JP2000010241A - Resin and base body for formation of image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a supporting body for the formation of image which uses rutile TiO2 and has high sharpness, excellent whiteness degree and productivity, by incorporating a dispersant and a specified polyolefin in which rutile TiO2 is dispersed. SOLUTION: This resin contains a dispersant and a polyolefin in which rutile TiO2 having 0.1 to 0.26 μm particle size is dispersed by at least 10 wt.%. The reflecting supporting body to be used has one or more resin coating layers on a supporting body. One or more image forming layers can be formed on the water-resistant resin coating layer. The rutile TiO2 is incorporated into one or all layers of the resin coating layers. It is preferable that a resin layer containing the smallest amt. of TiO2 is formed adjacently to the paper base body. Or, as for a single layer structure, the amt. of rutile TiO2 in the resin coating layer is preferably >=10 wt.% and <50 wt.% of the resin layer. As for a multilayered structure, the rutile pigment may be added to one layer or all layers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an image forming paper, and more particularly to an image forming paper having high sharpness, whiteness and excellent manufacturability.

[0002]

BACKGROUND OF THE INVENTION Silver halide photosensitivity on a reflective support
Various methods are available to improve the sharpness of photographic materials
Used. One such method is the use of paper supports.
Is to increase the amount of white pigment of resin laminated on top
(JP-A-03-156452 and JP-A-03-156)
439). However, TiO_Two As the content increases
Manufacturing costs rise. More TiO in resin
_Two Another problem when introducing is that extrusion quality is poor.
And produce poor quality sheets. TiO _Two Pigment
When extruding a polymer containing
Insoluble material accumulates on the substrate and hinders the extrusion process
You. Eventually, when this material accumulates, it cuts the extrudate,
Streaks in the machine direction (hereinafter simply referred to as "die line")
Is generated. Die line gets worse over time
Quality deterioration. To mitigate quality degradation,
Dies must be cleaned with frequent regimes. this
This interrupts the extrusion operation and is expensive, so pigments and pigments
Require hourly frequency depending on surface treatment and pigment addition
May be done.

A second method for improving sharpness is to use T
The use of a plurality of water-resistant resins laminated on the image forming side of paper having different iO ₂ contents (US Pat. No. 5,42,42).
9,916). The water resistant resin layer with the least amount of TiO ₂ is located on the resin layer closest to the paper substrate (US Pat. No. 5,573,898). US Patent 5,57
No. 3,898 teaches the use of rutile or anatase TiO ₂ for photographic supports. However, US Pat. No. 5,573,898 teaches that an anatase-type TiO ₂ is used to realize a white support and a rutile-type TiO ₂ is used to realize a sharp support. Anatase-type TiO ₂ required for producing a white support is expensive and has a problem of poor filterability and runnability during extrusion coating. If there is anatase TiO ₂ of high level to the outermost resin layer, the quality cause accumulation of material on the lip of the extruder causes a bad product. This method requires either multiple passes of a single extruder or the purchase of a new extruder (s) and die to make a single pass of multiple resin layers.

A third method for improving sharpness is to use
Natase TiO_Two Is rutile type TiO_Two By changing to
is there. Anatase TiO_Two Has a refractive index of 2.52
But rutile TiO_Two Is 2.76. Rutile type Ti
O_Two Large refractive index of anatase support
Less TiO to get the same sharpness as _Two 
Enables the addition amount of However, prior to the present invention, rutile
Type TiO_Two Is anatase TiO_Two Same as having
A support with whiteness and the same brightness cannot be provided
won.

[0005] Imaging supports require very white supports. TiO ₂ increases the reflectance or brightness of the support. Blue colorants are added to the resin-coated support to increase the apparent whiteness. With the addition of the blue colorant, the support becomes darker. Rutile TiO ₂ is inherently brighter than the anatase structure, but the rutile (> 0.26 μm) of the larger particles is more yellow. Therefore,
In the case of rutile over anatase, substantially more blue colorant is required to obtain the same blue support. As a result, supports with rutile TiO ₂ appear darker than supports with anatase TiO ₂ .

