resin and polyolefin resins constituting the polyolefin resin 
mixture used in the second invention, mention may be made of, for example, 
homopolymers such as polyethylene, polypropylene, polybutene and 
polypentene and copolymers comprising two or more .alpha.-olefins such as 
ethylene-propylene copolymer and ethylene-butylene copolymer. From the 
points of economy and melt-extrusion coatability, preferred are 
polyethylene resins such as low-density polyethylene; medium-density 
polyethylene; high-density polyethylene; straight chain low-density 
polyethylene; copolymers of ethylene with .alpha.-olefin such as propylene 
or butylene; and carboxy-modified polyethylene. The polyolefin resin and 
polyolefin resins constituting the polyolefin resin mixture may have 
various densities, MI, molecular weights and molecular weight 
distributions, but normally, density is preferably 0.90-0.97 g/cm.sup.3, 
MI is preferably 1-30, more preferably 3-15, and molecular weight is 
preferably 20,000-250,000. These polyolefin resins may be used singly or 
as mixtures. In case of the resin layer being of multi-layer structure, 
resins of different properties may be used, for example, a resin having an 
MI of 5-10 is used for outer layer and a resin having an MI of 2-10 is 
used for inner layer. 
The titanium dioxide pigment used in the second invention can be contained 
in resin layer by the methods mentioned for containing titanium dioxide in 
resin layer in the first invention. 
As fluorescent agents used in the second invention and methods for 
containing the fluorescent agents in resin layer, there may be used those 
which are used in the first invention. 
As color pigments and color dyes used in the second invention, there may be 
used optional ones, but preferred are inorganic or organic blue pigments 
or blue dyes and inorganic or organic magenta pigments or magenta dyes. 
Examples of the inorganic blue pigments and dyes include cobalt blue, 
Prussian blue and ultramarine and examples of organic blue pigments and 
dyes include cerulean blue, Phthalocyanine Blue and Chromophthal Blue A3R. 
Examples of inorganic magenta pigments and dyes include cobalt violet and 
fast violet. Examples of organic magenta pigments and dyes include 
quinacridone red. Amount of the inorganic blue pigments or dyes to be 
added to resin layer is preferably 0.025-0.5% by weight, more preferably 
0.05-0.2% by weight based on the weight of resin layer. Amount of organic 
blue pigments and dyes is preferably 0.001-0.1% by weight, more preferably 
0.0025-0.05% by weight. Amount of inorganic magenta Pigments and dyes is 
preferably 0.025-1.0% by weight, more preferably 0.05-0.4% by weight based 
on the weight of resin layer. Amount of organic magenta pigments and dyes 
is preferably 0.001-0.03% by eight, more preferably 0.002-0.015% by weight 
bused on the weight of resin layer. If the amount is too small, sufficient 
coloring effect cannot be obtained and if it is too large, not only 
brightness decreases, but also die lip stain is very conspicuous. 
It is preferred to contain an antioxidant in resin layer of resin-coated 
paper type photographic support of the second invention in order to more 
effectively prevent die lip stain in production of resin-coated paper. The 
same antioxidants and methods for containing the antioxidants as used in 
the first invention may also be used in the second invention. 
In the second invention, the resin layer preferably further contains the 
metal salts of fatty acids as mentioned in the first invention. 
In the second invention, the resin layer contains polyolefin resin, 
titanium dioxide pigment, fluorescent agent and color pigment or color dye 
and preferably further contains metal salt of fatty acid and antioxidant. 
In case of the resin layer having a multi-layer structure, optional layer 
may contain the titanium dioxide pigment, the fluorescent agent, the 
coloring pigment or dye, the metal salt of fatty acid and the antioxidant. 
Furthermore, in the second invention, the resin layer provided on the 
image-forming side and, if necessary, the resin layer provided on back 
side may contain various additives in proper combination in addition to 
the above-mentioned titanium dioxide pigment, fluorescent agent, coloring 
pigment or coloring dye, metal salt of fatty acid and antioxidant. 
The photographic support of the second invention can be produced by 
providing resin layer on a substrate by the method mentioned in the first 
invention. 
The substrates used in the first invention may also be used in the second 
invention. 
Besides, pulps which constitute paper used as substrate, sizing agents, 
polymer compounds and various additives as used in the first invention may 
also be used in the second invention. Paper can also be made in the same 
manner as in the first invention. 
Back coat layer and various photographic layers can be provided on 
photographic support in the same manner as in the first invention and thus 
photographic materials can be obtained. The resulting photographic support 
is applicable to various uses as mentioned in the first invention. 
Next, the third invention will be explained. 
The titanium dioxide pigment used in the third invention has a 
number-average diameter (as defined in the second invention) of 
0.110-0.150 .mu.m and carries on the surface at least one compound 
selected from the group consisting of magnesium compound, calcium compound 
and barium compound in an amount of 0.004-0.1% by weight in terms of metal 
based on the weight of the titanium dioxide pigment. 
In the third invention, titanium dioxide pigment may have rutile structure, 
anatase structure or mixed crystal structure comprising rutile structure 
and anatase structure. Further more, titanium dioxide pigments having 
these structures may be used in combination, but in order to obtain 
photographic support which can provide printed image especially high in 
sharpness, the titanium dioxide pigment preferably has rutile structure. 
If number-average diameter of titanium dioxide is less than 0.110 .mu.m, 
die lip stain occurs much when polyolefin resin composition containing the 
titanium dioxide is coated on a substrate and besides, printed image 
having sufficient sharpness cannot be obtained. If number-average diameter 
is more than 0.150 .mu.m, printed image having sufficient sharpness cannot 
be also obtained. The titanium dioxide pigment used in the third invention 
preferably has a number-average diameter of 0.115-0.135 .mu.m in order 
that die lip stain occurs little in production of photographic support and 
that printed image of high sharpness can be obtained. Titanium dioxide 
pigment having a number-average diameter of 0.110-0.150 .mu.m can be 
produced under the same conditions as mentioned in the second invention. 
The titanium dioxide pigment used in the third invention is produced by 
supporting on the surface at least one compound selected from the group 
consisting of magnesium compound, calcium compound and barium compound in 
an amount of 0.004-0.1% by weight in terms of metal based on the titanium 
dioxide pigment. If amount of the compound supported on the surface of 
titanium dioxide pigment is less than 0.004% by weight, much die lip stain 
occurs when polyolefin resin composition containing the titanium dioxide 
pigment is coated on a substrate and besides, printed image having high 
sharpness cannot be obtained. On the other hand, if the amount of the 
compound is more than 0.1% by weight, also much die lip stain occurs when 
polyolefin resin composition containing the titanium dioxide pigment is 
coated on a substrate and besides, printed image of high sharpness cannot 
be obtained. The amount of the compound supported on the surface of 
titanium dioxide pigment is preferably 0.006-0.07% by weight in terms of 
metal based on the weight of titanium dioxide. Calcium compounds, 
magnesium compounds and barium compounds supported on the surface of 
titanium dioxide are preferably water-soluble salts, but may be oxides or 
hydroxides. Examples of the calcium compounds include calcium chloride, 
calcium hydroxide, calcium oxide, calcium acetate, calcium citrate and 
calcium carbonate. Examples of the magnesium compounds include magnesium 
chloride, magnesium sulfate, magnesium hydroxide, magnesium oxide, 
magnesium acetate, magnesium citrate, and magnesium carbonate. Examples of 
the barium compounds include barium chloride, barium hydroxide and barium 
oxide. 
Supporting of calcium compound, magnesium compound, or barium compound on 
the surface of titanium dioxide can be carried out by adding the compound 
to titanium dioxide slurry at an optional stage in the step of making 
titanium dioxide slurry by suspending ground product of titanium dioxide 
clinker and the subsequent steps in the course of production of titanium 
dioxide pigment. Preferably, aqueous solution or suspension of the 
compound is added to titanium dioxide slurry at optional stage at or after 
wet grinding classification step to adsorb the compound onto the surface 
of titanium dioxide. 
As a result of the investigation conducted by the inventors, it has been 
found that amount of the magnesium compound, calcium compound or barium 
compound supported on the surface of titanium dioxide depends on various 
factors, e.g. kind of the compound, amount of the compound added and step 
at which the compound is added; properties of titanium dioxide particles 
such as particle diameter, specific surface area, crystal form and crystal 
structure; kind and amount of hydrated metal oxide with which the surface 
of titanium dioxide pigment is treated; and conditions of titanium dioxide 
slurry such as pH, temperature and concentration. Therefore, specific 
production conditions, especially kind and addition amount of the 
magnesium compound, calcium compound and barium compound can be determined 
by evaluating properties of polyolefin resin-coated paper type 
photographic supports produced by containing the pigment in resin layer 
which is produced under a series of combination of test conditions. 
Amount of the compound supported on the surface of titanium dioxide pigment 
is usually considerably smaller than the amount of the compound which has 
been added to titanium dioxide slurry. Specifically, amount of the 
magnesium compound, calcium compound or barium compound which has been 
supported on the surface of titanium dioxide can be obtained by analysis 
conducted in the following manner. 
1.0000 g of accurately weighed titanium dioxide pigment is put in a 
crucible and thereto is added 10 ml of 36 wt% hydrochloric acid solution 
of special grade. The crucible is closed and heated at 360.degree. 
C..+-.20.degree. C. for 15 minutes on a sand bath and cooled and then 
filtrated (if separation by the filtration is insufficient, centrifugal 
separation is also carried out in combination). The filtrate is washed 
with 10 ml of dilute hydrochloric acid obtained by diluting special grade 
36 wt% hydrochloric acid solution with 490 ml of distilled water and to 
the resulting filtrate is added 3 ml of a 3 wt% solution of special grade 
SrCl.sub.2.6H.sub.2 O in distilled water and total amount is adjusted to 
100 ml with distilled water to obtain a test liquid. This test liquid is 
subjected to atomic absorption spectrometry and concentration of calcium, 
magnesium or barium in the test liquid by previously obtained calibration 
curve and thus amount of the compound supported on the surface of titanium 
dioxide pigment is calculated. 
The titanium dioxide pigment used in the third invention is preferably that 
which has been subjected to a surface treatment with a specific amount of 
hydrated metal oxide containing at least aluminum or to an inside 
treatment with a specific amount of an aluminum compound and in addition, 
it may be subjected to both the surface treatment and the inside 
treatment. Especially, when the titanium dioxide pigment is produced by 
sulfuric acid method, the titanium dioxide pigment is preferably subjected 
to the surface treatment with a specific amount of aluminum-containing 
hydrated metal oxide from the point of designing of titanium dioxide 
pigment. 