A fourth method of improving sharpness and maintaining a white support is to combine rutile and anatase TiO ₂ (US Pat. No. 5,569,577). In our studies, in combination with anatase type TiO _2, imaging support having more than 5 wt% rutile TiO ₂ was found to lose the whiteness advantage of the anatase type TiO _2. Furthermore, the productivity is poor, and the material cost is high in the case of an anatase / rutile type blend.

The inkjet and thermal imaging sharpness is not determined by the type or amount of TiO ₂ ,
Determined by original image quality and printer. However, a problem with these types of imaging supports is to obtain very white and opaque supports.
Hiding power and opacity of rutile TiO ₂ is superior to anatase TiO _2, rutile TiO ₂ is too yellow.

A further problem with anatase TiO ₂ is that
Due to its thermal instability. If a large amount of metal soap (eg, calcium stearate) is not added to the resin layer, the anatase TiO ₂ will yellow during the extrusion process. Calcium stearate prevents anatase TiO ₂ from yellowing during extrusion. However, the stearate accumulates on the outer extruder parts and produces by-products that fall down on the finished imaging sheet and cause costly defects.

Finally, environmental effects and anatase type T
the manufacturing cost of the iO ₂ is worse than the production of rutile TiO _2. Rutile TiO ₂ can be produced by the sulfate method or chloride method, while anatase TiO ₂ can be produced only by the sulfate method. The chloride method is more environmentally friendly than the sulfuric acid method. The sulphate process produces large amounts of acid wasted and contaminated by the product.

[0010]

SUMMARY OF THE INVENTION Anatase TiO_Two 
Despite all the issues regarding
In manufacturing, to obtain high whiteness and lightness, rutile type T
iO_Two Rather than anatase TiO_Two Typically used
I have. However, rutile TiO_Two Is lower cost
The anatase type TiO_Two Than
White rutile TiO_Two It is desirable to use Further
Needed to get the same opacity and sharpness
Rutile type TiO_Two Is anatase TiO_Two Than
Also less. The present invention provides high sharpness, whiteness and excellent
Rutile TiO with improved manufacturability _Two Image formation using
A support is provided.

[0011]

SUMMARY OF THE INVENTION The present invention provides at least one
An image forming resin comprising a polyolefin in which rutile TiO ₂ having a particle size of 0.1 to 0.26 μm is dispersed at a concentration of 0% by weight and a dispersant. This resin is applied to a support to form an image forming substrate. An imaging layer can be placed on an imaging substrate to provide an imaging element. In a preferred embodiment, the imaging element is a photographic element.

[0012]

DETAILED DESCRIPTION OF THE INVENTION As used herein, the term "imaging element" refers to a laminated support for transferring an image to the support by techniques such as ink jet printing or thermal dye transfer, as well as silver halide images. Material that can be used with a support for The term "photographic element" refers to a material that utilizes photosensitive silver halide for image formation. In the case of thermal dye transfer or ink jet, the image layer coated on the imaging element may be, for example, gelatin, colored latex, polyurethane, polyester, polyvinyl chloride, poly (styrene-co-acrylonitrile) polycaprolactone, polyvinyl alcohol, polycarbonate , Polyvinylpyrrolidone, starch, methacrylate, acrylic acid polymers and copolymers, polyethylene oxide, cellulosic materials such as hydroxymethylcellulose and other materials known in the art, and silica, sol-gel, alumina, calcium carbonate, clay , talc, zinc oxide, zeolites, can be a porous receptors containing barium sulfate, TiO ₂ or mixtures thereof. A mordant such as a cationic polyester sulfonate may be introduced. The dye image-receiving layer can be present in any amount effective for the purpose intended.