The surface-treated titanium dioxide pigment used preferably in the third 
invention is produced by subjecting titanium dioxide after wet ground and 
classified to a surface treatment with an aluminum-containing hydrated 
metal oxide to coat the surface of the titanium dioxide pigment with an 
aluminum-containing metal composition in an amount of more than 0.2% by 
weight, but less than 1.8% by weight in terms of anhydrous metal oxide 
based on the weight of the titanium dioxide pigment and with a silicon 
composition in an amount of 0-0.4% by weight in terms of anhydrous silicon 
dioxide. If amount of the metal composition is 0.2% by weight or less, 
resin layer of resin-coated paper type photographic support containing the 
titanium dioxide pigment is inferior in weathering resistance. If it is 
1.8% by weight or more, die lip stain occurs much. The amount of the metal 
composition is preferably 0.35-1.5% by weight, more preferably 0.5-1.0% by 
weight in terms of anhydrous metal oxide based on the weight of the 
titanium dioxide pigment. The aluminum-containing hydrated metal oxide is 
preferably hydrated aluminum oxide. The amount of the silicon composition 
is 0-0.4% by weight, preferably 0-0.2% by weight in terms of anhydrous 
silicon dioxide. Other hydrated metal oxides such as hydrated titanium 
oxide can be used so as to coat with other metal components such as 
titanium in a total amount of 0-1.8% by weight in terms of anhydrous metal 
oxide. Further, the surface treatment can be carried out with a hydrated 
aluminum silicon oxide so as to coat with a silicon component in an amount 
of 0-0.4% by weight in terms of anhydrous silicon dioxide. 
The materials and methods used for surface treatment in the first invention 
can be used for surface treatment of titanium dioxide in the third 
invention. 
Further, the inside-treated titanium dioxide pigment used preferably in the 
third invention can be produced by subjecting titanium dioxide pigment to 
inside-treatment with an aluminum compound to contain therein an aluminum 
composition in an amount of more than 0.2% by weight, but less than 1.8% 
by weight in terms of aluminum oxide based on the weight of the titanium 
dioxide pigment. If amount of the aluminum composition is 0.2% by weight 
or less, weathering resistance of resin layer of resin-coated paper 
containing the titanium dioxide pigment is deteriorated. If it is 1.8% by 
weight or more, die lip stain occurs much and besides much microgrit 
appears. Preferred amount of the aluminum composition is 0.35-1.5% by 
weight in terms of aluminum oxide based on the weight of the titanium 
dioxide pigment. 
The materials and methods used for inside treatment of titanium dioxide in 
the first invention can be used in the inside treatment in the third 
invention. 
If necessary, the titanium dioxide pigment used in the third invention may 
be subjected to treatment with organic materials such as triethanolamine, 
trimethylolpropane, metal salts of fatty acids, and organopolysiloxane. 
The methods, apparatuses and materials mentioned in the first invention for 
production of titanium dioxide pigment in the first invention can be used 
as methods, apparatuses and materials for production of titanium dioxide 
pigment in the third invention. 
As polyolefin resins used in the third invention, there may be used those 
which are used in the first invention. 
In the third invention, there may be used the methods for containing 
titanium dioxide pigment in resin layer which are used in the second 
invention. 
As antioxidants and methods for containing them in resin layer used in the 
third invention, there may be used those which are referred to in the 
first invention. 
The metal salts of fatty acids referred to in the first invention can also 
be contained in resin layer in the third invention. 
The resin layer in the third invention preferably contains a fluorescent 
agent in order to reduce yellowing caused by titanium dioxide pigment to 
improve whiteness. Various fluorescent agents such as those of naphthalene 
type, stilbene type, thiophene type and coumarin type may be used, but 
considering improvement of whiteness, dispersibility in polyolefin resin, 
heat resistance, anti-bleeding out, weathering resistance and stability in 
photographic processing solution, bis(benzoxazolyl)naphthalene fluorescent 
agents having substituent and/or bis(benzoxazolyl)stilbene fluorescent 
agents having substituent are preferred. Specifically, there may be used 
the fluorescent agents and methods for containing the fluorescent agents 
in resin layer as mentioned in the first invention. 
Resin layer may further contain reagents as mentioned in the first 
invention such as inorganic or organic blue pigments or blue dyes; 
inorganic or organic magenta pigments or magenta dyes; and various 
additives. 
The photographic support of the third invention can be produced by 
providing resin layer on a substrate by the method as mentioned in the 
first invention. 
As the substrates used in the third invention, there may be used those 
which are referred to as substrates in the first invention. 
Furthermore, pulse which constitute paper used as substrate, sizing agents, 
polymer compounds, and various additives as mentioned in the first 
invention may also be used in the third invention. Making of paper may 
also be carried out in the same manner as in the first invention. 
Formation of backcoat layer and various photographic layers on the 
photographic support may also be carried out in the same manner as in the 
first invention and thus photographic materials are obtained. The 
resulting photographic materials can be applied to various uses as 
mentioned in the first invention.

DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION 
This invention is explained in more detail by the following examples. 
Examples 1-2 and Comparative Examples 1-11 
Rutile type titanium dioxide clinker produced in accordance with the 
production procedure of rutile type titanium dioxide pigment by sulfuric 
acid method was subjected to grinding and dressing and further subjected 
to wet grinding and classification to obtain titanium dioxide slurry 
containing substantially no coarse particles. This slurry was put in a 
reaction tank and pH of the slurry was raised to about 9.2 with sodium 
hydroxide. Then, this slurry was heated to about 70.degree. C. and 
thereafter, thereto was added an aqueous sodium aluminate-solution in an 
amount of 0.15% by weight, 0.75% by weight or 1.6% by weight in terms of 
Al.sub.2 O.sub.3 based on the dry weight of the titanium dioxide and the 
mixture was left to stand for 30 minutes. 
pH of the slurry was lowered to 7.0 by addition of 20% sulfuric acid and 
the slurry was aged for 2 hours. Thereafter, the original liquid of 
titanium dioxide slurry surface treated with hydrated alumina was 
filtrated by a filter press and successively, titanium dioxide cake in the 
filter press was washed with running water under predetermined conditions 
until the suspension electric conductivity defined hereabove reached 45 
.mu..nu./cm. 
Then, the titanium dioxide cake was dried and impact ground in a hammer 
mill having a quantitative feeder and further subjected to finishing 
grinding to produce rutile type titanium dioxide pigments the surface of 
which was treated with different amounts of hydrated alumina. 
50 parts by weight of low-density polyethylene having a density of 0.918 
g/cm.sup.3 and an MFR of 8.0 g/10 min or 3.5 g/10 min, 50 parts by weight 
of the titanium dioxide pigment obtained above or commercially available 
anatase type titanium dioxide pigment and 2.5 parts by weight of zinc 
stearate were well kneaded at 150.degree. C. by a Banbury mixer to prepare 
a masterbatch of titanium dioxide pigment. 
Separately, 50 parts by weight of the same low-density polyethylene as used 
for preparation of the above titanium dioxide pigment masterbatch, 50 
parts by weight of the above titanium dioxide or commercially available 
anatase type titanium dioxide pigment, 1.25 part by weight of ultramarine 
(#2000, manufactured by Daiichi Kasei Kogyo Co.) and 2.5 parts by weight 
of zinc stearate were well kneaded at 150.degree. C. by a Banbury mixer to 
prepare a titanium dioxide pigment masterbatch containing ultramarine. 
Furthermore, 0.28 part by weight of fluorescent agent [IX] mentioned 
hereinbefore and 0.28 part by weight of zinc stearate were previously well 
mixed and the resulting mixture was well kneaded with 40 parts by weight 
of the same low-density polyethylene as used for preparation of the above 
titanium dioxide pigment masterbatch in a Laboplast mill at 135.degree. C. 
to prepare a fluorescent agent masterbatch. 
On the other hand, a mixture of 50 parts by weight of bleached hardwood 
kraft pulp and 50 parts by weight of bleached softwood sulfite pulp was 
beaten to a Canadian standard freeness of 310 ml. To 100 parts by weight 
of this pulp were added 3 parts by weight of cationized starch, 0.2 part 
by weight of anionized polyacrylamide, 0.4 part by weight of an alkyl 
ketene dimer emulsion (as ketene dimer content) and 0.4 part by weight of 
polyamine-polyamide-epichlorohydrin resin and a paper of 160 g/m.sup.2 in 
basis weight was made from he mixture. The resulting wet paper was dried 
at 110.degree. C. and successively impregnated with an impregnation 
solution consisting of 3 parts by weight of a carboxy-modified polyvinyl 
alcohol, 0.05 part by weight of a fluorescent brightener, 0.002 part by 
weight of a blue dye, 0.2 part by weight of citric acid and 97 parts by 
weight of water at a coverage of 25 g/m.sup.2. Then, this paper was dried 
by hot air of 110.degree. C. and supercalendered at a linear pressure of 
90 kg/cm. Then, both sides of the paper were subjected to corona discharge 
treatment to obtain a paper substrate for resin-coated paper for 
photograph. 
On the back side of the paper substrate was coated a mixture (1:1 in weight 
ratio) of a high-density polyethylene (density 0.960 g/cm.sup.3, MFR=5 
g/l0 min) and a low-density polyethylene (density 0.923 g/cm.sup.3, MFR=5 
g/10 min) at a thickness of 30 .mu. at a resin temperature of 330.degree. 
C. using a melt extrusion coater. Then, a resin composition composed of 
the titanium dioxide pigment masterbatch obtained above, the titanium 
dioxide pigment masterbatch containing ultramarine obtained above and the 
fluorescent agent masterbatch obtained above, and a high-density 
polyethylene (density 0.970 g/cm.sup.3, MFR as shown in Table 1) and a 
low-density polyethylene (density: 0.920 g/cm.sup.3, MFR as shown in Table 
1) as diluent resins at the mixing ratio as shown in Table 1 was melt 
extrusion coated on the right side of the above paper substrate at a 
thickness of 30 .mu. at a resin temperature of 330.degree. C. to make 
polyethylene resin-coated papers of this invention and comparative 
polyethylene resin coated papers. The right side coated with polyethylene 
containing titanium dioxide pigment was finished to completely smooth 
glossy surface and the back side coated with polyethylene was finished to 
matte surface such as that of paper. 
Apparent whiteness of the side containing titanium dioxide pigment of the 
thus obtained Polyethylene resin-coated paper type photographic support 
was visually evaluated. Criteria for evaluation are as follows. 
".circleincircle." Extremely white 
".circle." Considerably white 
" " White 
".DELTA." Slightly yellow 
"X" Yellow 
Light resistance of the photographic support was evaluated in the following 
manner. 
Optical density of the right side after subjected to irradiation for 120 
hours by a fadomenter (FAL-25X-HCL manufactured by Suga Tester Co.) was 
measured by a densitometer (TD-504 manufactured by Macbeth Co.). The 
greater value of optical density indicates that degree of yellowing is 
great and light deterioration is conspicuous (inferior in light 
resistance). 