The photographic elements can be single color elements or multicolor elements. Multicolor elements have image dye-forming units sensitive to each of the three primary regions of the spectrum. Each unit can comprise a single emulsion layer or multiple emulsion layers sensitive to a given region of the spectrum. Element layers (including image forming unit layers)
Can be arranged in various orders as known in the art. In another format, the emulsions, each sensitive to the three primary regions of the spectrum, can be arranged as a single segmented layer.

[0014] The reflective support of the present invention comprises one or more resin coating layers on the support. One or more imaging layers can be placed on the water resistant resin coating layer.
Rutile TiO ₂ is contained in one or all of these resin coat layers. It is preferred to incorporate a resin layer containing the lowest amount of TiO ₂ next to the paper substrate. Rutile type Ti
Most preferably, the average pigment particle size of O ₂ is in the range of 0.1 to 0.26 μm. Pigments larger than 0.26 μm are too yellow for imaging element applications, and pigments smaller than 0.1 μm have poor opacity when dispersed in the polymer.

In the single-layer structure, the content of rutile-type TiO _{2 in} the resin coat layer is preferably more than 10% by weight and less than 50% by weight of the resin layer. When the rutile TiO ₂ content is less than 10% by weight, the imaging element has poor sharpness and opacity. Rutile TiO ₂ content of 50% by weight
Above this, the imaging element causes melt fracture problems during extrusion. In a multilayer structure, the rutile pigment can be present in one or all layers. The concentration of the small particle rutile pigment in each layer is preferably in the range of 0 to 50% by weight in each layer. The highest layer is the concentration of TiO _2, a concentration of the rutile pigment can be a 10 to 50% by weight of the layer.

The surface of the rutile TiO ₂ is coated with aluminum hydroxide, alumina or silica having a fluoride compound or fluorine ion, silicon hydroxide, silicon dioxide,
Boron oxide, barium-modified silica as described in U.S. Pat. No. 4,781,761, phosphate, zinc oxide, Z
inorganic compounds such as rO _2, etc., and polyhydric alcohols,
Organic treatment of a polyvalent amine, metal soap, alkyl titanate, polysiloxane, or the like, or treatment using a combination of the inorganic treatment agent and the organic treatment agent can be used. The amount of the surface treatment agent is preferably 0.2 to 2.0% based on the weight of titanium dioxide in the case of inorganic treatment, and 0.1 to 1% in the case of organic treatment.

Surprisingly, when TiO ₂ of small particle size was introduced into the resin layer of the imaging support, a sharp and white support was achieved. The small particle size rutile TiO ₂ resin layer provides the same white and lightness imaging support as current anatase systems. In addition, the small particle TiO ₂ imparts high sharpness and opacity to the imaging support. A small amount of small-particle rutile-type TiO ₂ can be added to the image-forming support resin layer to obtain the same sharpness and opacity as the highly filled anatase resin layer. Lower loadings of rutile pigment lower cost and die line tendency.

Further, rutile type TiO_Two Is hot yellow at the time of extrusion
Do not change. Small particle rutile TiO _Two With a large amount
Eliminates the need to use a stearate slip agent.
As the amount of stearate decreases, steer on the external extruder parts
Phosphoric acid accumulation is reduced, resulting in fewer defects and
The requirement for cleaning of the aircraft is reduced. Small particles in image forming resin layer
Child rutile type TiO_Two With high sharpness, poor
Low cost with transparency, whiteness, and excellent manufacturability
Generate a support.

The polymer and rutile TiO ₂ are mixed with each other in the presence of a dispersant. Examples of dispersants are metal salts of higher fatty acids such as sodium palmitate, calcium palmitate, sodium laurate, calcium stearate, aluminum stearate, magnesium stearate, zirconium octylate, higher aliphatic amides, and higher fatty acids. . The preferred dispersant is sodium stearate and the most preferred dispersant is zinc stearate. Both of these dispersants give excellent whiteness to the resin coat layer.