Furthermore, die lip stain was measured as follows: 
Using a screw type extrusion machine having an extruder bore of 65 mm and a 
melt extrusion machine having a 750 mm-wide T-die, melt extrusion was 
carried out at a resin temperature of 320.degree. C. and a screw rotation 
speed of 100 rpm for 2 hours. The number of stains formed on the lip die 
was counted. 
In order to measure sharpness of printed image, a color photographic paper 
comprising the above obtained resin-coated paper as a support was prepared 
as follows: First, the back side of the resin-coated paper was subjected 
to corona discharge treatment and was coated with a backcoat layer 
comprising a composition of colloidal silica:styrene acrylate latex=1:1 in 
a dry weight ratio at a coverage of 0.4 g/m.sup.2. Then, resin surface of 
the right side of the resin-coated paper containing titanium dioxide 
pigment was subjected to corona discharge treatment and then provided with 
a blue-sensitive emulsion layer containing yellow-coloring coupler, an 
interlayer containing an anti-color mixing agent, a green-sensitive 
emulsion layer containing a magenta-color coupler, an ultraviolet 
absorbing layer containing ultraviolet absorber, a red-sensitive emulsion 
layer containing a cyan-coloring coupler, and a protective layer to obtain 
a color photographic paper. Each emulsion layer contained silver 
chlorobromide in an amount of 0.6 g/m.sup.2 in terms of silver nitrate and 
in addition gelatin necessary for production and dispersion of silver 
halide and film-formation. The emulsion layers further contained suitable 
amounts of antifoggant, sensitizing dye, coating aid, hardener, thickener 
and filter dye. 
A resolving power chart was brought into close contact with the 
photographic paper, followed by exposing to green light and color 
developing to obtain a test sheet. Image on this test sheet was subjected 
to measurement by a microdensitometer and contrast transfer function 
(hereinafter referred to as "CTF") was obtained as sharpness of the image 
in the green-sensitive layer using a personal computer according to 
ordinary method. Sharpness of printed image on resin-coated paper was 
evaluated thereby. The layer value of CTF means higher sharpness of 
printed image. 
The results are shown in Table 2. 
TABLE 1 
__________________________________________________________________________ 
Kind of titanium dioxide 
pigment Masterbatch 
Coating Amount of 
Total 
amount of 
Amount 
Amount 
fluores- 
amount 
surface 
of white 
of blue 
cent agent 
of MFR of 
treating 
master- 
master- 
master- 
master- 
base resin 
Crystal form 
agent*.sup.3 
batch*.sup.4 
batch*.sup.5 
batch batch 
of master- 
of titanium 
(% by (part by 
(part by 
(part by 
(part by 
batch 
dioxide 
weight) 
weight) 
weight) 
weight) 
weight) 
(g/10 min) 
__________________________________________________________________________ 
Comparative 
Example 
1 Rutile type*.sup.1 
0.15 18.8 7.2 3 29 8.0 
2 Rutile type*.sup.1 
0.15 18.8 7.2 3 29 3.5 
Example 
1 Rutile type*.sup.1 
0.75 18.8 7.2 3 29 8.0 
2 Rutile type*.sup.1 
0.75 26.0 0 3 29 8.0 
Comparative 
Example 
3 Rutile type*.sup.1 
0.75 18.8 7.2 3 29 3.5 
4 Rutile type*.sup.1 
0.75 26.0 0 3 29 3.5 
5 Rutile type*.sup.1 
0.75 18.8 7.2 0 26 8.0 
6 Rutile type*.sup.1 
0.75 26.0 0 0 26 8.0 
7 Rutile type*.sup.1 
0.75 28.8 7.2 0 26 3.5 
8 Rutile type*.sup.1 
0.75 26.0 0 0 26 3.5 
9 Rutile type*.sup.1 
1.60 18.8 7.2 3 29 8.0 
10 Rutile type*.sup.1 
1.60 18.8 7.2 3 29 3.5 
11 Anatase 
1.55 18.8 7.2 0 26 8.0 
type*.sup.2 
__________________________________________________________________________ 
Diluent resin 
High-density polyethylene 
High-density polyethylene 
Weighted- 
Amount Amount mean MFR of 
(part by 
MFR (part by 
MFR resin*.sup.6 
weight) 
(g/10 min) 
weight) 
(g/10 min) 
(g/10 min) 
__________________________________________________________________________ 
Comparative 
Example 
1 20 7.0 51 6.0 6.78 
2 20 3.0 51 3.5 3.60 
Example 
1 20 7.0 51 6.0 6.78 
2 20 7.0 51 6.0 6.78 
Comparative 
Example 
3 20 4.0 51 3.5 3.60 
4 20 4.0 51 3.0 3.60 
5 20 7.0 51 6.0 6.72 
6 20 7.0 54 6.0 6.72 
7 20 4.0 54 3.5 3.60 
8 20 4.0 54 3.5 3.60 
9 20 7.0 51 6.0 6.78 
10 20 4.0 51 3.5 3.60 
11 20 7.0 54 6.0 6.72 
__________________________________________________________________________ 
*.sup.1 Rutile type titanium dioxide pigment produced by sulfuric acid 
method mentioned herebefore. 
*.sup.2 Commercially available anatase type titanium dioxide pigment 
produced by sulfuric acid method. 
*.sup.3 Amount of aluminum composition coated on the surface of titanium 
dioxide by surface treatment with hydrated alumina is shown by % by weigh 
in terms of Al.sub.2 O.sub.3 based on the dry weight of titanium dioxide. 
*.sup.4 Amount of masterbatch of titanium dioxide pigment is shown in par 
by weight. 
*.sup.5 Amount of masterbatch of titanium dioxide containing ultramarine 
is shown in part by weight. 
*.sup.6 This is the same as that mentioned herebefore. 
TABLE 2 
______________________________________ 
CTF Light 
Total (sharpness 
resistance 
Apparent 
number of of printed 
(optical 
whiteness 
die lip stain*.sup.7 
image)*.sup.8 
density) 
______________________________________ 
Comparative 
Example 
1 .largecircle. 
0 0.67 0.11 
2 .largecircle. 
0 0.68 0.11 
Example 
1 .largecircle. 
4 0.71 0.05 
2 .circle..DELTA. 
1 0.71 0.05 
Comparative 
Example 
3 .largecircle. 
21 0.71 0.05 
4 .circle..DELTA. 
11 0.70 0.05 
5 .DELTA. 2 0.71 0.04 
6 X 0 0.71 0.04 
7 .DELTA. 14 0.71 0.04 
8 X 7 0.70 0.04 
9 .largecircle. 
68 0.68 0.05 
10 .largecircle. 
100 or more 
0.69 0.05 
11 .circle..DELTA. 
100 or more 
0.56 0.04 
______________________________________ 
*.sup.7 Total number of die lip stain formed on the front and rear of the 
die lip. 
*.sup.8 A value at a line density = 5/mm. 
As is clear from Table 2, the resin-coated paper type photographic supports 
of the first invention which had on its image-forming side a resin layer 
comprising a rutile type titanium dioxide pigment the surface of which was 
coated with aluminum composition in an amount of more than 0.2% by weight, 
but less than 1.5% by weight in terms of Al.sub.2 O.sub.3 based on the 
weight of the titanium dioxide, a substituent-containing 
bis(benzoxazolyl)stilbene fluorescent agent, and a polyolefin resin having 
a weighted-mean MFR of more than 4.0 g/l0 min, but less than 9.5 g/l0 min 
(Examples 1 and 2) were photographic supports which were high in sharpness 
of printed image, high in lightness and apparent whiteness and besides 
showed very little die lip stain at production of the photographic support 
and thus had good surface property. 
On the other hand, the comparative photographic supports (Comparative 
Examples 1-11) had respective defects. 
That is, when anatase type titanium dioxide pigment was used (Comparative 
Example 11), sharpness of printed image was low. Even if rutile type 
titanium dioxide pigment was used, when the surface thereof was coated 
with a metal composition in an amount of 0.2% by weight or less in terms 
of anhydrous metal oxide based on the weight of the titanium dioxide 
(Comparative Examples 1 and 2), light resistance was inferior. When 
titanium dioxide pigment the surface of which was coated with a metal 
composition in an amount of 1.5% by weight or more in terms of anhydrous 
metal oxide based on the weight of the titanium dioxide was used 
(Comparative Examples 9 and 10), much die lip stain occurred. When 
weighted-mean MFR of polyolefin resin was 4.0 g/l0 min or less 
(Comparative Examples 3, 4, 7 and 8), also much die lip stain occurred. 
Further, when fluorescent agent was not contained (Comparative Examples 
5-8), resin surface on the image forming side of the photographic support 
was yellowed. 
Examples 3-10 
Procedure of Example 1 was repeated except that a low-density polyethylene 
resin for masterbatch used in Example 1 to which was previously added 
tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methine in 
an amount as shown in Table 3 was used as low-density polyethylene resin 
for masterbatch. 
The results are shown in Table 3. 
TABLE 3 
______________________________________ 
Total 
Amount of Apparent number CTF (sharpness 
antioxidant*.sup.9 
white- of die lip 
of printed 
Example 
(ppm) ness*.sup.10 
stain*.sup.10 
image)*.sup.10 
______________________________________ 
3 0 .largecircle. 
4 0.70 
4 10 .largecircle. 
2 0.71 
5 20 .largecircle. 
0 0.71 
6 150 .largecircle. 
0 0.70 
7 300 .largecircle. 
0 0.71 
8 500 .largecircle. 
1 0.69 
9 1000 .largecircle. 
3 0.67 
10 2000 .largecircle. 
7 0.67 
______________________________________ 
*.sup.9 Amount (ppm) of antioxidant based on the weight of resin 
composition on the side containing titanium dioxide pigment. 
*.sup.10 Same as in Table 2. 
As can be seen from Table 3, die lip stain was highly inhibited by adding a 
suitable amount of antioxidant to resin composition as the preferred 
embodiment of the first invention. It can also be recognized that the 
amount of antioxidant is preferably 10-500 ppm, especially preferably 
20-300 ppm based on the resin composition and if the amount is more than 
1000 ppm, die lip stain rather increases. As mentioned above, it can be 
seen that the photographic support of the first invention containing a 
suitable amount of antioxidant is an excellent photographic support which 
provides high sharpness of printed image, is apparently white and besides 
shows little die lip stain at production of the support and thus has good 
surface property. 
Examples 11-17 and Comparative Examples 12-16 
The procedure of Example 5 was repeated except that the titanium dioxide 
pigment prepared in the following manner was used in place of the rutile 
type titanium dioxide pigment used in Example 6. 
The rutile type titanium dioxide clinker obtained after the calcination in 
the sulfuric acid method explained herebefore was subjected to grinding 
and dressing and further to wet grinding and classification to obtain a 
titanium dioxide slurry containing substantially no coarse titanium 
dioxide particles. 
This slurry was charged in a reaction tank and pH of the slurry was raised 
to about 9.2 with sodium hydroxide. The slurry was heated to about 
70.degree. C.. Thereafter, to the slurry were added aqueous sodium 
aluminate solution or/and aqueous sodium silicate solution so that the 
surface of the titanium dioxide was coated with metal composition in an 
amount as shown in Table 4 in terms of Al.sub.2 O.sub.3 or/and SiO.sub.2 
based on the dry weight of the titanium dioxide and then the slurry was 
left to stand for 30 minutes. In the case of coating the surface with 
hydrated titanium oxide, before raising pH of titanium dioxide slurry with 
sodium hydroxide, aqueous titanyl sulfate solution was added to the slurry 
so that the surface was coated with titanium composition in an amount as 
shown in Table 4 in terms of TiO.sub.2 based on the dry weight of the 
titanium dioxide. Thereafter, rutile type titanium dioxide pigments as 
shown in Table 4 were prepared in the same manner as in Example 1. 
The results obtained are shown in Table 4. 
TABLE 4 
__________________________________________________________________________ 
CTF*.sup.12 
Light*.sup.12 
Kind of compound coated on the 
Total*.sup.12 
(sharp- 
resis- 
surface of rutile type titanium 
Apparent 
number of 
ness of 
tance 
dioxide pigment and coating amount*.sup.11 
white- 
die lip 
printed 
(optical 
Al.sub.2 O.sub.3 
SiO.sub.2 
TiO.sub.2 
Total amount 
ness*.sup.12 
stain image) 
density) 
__________________________________________________________________________ 
Example 
11 0.25 
0 0 0.25 .largecircle. 
0 0.70 0.07 
12 0.5 0 0 0.5 .largecircle. 
0 0.71 0.05 
13 0.75 
0 0 0.75 .largecircle. 
0 0.71 0.05 
14 1.0 0 0 1.0 .largecircle. 
0 0.70 0.05 
15 1.25 
0 0 1.25 .largecircle. 
1 0.71 0.05 
16 0.5 0.1 
0 0.6 .largecircle. 
3 0.70 0.05 
17 0.5 0.1 
0.1 
0.7 .largecircle. 
4 0.70 0.05 
Comparative 
Example 
12 0.15 
0 0 0.15 .largecircle. 
0 0.68 0.11 
13 1.6 0 0 1.6 .largecircle. 
52 0.68 0.05 
14 0 0.5 
0 0.5 .largecircle. 
63 0.69 0.06 
15 1.0 0 0.6 
1.6 .largecircle. 
57 0.68 0.05 
16 0.75 
0.5 
0 1.25 .largecircle. 
more than 
0.68 0.05 
100 
__________________________________________________________________________ 
*.sup.11 Amount (% by weight) of metal composition coated on the surface 
of titanium dioxide in terms of Al.sub.2 O.sub.3, SiO.sub.2 and TiO.sub.2 
based on the dry weight of titanium dioxide when the surface of titanium 
dioxide was treated with hydrated alumina, hydrated silicon dioxide and/o 
hydrated titanium dioxide 
*.sup.12 Same as in Table 2. 
As can be seen from Table 4, the photographic supports (Examples 11-17) of 
the first invention where rutile type titanium dioxide the surface of 
which was coated with aluminum-containing metal component in an amount of 
more than 0.2% by weight, but less than 1.5% by weight in terms of 
anhydrous metal oxide based on the weight of the titanium dioxide and with 
silicon component in an amount of 0-0.4% by weight in terms of anhydrous 
silicon oxide was used as titanium dioxide pigment in resin layer of 
resin-coated paper were excellent photographic supports which can provide 
high sharpness of printed image, are apparently white and show little die 
lip stain at production thereof and thus have good surface property. 
Furthermore, it can be recognized that hydrated alumina is preferred as 
the surface treating agent for titanium dioxide from the points of 
inhibition of die lip stain and light resistance of photographic support, 
and coating amount thereof is preferably 0.4-1.25% by weight in terms of 
Al.sub.2 O.sub.3 based on the weight of titanium dioxide. 
On the other hand, the comparative photographic supports (Comparative 
Examples 12-16) had problems. That is, even if rutile type titanium 
dioxide was used, when surface thereof was coated with metal composition 
in an amount of 1.5% by weight or more in terms of anhydrous metal oxide 
based on the weight of titanium dioxide (Comparative Examples 13 and 15) 
and when the surface thereof was coated with silicon composition in an 
amount of 0.5% by weight or more in terms of SiO.sub.2 based on the weight 
of titanium dioxide (Comparative Examples 14 and 16), much die lip stain 
occurred. Furthermore, when titanium dioxide the surface of which was 
coated with metal composition in an amount of 0.25% by weight or less in 
terms of anhydrous metal oxide based on the weight of titanium dioxide wa 
used (Comparative Example 12), light resistance was inferior. 
Examples 18-25 and Comparative Example 17 
Procedure of Example 5 was repeated except that content of fluorescent 
agent [IX] in the resin layer was changed as shown in Table 5. In this 
case, in order not to change weighted-mean MFR of polyethylene resin, when 
content of the fluorescent agent was reduced, amount of masterbatch of the 
fluorescent agent was reduced and low-density polyethylene used for 
preparation of said masterbatch was added as diluent resin in an amount 
corresponding to the reduced amount of masterbatch of the fluorescent 
agent. On the other hand, when content of the fluorescent agent was 
increased, masterbatch of the fluorescent agent prepared in the same 
manner as in Example 1 was added to low-density polyethylene corresponding 
to the diluent resin in Example 5 (namely, low-density polyethylene 
corresponding to the diluent resin in Example 1) and amount of low-density 
polyethylene for diluent resin corresponding to the amount of the added 
masterbatch of fluorescent agent was reduced. 
The results obtained are shown in Table 5. 
TABLE 5 
______________________________________ 
Content of Total number 
fluorescent agent in 
Apparent of die lip 
resin layer (mg/m.sup.2) 
whiteness*.sup.13 
stain*.sup.13 
______________________________________ 
Comparative 
0 .DELTA. 0 
Example 
17 
Example 
18 0.1 .DELTA. 0 
19 0.2 .DELTA. 0 
20 0.5 .largecircle. 
0 
21 3 .largecircle. 
0 
22 6.3 .largecircle. 
0 
23 15 .largecircle. 
1 
24 25 .largecircle. 
2 
25 50 .largecircle. 
4 
______________________________________ 
*.sup.13 Same as in Table 2. 
As is clear from Table 5, when content of the fluorescent agent in resin 
layer is less than 0.3 mg/m.sup.2, apparent whiteness of the image forming 
side of photographic support is insufficient and when it is more than 25 
mg/m.sup.2, die lip stain tends to occur much. Thus, it can be seen that 
the content is preferably 0.3-25 mg/m.sup.2. As shown above, the 
photographic supports of this invention which contain a proper amount of 
fluorescent agent show little die lip stain at production thereof and thus 
have good surface property, can provide printed images of high sharpness 
and besides have high apparent whiteness. 
Examples 26-34 and Comparative Examples 18-20 
procedure of Example 5 was repeated except that low-density polyethylene 
for masterbatch and low-density polyethylene and hi9h-density polyethylene 
for diluent resins having substantially the same density as of those used 
in Example 6, but having MFR as shown in Table 6 were used in place of 
those which were used in Example 6. 
The results obtained are shown in Table 6. 
Degree of neck-in of resin at production of photographic support was 
visually evaluated relative to influence thereof on processability and is 
shown as degree of neck-in which affected processability. Criteria for 
evaluation are as follows: 
Neck-in causes no problem for processability ".circle." 
Neck-in sometimes causes problem for processability ".DELTA." 
Neck-in causes some problem for processability ".DELTA." 
Neck-in causes problem for processability "x" 
TABLE 6 
__________________________________________________________________________ 
MFR of high- 
MFR of low- 
MFR of resin 
density poly- 
density Weighted- 
for ethylene for 
polyethylene for 
mean MFR of 
masterbatch 
diluent resin 
diluent resin 
resin*.sup.14 
(g/10 min) 
(g/10 min) 
(g/10 min) 
(g/10 min) 
__________________________________________________________________________ 
Comparative 
3.5 4.0 3.5 3.60 
Example 
18 
Example 
26 5.5 4.0 3.5 4.18 
27 3.5 7.0 6.0 5.48 
28 10.0 4.0 3.5 5.49 
29 3.5 7.0 8.0 6.50 
30 6.0 9.0 6.0 6.60 
31 8.0 7.0 6.0 6.78 
32 6.0 7.0 8.0 7.22 
33 6.0 7.0 10.0 8.24 
34 10.0 7.0 10.0 9.40 
Comparative 
Example 
19 10.0 7.0 12.0 10.42 
20 12.0 9.0 12.0 11.40 
__________________________________________________________________________ 
Total number 
CTF (sharpness 
Apparent 
of die lip 
of printed 
Degree of 
whiteness*.sup.14 
stain*.sup.14 
image)*.sup.14 
neck-in 
__________________________________________________________________________ 
Comparative 
.largecircle. 
14 0.70 .largecircle. 
Example 
18 
Example 
26 .largecircle. 
7 0.70 .largecircle. 
27 .largecircle. 
3 0.71 .largecircle. 
28 .largecircle. 
2 0.70 .largecircle. 
29 .largecircle. 
0 0.71 .largecircle. 
30 .largecircle. 
0 0.71 .largecircle. 
31 .largecircle. 
0 0.71 .largecircle. 
32 .largecircle. 
0 0.71 .largecircle. 
33 .largecircle. 
0 0.70 .circle..DELTA. 
34 .largecircle. 
0 0.69 .circle..DELTA. 
Comparative 
Example 
19 .largecircle. 
0 0.68 .DELTA. 
20 .largecircle. 
0 0.67 .DELTA..about.X 
__________________________________________________________________________ 
*.sup.14 Same as in Table 2. 
As is clear from Table 6, the photographic supports of the first invention 
in which weighted-mean MFR of polyolefin resin constituting the resin 
layer is within the range of 4.0-9.5 g/l0 min (Examples 26-34) have no 
problems in processability at production thereof, show little die lip 
stain and thus have good surface property, can provide printed image of 
high sharpness and have high apparent whiteness. It can also be seen that 
the weighted-mean MFR of resin is preferably 5.0-8.0 g/10 min so that 
formation of die lip stain can be more effectively inhibited and neck-in 
does not deteriorate processability. 
On the other hand, in case of the comparative support in which 
weighted-mean MFR of resin is lower than 4.0 g/10 min (Comparative Example 
18), much die lip stain occurred. Further, in case of the comparative 
supports in which weighted-mean MFR of resin was higher than 9.5 g/l0 min 
(Comparative Examples 19 and 20), degree of neck-in was great to cause 
problem for processability and besides, sharpness of printed image 
decreased. 
Example 35 
Procedure of Example 1 was repeated except that titanium dioxide pigment 
prepared in the following manner was used in place of the rutile type 
titanium dioxide pigment used in Example 1 to obtain the similar results 
to those obtained in Example 1. 