For photographic applications, a slightly bluish white substrate is preferred. Preferably, the layer of the water resistant resin coating contains a bluing agent and a colorant such as a magenta or red pigment. Applicable bluing agents include commonly known pigments, for example, ultramarine blue, cobalt blue, oxide cobalt phosphate, quinacridone pigments, and mixtures thereof. Applicable red or magenta colorants are quinacridones and ultramarines. In addition, the water-resistant resin may include a fluorescent agent that absorbs energy in the UV region and emits light widely in the blue region. One or a combination of the optical brighteners described in U.S. Pat. No. 3,260,715 can be incorporated into the resin coating.

The water resistant resin coating may include an antioxidant (s) (eg, a hindered phenol primary antioxidant used alone or in combination with a secondary antioxidant). Examples of hindered phenol primary antioxidants include pentaerythrityltetrabis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] (for example, Irganox 1010), octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (for example, Irganox 1076), 3,5-bis (1,1-dimethylbenzenebenzenepropanoate) )-
4-hydroxy-2 [3- [3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] -1-oxopropyl] hydrazide (e.g., MD1024), 2,
2′-thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (for example, Irganox 1035), 1,3,5-trimethyl-2,
4,6-tri (3,5-di-t-butyl-4-hydroxybenzyl) benzene (eg, Irganox 1330), but is not limited to these examples. Secondary antioxidants include triphenyl phosphites (eg, Irga
stab TPP), tri (n-propylphenyl-phosphite) (eg, Irgastab SN-55), 2,4-bis (1,
1-dimethylphenyl) phosphite (eg, Irgafo
organic alkyl and aryl phosphites, including examples such as s 168).

Suitable polyolefins for the water-resistant layer (s) include polyethylene, polypropylene, polymethylpentene, polystyrene, polybutylene and mixtures thereof. Also useful are copolymers of polyethylene, propylene and ethylene, such as olefin copolymers including hexene, butene, and octene. Polyethylene is preferred because it is inexpensive and has the desired coating properties. For polyethylene, what can be used are high density polyethylene, low density polyethylene, linear low density polyethylene, and polyethylene blends.

Other suitable polymers which may be included in the polyolefin include aromatic, aliphatic or cycloaliphatic dicarboxylic acids having 4 to 20 carbon atoms and aliphatic or cycloaliphatic glycols having 2 to 24 carbon atoms. And polyesters made from the same. Examples of suitable dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, 1,4- Includes cyclohexanedicarboxylic acid, sodiosulfoisophthalic acid and mixtures thereof. Examples of suitable glycols include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, 1,4-cyclohexanedimethanol,
Includes diethylene glycol, other polyethylene glycols and mixtures thereof. Preferred continuous matrix polyesters have a repeating unit derived from terephthalic acid or naphthalenedicarboxylic acid and at least one glycol selected from ethylene glycol, 1,4-butanediol and 1,4-cyclohexanedimethanol. Polyethylene terephthalate (which may be modified with small amounts of other monomers) is particularly preferred.
Other suitable polyesters include liquid crystal copolyesters formed by including a suitable small amount of an auxiliary acid component (eg, stilbene dicarboxylic acid). Examples of such liquid crystal copolyesters are described in U.S. Pat.
No. 7, No. 4,459,402 and No. 4,468,510.

Useful polyamides include nylon 6 (polycaprolactam), nylon 66 (polyhexamethylene adipamide) and mixtures thereof. Polyamide copolymers are also suitable continuous phase polymers.
An example of a useful polycarbonate is bisphenol-A polycarbonate. Cellulosic esters suitable for use as the continuous phase polymer of the composite sheet include cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, and mixtures and copolymers thereof. Useful polyvinyl resins include polyvinyl chloride, polyvinyl acetal, and mixtures thereof. Copolymers of vinyl resins can also be used.