In accordance with steps of production of rutile type titanium dioxide 
pigment by chlorine method mentioned hereinbefore and using the similar 
apparatus to that disclosed in U.S. Pat. No. 3,121,641, calcination 
decomposition was carried out by feeding, into a burning reaction column 
of 1500.degree. C., simultaneously titanium tetrachloride, oxygen and 
aluminum chloride so that amount of aluminum compound was 0.15% by weight, 
0.75% by weight or 1.6% by weight in terms of Al.sub.2 O.sub.3 based on 
the weight of the titanium dioxide, followed by decomposition, grinding 
and dressing by centrifugal roller mill, and further wet grinding and 
classification to prepare titanium dioxide slurry containing substantially 
no coarse particles. This titanium dioxide slurry was subjected to the 
same subsequent treatments of filtration, washing, drying and finishing 
grinding as in Example 1 to prepare rutile type titanium dioxide pigment 
inside-treated with the aluminum compound. 
Examples 36-38 
Procedure of Example 5 was repeated except that 
octadecyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate, 
2,2',2"-tris[3,5-di-tert-butyl-(4-hydroxyphenyl)propionyloxy]ethylisocyanu 
rate or 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate 
was used in place of 
tetrakis[methylene-(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)]methane as 
antioxidant. The similar results to those of Example 6 were obtained. 
Examples 39-48 
Procedure of Example 5 was repeated except that fluorescent agent 
(I)-(VIII) or (X)-(XI) mentioned hereinbefore was used in place of 
fluorescent agent (IX). 
As a result, excellent photographic supports were obtained as in Example 5. 
Examples 49-52 and Comparative Examples 21-35 
Rutile type titanium dioxide clinker produced in accordance with the 
production procedure of rutile type titanium dioxide pigment by sulfuric 
acid method mentioned hereinbefore under calcination conditions 
predetermined so as to gain the particle diameter shown in Table 7 was 
subjected to grinding and dressing and further subjected to wet grinding 
and classification to obtain titanium dioxide slurry containing 
substantially no coarse particles. This slurry was put in a reaction tank 
and pH of the slurry was raised to about 9.2 with sodium hydroxide. Then, 
this slurry was heated to about 70.degree. C. and thereafter, thereto was 
added an aqueous sodium aluminate solution in an amount of 0.75% by weight 
or 1.9% by weight in terms of Al.sub.2 O.sub.3 based on the dry weight of 
the titanium dioxide and the mixture was kept for 30 minutes. 
pH of the slurry was lowered to 7.0 by addition of 20% sulfuric acid and 
the slurry was aged for 2 hours. Thereafter, the original liquid of 
titanium dioxide slurry surface-treated with hydrated alumina was 
filtrated by a filter press and successively, titanium dioxide cake in the 
filter press was washed with running water under predetermined conditions 
until the suspension electric conductivity defined hereabove reached 4 
.mu..OMEGA./cm. 
Then, the titanium dioxide cake was dried and impact ground in a hammer 
mill having a quantitative feeder and further subjected to finishing 
grinding to produce rutile type titanium dioxide pigments the surface of 
which was treated with different amounts of hydrated alumina and which 
were different in particle diameter. 
50 parts by weight of low-density polyethylene having a density of 0.918 
g/cm.sup.3 and an MFR of 8.0 g/10 min, 50 parts by weight of the titanium 
dioxide pigment obtained above and 2.5 parts by weight of zinc stearate 
were well kneaded at 150.degree. C. by a Banbury mixer to prepare a 
masterbatch of titanium dioxide pigment. 
Furthermore, 0.28 part by weight of fluorescent agent [IX] mentioned 
hereinbefore and 0.28 part by weight of zinc stearate were previously well 
mixed and the resulting mixture was well kneaded with 40 parts by weight 
of the same low-density polyethylene as used for preparation of the above 
titanium dioxide pigment masterbatch by Laboplastmill at 135.degree. C. to 
prepare a fluorescent agent masterbatch. 
Furthermore, 50 parts by weight of Hostaperm pink E (manufactured by 
Hoechst AG) and 50 parts by weight of Sun Wax 171-P (polyethylene wax 
having a molecular weight of about 1500 and a softening point of 
105.degree. C.) were melt kneaded in a heating kneader and then subjected 
to dispersion treatment by a hot triple roll mill to obtain a flaky 
colored preblend. 0.2 part by weight of this preblend, 50 parts by weight 
of the same low-density polyethylene as used for preparation of the above 
titanium dioxide pigment masterbatch, 50 parts by weight of the above 
titanium dioxide pigment and 2.5 parts by weight of zinc stearate were 
well mixed by a Banbury mixer at 150.degree. C. to prepare a titanium 
dioxide pigment masterbatch containing quinacridone pigment. 
Furthermore, 50 parts by weight of the same low-density polyethylene as 
used for preparation of the above titanium dioxide pigment masterbatch, 50 
parts by weight of the above titanium dioxide pigment, 1.25 part by weight 
of ultramarine (#2000 manufactured by Daiichi Kasei Co.) and 2.5 parts by 
weight of zinc stearate were well kneaded by a Banbury mixer at 
150.degree. C. to prepare a titanium dioxide pigment masterbatch 
containing ultramarine. 
Then, on the back side of the same paper substrate as used in Example 1 was 
coated a mixture (1:1 in weight ratio) of a high-density polyethylene 
(density: 0.960 g/cm.sup.3, MFR=5 g/10 min) and a low-density polyethylene 
(density: 0.923 g/cm.sup.3, MFR=5 g/10 min) at a thickness of 30.mu. at a 
resin tempera a melt extrusion coater. Then, a resin composition composed 
of the titanium dioxide pigment masterbatch obtained above, the titanium 
dioxide pigment masterbatch containing ultramarine obtained above and the 
fluorescent agent masterbatch obtained above, the titanium dioxide pigment 
masterbatch containing quinacridone pigment obtained above and 20 parts by 
weight of a high-density polyethylene (density: 0.970 g/cm.sup.3, MFR 7.0 
g/10 min) and 49 parts by weight of a low-density polyethylene (density: 
0.920 g/cm.sup.3, MFR: 6.0 g/10 min) (54 parts by weight when fluorescent 
agent masterbatch was not added) as diluent resins at the mixing ratio as 
shown in Table 7 was melt extrusion coated on the right side of the above 
paper substrate at a thickness of 30 .mu.m at a resin temperature of 
320.degree. C. to make polyethylene resin-coated paper type photographic 
supports of the second invention and comparative photographic supports. 
The right side coated with polyethylene containing titanium dioxide 
pigment was finished to completely smooth glossy surface and the back side 
coated with polyethylene was finished to matter surface such as that of 
paper. 
Apparent whiteness of the side containing titanium dioxide pigment of the 
thus obtained polyethylene resin-coated paper type photographic support 
was evaluated in the same manner as in Example 1. 
Further, degree of die lip stain was measured in the same manner as in 
Example 1. 
In the same manner as in Example 1, color photographic papers having the 
above photographic support were produced and sharpness of printed images 
was measured. 
The results obtained are shown in Table 7. 
TABLE 7 
__________________________________________________________________________ 
Titanium dioxide pigment 
Coating amount 
Amount of masterbatch (parts by weight) 
Particle 
of surface Fluorescent 
diam- 
treating 
White 
Blue agent Red 
eter*.sup.15 
agent*.sup.16 
master- 
master- 
master- 
master- 
(.mu.m) 
(% by weight) 
batch*.sup.16 
batch*.sup.16 
batch batch*.sup.17 
__________________________________________________________________________ 
Comparative 
Example 
21 0.101 
0.75 26.0 0 0 0 
22 0.101 
0.75 16.2 7.2 5 2.6 
23 0.101 
1.9 16.2 7.2 5 2.6 
24 0.124 
0.16 16.2 7.2 5 2.6 
25 0.124 
0.75 26.0 0 0 0 
26 0.124 
0.75 23.4 0 0 2.6 
27 0.124 
0.75 26.0 0 5 0 
Example 
49 0.124 
0.75 23.4 0 5 2.6 
50 0.124 
0.75 19.8 3.6 5 2.6 
Comparative 
Example 
28 0.124 
0.75 18.8 7.2 0 0 
29 0.124 
0.75 16.2 7.2 0 2.6 
Example 
51 0.124 
0.75 18.8 7.2 5 0 
52 0.124 
0.75 16.2 7.2 5 2.6 
Comparative 
Example 
30 0.124 
1.9 26.0 0 0 0 
31 0.124 
1.9 18.8 7.2 0 0 
32 0.124 
1.9 16.2 7.2 5 2.6 
33 0.167 
0.75 26.0 0 0 0 
34 0.167 
0.75 16.2 7.2 5 2.6 
35 0.167 
1.9 16.2 7.2 5 2.6 
__________________________________________________________________________ 
Amount of low- CTF 
density polyethylene 
Total number 
(Sharpness 
for diluent resin 
of die lip 
of printed 
Apparent 
(part by weight) 
stain*.sup.16 
image)*.sup.16 
whiteness 
__________________________________________________________________________ 
Comparative 
Example 
21 54 8 0.69 X 
22 49 18 0.68 .circleincircle. 
23 49 more than 100 
0.69 .circleincircle. 
24 49 3 0.69 .circleincircle. 
25 54 1 0.72 X 
26 54 3 0.72 X 
27 49 3 0.72 .DELTA. 
Example 
49 49 4 0.72 .largecircle. 
50 49 5 0.72 .circleincircle. 
Comparative 
Example 
28 54 3 0.71 X 
29 54 4 0.72 .DELTA. 
Example 
51 49 4 0.72 .largecircle. 
52 49 5 0.72 .circleincircle. 
Comparative 
Example 
30 54 65 0.72 X 
31 54 more than 100 
0.71 X 
32 49 more than 100 
0.71 .circleincircle. 
33 54 2 0.65 X 
34 49 10 0.65 .circleincircle. 
35 49 more than 100 
0.65 .circleincircle. 
__________________________________________________________________________ 
*.sup.15 Numberaverage diameter defined hereinbefore. 
*.sup.16 Same as in Table 1 
*.sup.17 Amount (part by weight) of titanium dioxide pigment containing 
quinacridone pigment. 
As is clear from Table 7, the resin-coated paper type photographic supports 
of the second invention which contain in the resin layer on the 
image-forming side a titanium dioxide pigment which have a number-average 
diameter of 0.110-0.150 .mu.m and surface of which is coated with aluminum 
composition in an amount of more than 0.2% by weight, but less than 1.9% 
by weight in terms of Al.sub.2 O.sub.3 based on the weight of the titanium 
dioxide, a substituent-containing bis(benzoxazolyl)-stilbene fluorescent 
agent and a coloring pigment (Examples 49-52) provide printed images of 
high sharpness, are high in brightness and in apparent whiteness, show 
little die lip stain at production thereof and thus are good in surface 
property. It can be seen that especially the photographic supports where 
blue type pigment and magenta type pigment are used in combination in 
resin layer (Examples 49 and 52) are superior in apparent whiteness. 
On the other hand, it can be seen that comparative photographic supports 
(Comparative Examples 21-35) have problems. That is, photographic supports 
(Comparative Examples 21-23) containing titanium dioxide pigment of less 
than 0.110 .mu.m in particle diameter in resin layer showed much die lip 
stain and gave printed images of low sharpness. The photographic support 
(Comparative Example 21) containing neither coloring pigment nor 
fluorescent agent in resin layer was less in formation of lie lip stain, 
but considerably inferior in apparent whiteness. On the other hand, those 
which contained titanium dioxide pigment having a particle diameter of 
more than 0.150 .mu.m (Comparative Examples 33-35) gave printed images of 
low sharpness. Furthermore, even if photographic support contained 
titanium dioxide pigment having a particle diameter of 0.110-0.150 .mu.m 
in resin layer, when coating amount of the aluminum composition on the 
surface of titanium dioxide pigment was 1.8% by weight or more 
(Comparative Examples 30-32), occurrence of die lip stain was much and 
when the coating amount was 0.2% by weight or less (Comparative Example 
24), many fine foreign matters or particles called microgrit were formed 
on the surface of resin containing the titanium dioxide pigment and 
besides, the surface yellowed when subjected to irradiation for 120 hours 
by a fadeometer (FAL-25X-HCL manufactured by Suga Tester Co.). 
Furthermore, when resin layer contained neither the fluorescent agent nor 
coloring pigment (Comparative Examples 25-29), apparent whiteness was very 
low. 
Examples 53-57 and Comparative Examples 36-39 
Procedure of Example 52 was repeated except that titanium dioxide pigments 
having the number-average diameter shown in Table 8 was used in place of 
the titanium dioxide pigment used in Example 53. 
The results obtained are shown in Table 8. 
TABLE 8 
______________________________________ 
Particle 
diameter Total CTF 
of titanium 
number (sharpness 
dioxide pigment 
of die lip 
of printed 
Apparent 
(.mu.m)*.sup.18 
stain*.sup.18 
image)*.sup.18 
whiteness 
______________________________________ 
Comparative 
Example 
36 0.096 25 0.67 .circleincircle. 
37 0.101 17 0.68 .circleincircle. 
Example 
53 0.110 9 0.70 .circleincircle. 
54 0.115 6 0.72 .circleincircle. 
55 0.124 5 0.72 .circleincircle. 
56 0.135 4 0.71 .circleincircle. 
57 0.148 4 0.68 .circleincircle. 
Comparative 
Example 
38 0.167 4 0.65 .circleincircle. 
39 0.187 3 0.64 .circleincircle. 
______________________________________ 
*.sup.18 Same as in Table 7. 
As can be seen from Table 8, the resin-coated paper type photographic 
supports of the second invention (Examples 53-57) containing titanium 
dioxide pigment of 0.110-0.150 .mu.m in number-average diameter in the 
resin layer on the image-forming side are excellent photographic supports 
which can provide printed image of high sharpness, show little formation 
of die lip stain at production thereof and thus have good surface property 
and high apparent whiteness. It can be recognized that especially the 
photographic supports containing titanium dioxide pigment of 0.115-0.135 
.mu.m in number-average diameter in resin layer can provide printed image 
of especially high sharpness and show very little die lip stain and thus 
are especially excellent. 
On the other hand, those which contained titanium dioxide pigment having a 
number-average diameter of less than 0.110 .mu.m in resin layer 
(Comparative Examples 36-37) showed much die lip stain and gave printed 
image of low sharpness. Those which contained titanium dioxide pigment 
having a number-average diameter of more than 0.150 .mu.m in resin layer 
(Comparative Examples 38-39) provided printed image of low sharpness. 
Examples 58-66 
Procedure of Example 52 was repeated except that as the low-density 
polyethylene resin for master-batch was used the low-density polyethylene 
resin for masterbatch used in Example 52 to which 
tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)]-methane 
was previously added in such amount as shown in Table 9 as antioxidant. 
The results obtained are shown in Table 9. 
TABLE 9 
______________________________________ 
Total CTF 
Amount of number (sharpness 
antioxidant*.sup.19 
of die lip 
of printed 
Apparent 
Example 
(ppm) stain*.sup.20 
image)*.sup.20 
whiteness 
______________________________________ 
58 0 5 0.72 .circleincircle. 
59 10 3 0.73 .circleincircle. 
60 20 1 0.72 .circleincircle. 
61 150 0 0.73 .circleincircle. 
62 300 0 0.73 .circleincircle. 
63 500 1 0.71 .circleincircle. 
64 1000 1 0.71 .circleincircle. 
65 1500 2 0.70 .circleincircle. 
66 2000 4 0.69 .circleincircle. 
______________________________________ 
*.sup.19 Amount (ppm) of antioxidant added based on the resin composition 
on the side containing titanium dioxide pigment. 
*.sup.20 Same as in Table 1. 
As can be seen from Table 9, die lip stain was highly inhibited by 
containing an antioxidant in resin layer. It can also be recognized that 
the content of antioxidant is preferably 10-1500 ppm, especially 
preferably 20-1000 ppm based on the resin composition. As mentioned above, 
it can be seen that the photographic support of the second invention 
containing a suitable amount of antioxidant is an excellent photographic 
support which provides high sharpness of printed image and besides shows 
little die lip stain at production of the support and thus has good 
surface property. 
Examples 67-74 and Comparative Examples 40-44 
The procedure of Example 62 was repeated except that the titanium dioxide 
pigment having a number-average diameter of 0.124 .mu.m and coated with 
metal composition in an amount as shown in Table 10 was used in place of 
the titanium dioxide pigment used in Example 62. 
In this case, the titanium dioxide pigment surface-treated with various 
kinds and amounts of hydrated metal oxide was prepared in the following 
manner. 
The titanium dioxide slurry prepared in the same manner as in Example 49 
was charged in a reaction tank and pH of the slurry was raised to about 
9.2 with sodium hydroxide. The slurry was heated to about 70.degree. C. 
Thereafter, to the slurry were added aqueous sodium aluminate solution 
or/and aqueous sodium silicate solution so that the surface of the 
titanium dioxide was coated with metal composition in an amount as shown 
in Table 10 in terms of Al.sub.2 O.sub.3 or/and SiO.sub.2 based on the dry 
weight of the titanium dioxide and then the slurry was left to stand for 
30 minutes In the case of coating the surface with hydrated titanium 
oxide, before raising pH of titanium dioxide slurry with sodium hydroxide, 
aqueous titanyl sulfate solution was added to the slurry so that the 
surface was coated with titanium composition in an amount as shown in 
Table 10 in terms of TiO.sub.2 based on the dry weight of the titanium 
dioxide. Thereafter, rutile type titanium dioxide pigments as shown in 
Table 10 were prepared in the same manner as in Example 49. 
The results obtained are shown in Table 10. 
TABLE 10 
__________________________________________________________________________ 
Kind and amount of surface treating 
agent coated on titanium dioxide 
Total number 
Sharpness 
pigment*.sup.21 of die lip 
of printed 
Apparent 
Al.sub.2 O.sub.3 
SiO.sub.2 
TiO.sub.2 
Total amount 
stain*.sup.21 
image*.sup.21 
whiteness 
__________________________________________________________________________ 
Example 
67 0.25 
0 0 0.25 0 0.71 .circleincircle. 
68 0.5 0 0 0.5 0 0.73 .circleincircle. 
69 0.75 
0 0 0.75 0 0.73 .circleincircle. 
70 1.0 0 0 1.0 0 0.73 .circleincircle. 
71 1.25 
0 0 1.25 1 0.72 .circleincircle. 
72 1.7 0 0 1.7 8 0.71 .circleincircle. 
73 0.5 0.1 
0 0.6 3 0.72 .circleincircle. 
74 0.5 0.1 
0.1 
0.7 4 0.72 .circleincircle. 
Comparative 
Example 
40 0.19 
0 0 0.15 0 0.69 .circleincircle. 
41 1.9 0 0 1.9 69 0.70 .circleincircle. 
42 0 0.5 
0 0.5 86 0.70 .circleincircle. 
43 1.3 0 0.6 
1.9 75 0.71 .circleincircle. 
44 0.75 
0.5 
0 0.25 more than 
0.69 .circleincircle. 
100 
__________________________________________________________________________ 
*.sup.21 Same as in Table 1. 
As can be seen from Table 10, the photographic supports (Examples 67-74) of 
the second invention where titanium dioxide the surface of which was 
coated with aluminum-containing metal composition in an amount of more 
than 0.2% by weight, but less than 1.8% by weight in terms of anhydrous 
metal oxide based in the weight of the titanium dioxide and with silicon 
composition in an amount of 0-0.4% by weight in terms of silicon dioxide 
was used as titanium dioxide pigment in resin layer of resin-coated paper 
were excellent photographic supports which can provide high sharpness of 
printed image, are apparently white and show little die lip stain at 
production thereof and thus have good surface property. Furthermore, it 
can be recognized that hydrated alumina is preferred as the surface 
treating agent for titanium dioxide from the points of inhibition of die 
lip stain and coating amount thereof is preferably 0.4-1.25% by weight in 
terms of Al.sub.2 O.sub.3 based on the weight of titanium dioxide. 
On the other hand, the comparative photographic supports (Comparative 
Examples 40-44) had problems. That is, when surface thereof was coated 
with metal composition in an amount of 1.8% by weight or more in terms of 
anhydrous metal oxide based on the weight of titanium dioxide (Comparative 
Examples 41 and 43) and when the surface thereof was coated with silicon 
composition in an amount of 0.5% by weight or more in terms of SiO.sub.2 
based on the weight of titanium dioxide (Comparative Examples 42 and 44), 
much die lip stain occurred. Furthermore, when titanium dioxide the 
surface of which was coated with metal composition in an amount of 0.2% by 
weight or less in terms of anhydrous metal oxide based on the weight of 
titanium dioxide was used (Comparative Example 40), light resistance was 
inferior. 
Examples 75-77 
Procedure of Example 62 was repeated except that 
octadecyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate, 
2,2',2"-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethylisocyanu 
rate or 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurate 
was used in place of 
tetrakis[methylene-(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)]methane as 
antioxidant. The similar results to those of Example 62 were obtained. 
Examples 78-86 and Comparative Example 45 
Procedure of Comparative Example 31 was repeated except that content of 
fluorescent agent [IX] in the resin layer in Example 62 was changed as 
shown in Table 11. In this case, when content of the fluorescent agent was 
reduced, amount of masterbatch of the fluorescent agent was reduced and 
low-density polyethylene used for preparation of said masterbatch was 
added as diluent resin in an amount corresponding to the amount reduced. 
On the other hand, when content of the fluorescent agent was increased, 
masterbatch of the fluorescent agent prepared in the same manner as in 
Example 53 was added to low-density polyethylene corresponding to the 
diluent resin in Example 62 (namely, low-density polyethylene 
corresponding to the diluent resin in Example 52) and amount of 
low-density polyethylene for diluent resin corresponding to the amount in 
the added masterbatch of fluorescent agent was reduced. 
The results obtained are shown in Table 11. 
TABLE 11 
______________________________________ 
Content of Total number 
fluorescent agent in 
Apparent of die lip 
resin layer (mg/m.sup.2) 
whiteness*.sup.22 
stain*.sup.22 
______________________________________ 
Comparative 
0 .DELTA. 0 
Example 
45 
Example 
78 0.1 .DELTA. 0 
79 0.2 .DELTA. 0 
80 0.5 .largecircle. 
0 
81 3 .circleincircle. 
0 
82 6.3 .circleincircle. 
0 
83 10.5 .circleincircle. 
0 
84 15 .circleincircle. 
1 
85 25 .circleincircle. 
2 
86 50 .circleincircle. 
5 
______________________________________ 
*.sup.22 Same as in Table 2. 
As is clear from Table 11, when content of the fluorescent agent in resin 
layer is less than 0.3 mg/m.sup.2, apparent whiteness of the image forming 
side of photographic support is insufficient and when it is more than 25 
mg/m.sup.2, die lip stain tends to occur much. Thus, it can be seen that 
the content is preferably 0.3-25 mg/m.sup.2. As shown above, the 
photographic supports of the second invention which contain a proper 
amount of fluorescent agent show little die lip stain at production 
thereof and thus have good surface property, can provide printed images of 
high sharpness and besides have high apparent whiteness 
Examples 77-96 
Example 83 was repeated except that fluorescent agent (I)-(VIII) or 
(X)-(XI) was used in place of fluorescent agent (IX). 
As a result, excellent photographic supports were obtained as in Example 
83. 
Example 97 
Procedure of Example 52 was repeated except that titanium dioxide pigment 
prepared in the following manner was used in place of the rutile type 
titanium dioxide pigment used in Example 52 to obtain the similar results 
to those obtained in Example 52. 
In accordance with steps of production of rutile type titanium dioxide 
pigment by chlorine method mentioned hereinbefore and using the similar 
apparatus to that disclosed in U.S. Pat. No. 3,121,641, calcination 
decomposition was carried out by feeding, into a burning reaction column 
of 1500.degree. C., simultaneously titanium tetrachloride, oxygen and 
aluminum chloride so that amount of aluminum compound 0.15% by weight, 
0.75% by weight or 1.6% by weight in terms of Al.sub.2 O.sub.3 based on 
the weight of titanium dioxide pigment, followed by decomposition, 
grinding and dressing by centrifugal roller mill, further wet grinding and 
classification to obtain a titanium dioxide slurry containing 
substantially no coarse particles. This titanium dioxide slurry was 
subjected to the same subsequent treatments of filtration, washing, drying 
and finishing grinding as in Example 52 to prepare rutile type titanium 
dioxide pigment inside-treated with the aluminum compound. 
Examples 98-102 and Comparative Examples 46-49 
Example 52 was repeated except that anatase type titanium dioxide pigment 
prepared in the following manner was used in place of the rutile type 
titanium dioxide pigment used in Example 55. 
Anatase type titanium dioxide clinker prepared under hydrolysis conditions 
and calcination conditions predetermined so that the particle diameter 
reached that shown in Table 12 in accordance with procedure for production 
of anatase type titanium dioxide pigment by sulfuric acid method mentioned 
hereinbefore was subjected to grinding and dressing and further to wet 
grinding and classification to obtain titanium dioxide pigment slurry 
containing substantially no course particles of titanium dioxide. This 
slurry was put in a reaction tank to coat the surface of the titanium 
dioxide with hydrated aluminum oxide in an amount of 0.75% by weight in 
terms of Al.sub.2 O.sub.3 based on the dry weight of the titanium dioxide 
in the same manner as in Example 1, followed by washing, drying, and 
finishing grinding to obtain anatase type titanium dioxide pigments coated 
with hydrated aluminum oxide which were different in particle diameter. 
The results obtained are shown in Table 12. 
TABLE 12 
______________________________________ 
Particle 
diameter 
of titanium 
Total CTF 
dioxide number (sharpness 
pigment*.sup.23 
of die lip 
of printed 
Apparent 
(.mu.m) stain*.sup.23 
image)*.sup.23 
whiteness 
______________________________________ 
Comparative 
Example 
46 0.094 27 0.54 .circleincircle. 
47 0.102 18 0.55 .circleincircle. 
Example 
98 0.110 10 0.57 .circleincircle. 
99 0.117 6 0.58 .circleincircle. 
100 0.125 5 0.58 .circleincircle. 
101 0.135 4 0.58 .circleincircle. 
102 0.149 4 0.57 .circleincircle. 
Comparative 
Example 
48 0.165 4 0.55 .circleincircle. 
49 0.187 3 0.54 .circleincircle. 
______________________________________ 
*.sup.23 Same as in Table 1. 
As can be seen from Table 12, the resin-coated paper type photographic 
supports of the second invention (Examples 98-102) containing titanium 
dioxide pigment which had a number-average diameter of 0.110-0.150 .mu.m 
and the surface of which was coated with a specific amount of aluminum 
composition, fluorescent agent and color pigment in the resin layer on the 
image-forming side are excellent photographic supports which can provide 
printed image of high sharpness, is apparently white, show little 
formation of die lip stain at production thereof and thus have good 
surface property. 
On the other hand, it can be seen that comparative photographic supports 
(Comparative Examples 46-49) have problems. 
That is, those which contained titanium dioxide pigment having a 
number-average diameter of less than 0.110 .mu.m in resin layer 
(Comparative Examples 46-47) showed much die lip stain and 9ave printed 
image of low sharpness. Those which contained titanium dioxide pigment 
having a number-average diameter of more than 0.150 .mu.m in resin layer 
(Comparative Examples 48-49) provided printed image of low sharpness. 
Examples 103-108 and Comparative Examples 50-62 
Rutile type titanium dioxide clinker prepared under such calcination 
conditions that particle diameter reached that shown in Table 13 in 
accordance with procedure of production of rutile type titanium dioxide 
pigment by sulfuric acid method referred to hereinbefore was subjected to 
grinding and dressing and further to wet grinding and classification to 
obtain titanium dioxide slurry containing substantially no coarse 
particles of titanium dioxide. This slurry was put in a reaction tank and 
thereto was added 10 wt% aqueous solution of CaCl.sub.2.6.H.sub.2 O so 
that calcium compound was supported on the surface of titanium dioxide 
particles in an amount of 0,04% by weight in terms of calcium based on the 
weight of the titanium dioxide. Then, pH of the slurry was raised to about 
9.2 with sodium hydroxide. Then, this slurry was heated to about 
70.degree. C. and thereafter, thereto was added an aqueous sodium 
aluminate solution in an amount of 0.75% by weight in terms of Al.sub.2 
O.sub.3 based on the dry weight of the titanium dioxide and the mixture 
was left to stand for 30 minutes. 
pH of the slurry was lowered to 7.0 by addition of 20% sulfuric acid and 
the slurry was aged for 2 hours. Thereafter, the original liquid of 
titanium dioxide slurry surface treated with hydrated alumina was 
filtrated by a filter press and successively, titanium dioxide cake in the 
filter press was washed with running water under predetermined conditions 
until the suspension electric conductivity defined hereabove reached 45 
.mu..OMEGA./cm. 
Then, the titanium dioxide cake was dried and impact ground in a hammer 
mill having a quantitative feeder and further subjected to finishing 
grinding to produce rutile type titanium dioxide pigments of different 
particle diameter which supported calcium compound on the surface. 
50 parts by weight of low-density polyethylene having a density of 0.918 
g/cm.sup.3 and an MFR of 8.0 g/10 min or a low-density polyethylene having 
a density of 0.918 g/cm.sup.3 and an MFR of 8.0 g/10 min and containing 
135 ppm of 
tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)]methane as 
an antioxidant, 50 parts by weight of the titanium dioxide pigment 
obtained above and 2.5 parts by weight of zinc stearate were well kneaded 
at 150.degree. C. by a Banbury mixer to prepare a masterbatch of titanium 
dioxide pigment. 
Separately, 50 parts by weight of the same low-density polyethylene as used 
for preparation of the above titanium dioxide pigment masterbatch, 50 
parts by weight of the above titanium dioxide, 1.25 part by weight of 
ultramarine (#2000, manufactured by Daiichi Kasei Kogyo Co.) and 2.5 parts 
by weight of zinc stearate were well kneaded at 150.degree. C. by a 
Banbury mixer to prepare a titanium dioxide pigment masterbatch containing 
ultramarine. 
Furthermore, 0.28 part by weight of fluoroescent agent [IX] mentioned 
hereinbefore and 0.28 part by weight of zinc stearate were previously well 
mixed and the resulting mixture was well kneaded with 40 parts by weight 
of the same low-density polyethylene as used for preparation of the above 
titanium dioxide pigment masterbatch in a Laboplastmill at 135.degree. C. 
to prepare a fluorescent agent masterbatch. 
On the back side of the same paper substrate as used in example 1 was 
coated a mixture (1:1 in weight ratio) of a high-density polyethylene 
(density: 0.960 g/cm.sup.3, MFR=5 g/10 min) and a low-density polyethylene 
(density: 0.923 g/cm.sup.3, MFR=5 g/10 min) at a thickness of 30 .mu.m at 
a resin temperature of 330.degree. C. using a melt extrusion coater. Then, 
a resin composition composed of 18.8 parts by weight of the titanium 
dioxide pigment masterbatch obtained above, 7.2 parts by weight of the 
titanium dioxide pigment masterbatch containing ultramarine obtained 
above, 3.0 parts by weight of the fluorescent agent masterbatch obtained 
above, 20 parts by weight of a high-density polyethylene (density: 0.970 
g/cm.sup.3, MFR: 7.0 g/10 min) and 51 parts by weight of a low-density 
polyethylene (density: 0.920 g/cm.sup.3, MFR: 6.0 g/10 min) as diluent 
resins was melt extrusion coated on the right side of the above paper 
substrate at a thickness of 30 .mu.m at a resin temperature of 330.degree. 
C. to make polyethylene resin-coated papers of the third invention and 
comparative supports. The right side coated with polyethylene containing 
titanium dioxide pigment was finished to completely smooth glossy surface 
and the back side coated with polyethylene was finished to matter surface 
such as that of paper. 
Apparent whiteness of the side containing titanium dioxide pigment of the 
thus obtained polyethylene resin-coated paper type photographic support 
was evaluated in the same manner as in Example 1. 
Die lip stain and sharpness of printed image were also evaluated in the 
same manner as in Example 1. 
The results obtained are shown in Table 13. 
TABLE 13 
__________________________________________________________________________ 
In resin layer 
Particle diameter 
Presence or 
Total 
CTF 
of titanium 
Presence or 
absence of 
number 
(sharpness 
Apparent 
dioxide pigment 
absence of 
fluorescent 
of die lip 
of printed 
white- 
(.mu.m)*.sup.24 
antioxidant 
agent stain*.sup.24 
image)*.sup.24 
ness 
__________________________________________________________________________ 
Comparative 
Example 
50 0.096 Absent 
Present 
16 0.67 .largecircle. 
51 0.101 " " 10 0.69 .largecircle. 
52 0.110 " " 5 0.71 .largecircle. 
53 0.115 " " 4 0.71 .largecircle. 
54 0.124 " " 3 0.70 .largecircle. 
55 0.135 " " 3 0.68 .largecircle. 
56 0.148 " " 3 0.65 .largecircle. 
57 0.167 " " 3 0.64 .largecircle. 
58 0.187 " " 3 0.67 .largecircle. 
59 0.096 Present 
" 7 0.69 .largecircle. 
60 0.101 " " 4 0.71 .largecircle. 
Example 
103 0.110 " " 2 0.71 .largecircle. 
104 0.115 " " 0 0.71 .largecircle. 
105 0.124 " " 0 0.71 .largecircle. 
106 0.124 " Absent 
0 0.71 .DELTA. 
107 0.135 " Present 
0 0.70 .largecircle. 
108 0.148 " " 0 0.68 .largecircle. 
Comparative 
Example 
61 0.167 " " 0 0.65 .largecircle. 
62 0.187 " " 1 0.64 .largecircle. 
__________________________________________________________________________ 
*.sup.24 Same as in Table 7 
As can be seen from Table 13, the resin-coated paper type photographic 
supports of the third invention which contain in the resin layer on the 
image forming side a titanium dioxide pigment which has a number-average 
diameter of 0.110-0.150 .mu.m and which supports calcium compound on the 
surface and an antioxidant (Examples 103-108) provide printed images of 
high sharpness and show less die lip stain at production thereof and thus 
are good in surface property It can be further seen that especially the 
photographic supports which contain titanium dioxide pigment having a 
particle size of 0.115-0.135 .mu.m in the resin layer (Examples 104-107) 
can provide printed image of especially high sharpness and show little die 
lip stain and thus are especially excellent. Furthermore, photographic 
supports contain fluorescent agent in resin layer (Examples 103-105 and 
107-108) are superior in apparent whiteness to that which contains no 
fluorescent agent (Example 106) and thus are especially excellent. 
On the other hand, it can be seen that comparative photographic supports 
(Comparative Examples 50-62) have problems. 
That is, photographic supports containing no antioxidant (Comparative 
Examples 50-58) showed much die lip stain and those which contain titanium 
dioxide pigment having a particle diameter of more than 0.150 .mu.m 
(Comparative Examples 61-62) provide printed image of low sharpness. 
Example 109 
Example 105 was repeated except that titanium dioxide pigment which had a 
number-average diameter of 0.124 .mu.m and which supported on the surface 
a calcium compound in an amount as shown in Table 14 in terms of calcium 
based on the weight of titanium dioxide was used. 
The results obtained are shown in Table 14. 
TABLE 14 
__________________________________________________________________________ 
Amount of calcium compound 
Total CTF 
supported on the surface of 
number 
(sharpness 
Apparent 
particles of titanium dioxide 
of die lip 
of printed 
white- 
pigment (% by weight)*.sup.25 
stain*.sup.26 
image)*.sup.26 
ness*.sup.26 
__________________________________________________________________________ 
Comparative 
Example 
63 0 4 0.67 .largecircle. 
64 0.001 4 0.67 .largecircle. 
65 0.002 2 0.69 .largecircle. 
Example 
109 0.004 1 0.70 .largecircle. 
110 0.01 0 0.71 .largecircle. 
111 0.04 0 0.71 .largecircle. 
112 0.07 0 0.70 .largecircle. 
Comparative 
Example 
66 0.10 1 0.69 .largecircle. 
67 0.15 2 0.67 .largecircle. 
__________________________________________________________________________ 
*.sup.25 Amount (% by weight) in terms of calcium based on the weight of 
titanium dioxide. 
*.sup.26 Same as in Table 2. 
As can be seen from Table 14, the resin-coated type photographic supports 
of the third invention which contain in the resin layer titanium dioxide 
pigment the surface of which supports on the surface a calcium compound in 
an amount of 0.004-0.1% by weight based on the weight of the titanium 
dioxide (Examples 109-112) provide printed images of high sharpness and 
show occurrence of little die lip stain and thus have good surface 
property On the other hand, comparative supports (Comparative Examples 
63-67) support calcium compound in an amount of less than 0.004% by weight 
or more than 0.1% by weight in terms of calcium based on the weight of 
titanium dioxide provide printed image of low sharpness and show much die 
lip stain. 
Examples 113-120 and Comparative Examples 68 
Procedure of Example 102 was repeated except that as the low-density 
polyethylene resin for master-batch, was used the low-density polyethylene 
resin for masterbatch used in Example 103 to which 
tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)]-methane 
was previously added in such amount as shown in Table 15 as antioxidant. 
The results obtained are shown in Table 15. 
TABLE 15 
______________________________________ 
Total CTF 
Amount of 
number (sharpness 
antioxidant*.sup.27 
of die lip 
of printed 
Apparent 
(ppm) stain*.sup.28 
image)*.sup.28 
whiteness 
______________________________________ 
Comparative 
0 5 0.70 .largecircle. 
Example 
68 
Example 
113 10 2 0.71 .largecircle. 
114 20 0 0.71 .largecircle. 
115 60 0 0.71 .largecircle. 
116 150 0 0.71 .largecircle. 
117 300 0 0.71 .largecircle. 
118 500 1 0.70 .largecircle. 
119 1000 2 0.69 .largecircle. 
120 2000 3 0.68 .largecircle. 
______________________________________ 
*.sup.27 Addition amount (ppm) based on the resin composition on the side 
containing titanium dioxide. 
*.sup.28 Same as in Table 13. 
As can be seen from Table 15, occurrence of die lip stain can be 
effectively inhibited by containing an antioxidant in resin layer of 
resin-coated paper type photographic support. It can be also seen that 
content of the antioxidant is preferably 10-1000 ppm, especially 
preferably 20-500 ppm based on the resin composition. Thus, it can be seen 
that the photographic supports of the third invention containing a proper 
amount of antioxidant can provide printed image of high sharpness and show 
little die lip stain at production thereof and thus have good surface 
property. 
Examples 121 and 122 
Example 109 was repeated except that titanium dioxide pigment having a 
number-average diameter of 0.124 .mu.m and supporting on the surface 
various amounts of a magnesium compound or a barium compound was used in 
place of the titanium dioxide pigment used in Example 109. 
In this case, the titanium dioxide was prepared in the same manner as in 
Example 103 and MgSO.sub.4.7H.sub.2 O or BaCl.sub.2.2H.sub.2 O was used in 
place of CaCl.sub.2.6H.sub.2 O used in Example 103. 
Similar results to those of Example 109 were obtained. 
Examples 123-125 
Example 113 was repeated except that 
octadecyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate, 
2,2',2"-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)-propionyloxy]ethylisocyan 
urate or 1,3,5-tris(4-tertbutyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate 
was used in place of the antioxidant 
tetrakis[methylene(3,5-ditert-butyl-4-hydroxy-hydrocinnamate)]methane used 
in Example 109, to obtain the similar results to those of Example 113. 
Examples 126-127 and Comparative Examples 69-73 
Example 103 was repeated except that anatase type titanium dioxide pigment 
prepared in the following manner was used in place of the rutile type 
titanium dioxide pigment used in Example 103. 
Anatase type titanium dioxide clinker prepared under hydrolysis and 
calcination conditions predetermined so that particle diameter reached 
that shown in Table 16 in accordance with procedure of production of 
anatase type titanium dioxide pigment by sulfuric acid method referred to 
hereinbefore was subjected to grinding and dressing and further to wet 
grinding and classification to obtain titanium dioxide slurry containing 
substantially no coarse particles of titanium dioxide. This slurry was put 
in a reaction tank and thereto was added 10 wt% aqueous solution of 
CaCl.sub.2.6H.sub.2 O so that calcium compound was supported on the 
surface of titanium dioxide particles in an amount of 0.04% by weight in 
terms of calcium based on the weight of the titanium dioxide. Then, the 
titanium dioxide was subjected to surface-treatment with hydrated aluminum 
oxide as in Example 103, then to washing, drying and finishing grinding to 
obtain anatase type titanium dioxide pigment different in particle 
diameter which supported calcium compound on the surface. 
The results obtained are shown in Table 16. 
TABLE 16 
__________________________________________________________________________ 
Resin layer 
Particle diameter 
Presence or 
Total 
CTF 
of titanium 
Presence or 
absence of 
number 
(sharpness 
Apparent 
dioxide pigment 
absence of 
fluorescent 
of die lip 
of printed 
white- 
(.mu.m)*.sup.29 
antioxidant 
agent stain*.sup.29 
image)*.sup.29 
ness 
__________________________________________________________________________ 
Comparative 
Example 
69 0.108 Absent 
Present 
7 0.54 .largecircle. 
70 0.122 " " 3 0.58 .largecircle. 
71 0.153 " " 3 0.55 .largecircle. 
72 0.108 Present 
" 2 0.54 .largecircle. 
Example 
126 0.122 " " 0 0.58 .largecircle. 
127 0.122 " Absent 
0 0.58 .circle..DELTA. 
Comparative 
0.153 " Present 
0 0.55 .largecircle. 
Example 
73 
__________________________________________________________________________ 
*.sup.29 Same as in Table 13. 
As can be seen from Table 16, the resin-coated paper type photographic 
supports of the third invention which contain in resin layer thereof 
titanium dioxide pigment which has a particle diameter of 0.110-0.150 
.mu.m and supports on the surface a calcium compound and an antioxidant 
(Examples 126-127) provide printed image of high sharpness, show a little 
die lip stain at production thereof and thus have good surface property. 
On the other hand, the comparative photographic supports (Comparative 
Examples 69-73) have problems. 
That is, it can be seen that those which contain no antioxidant in resin 
layer (Comparative Examples 69-71) show formation of much die lip stain 
and that which contains antioxidant, but contains titanium dioxide pigment 
having a particle diameter of less than 0.110 .mu.m (Comparative Example 
72) shows formation of much die lip stain and provides printed image of 
low sharpness and on the other hand, that which contains titanium dioxide 
having a particle diameter of more than 0.150 .mu.m (Comparative Example 
73) provides printed image of low sharpness.