The small particle rutile TiO ₂ , colorant, slip agent, optical brightener, and antioxidant are introduced together with or separately from the polymer in a mixer. A concentrate of the additives in the form of pellets is generally used. The concentration of the rutile pigment can be from 20% to 80% by weight of the masterbatch. The masterbatch is then sufficiently diluted for use with the water resistant resin.

The support on which the water-resistant resin layer is laminated can be a polymer, synthetic paper, woven fabric, woven polymer fiber, or cellulose fiber paper support, or a laminate thereof. Further, the base material is U.S. Pat.
Microporous polyethylene terephthalate as disclosed in US Pat. Nos. 994,312 and 5,055,371 can also be obtained. A preferred support is photographic grade cellulose fiber paper.

The chemical sensitization of an emulsion generally uses a sensitizer. For example, sulfur-containing compounds (eg, allyl isothiocyanate, sodium thiosulfate, and allyl thiourea); reducing agents (eg, polyamines and divalent stannous salts); noble metal compounds (eg, gold, platinum); and polymers A reagent (eg, a polyalkylene oxide). Heat treatment is used to complete chemical sensitization as described. Spectral sensitization is performed using a combination of dyes designed for the desired wavelength region in the visible or infrared spectrum. It is known to add such dyes both before and after heat treatment.

After spectral sensitization, the emulsion is coated on a support. Various coating techniques include dip coating, air knife coating, curtain coating, and extrusion coating. The silver halide emulsion used in the present invention can have any halide distribution. Accordingly, silver halide emulsions include silver chloride, silver chloroiodide, silver bromide, silver bromochloride, silver chlorobromide, silver iodochloride, silver iodobromide, silver bromoiodochloride, silver chloroiodobromide, and silver iodobromide. It can comprise silver bromochloride and silver iodochlorobromide.
However, it is preferred that the emulsion is primarily a silver chloride emulsion. "Predominantly silver chloride" means that the emulsion grains are greater than 50 mole percent silver chloride. Preferably this is 90
More than mol% silver chloride, optimally 95 mol% silver chloride.

The silver halide emulsions can contain grains of any size and morphology. Thus, the particles
It can take the form of cubic, octahedral, cubo-octahedral, or any other form inherent in cubic lattice silver halide grains. Further, the grains can be irregular, such as spherical or tabular grains. Grains having a tabular or cubic morphology are preferred.

The photographic element of the present invention is manufactured by TH James
Theory of the Photographic Process, 4th edition, T.
H. James, Macmillan Publishing Co., Inc., 1977, 1
The emulsions described on pages 51 to 152 can be used. It is known that reduction sensitization enhances the photographic sensitivity of silver halide emulsions. In general, reduction sensitized silver halide emulsions exhibit good photographic speed, but they often suffer from undesirable fog and poor storage stability.

By adding a reduction sensitizer (a reagent for reducing silver ions to form metallic silver atoms) or by adding a high p
H (excess hydroxide ion) and / or low pAg
By providing a reducing environment such as (excess silver ions), reduction sensitization can be intentionally performed. During precipitation of the silver halide emulsion, unintentional reduction sensitization may occur if, for example, a silver nitrate solution or an alkali solution is added rapidly or emulsion grains are formed without mixing well. Also, precipitation of silver halide emulsions in the presence of ripening agents (grain growth improvers) such as thioethers, selenoethers, thioureas, or ammonia also tends to promote reduction sensitization.

Examples of reduction sensitizers and reducing environments that can be used during precipitation or spectral / chemical sensitization to reduce and sensitize emulsions include:
It includes ascorbic acid derivatives, tin compounds, polyamine compounds, and thiourea dioxide-based compounds described in U.S. Patent Nos. 2,487,850 and 2,512,925 and British Patent No. 789,823. Dimethylamine borane, stannous chloride, hydrazine, high pH (pH 8-1
Specific examples of reduction sensitizers or conditions, such as 1) and low pAg (pAg 1-7) ripening, are described in Potographic Sc
ience and Engineering, 23,113 (1979)
Discussed by llier. Examples of methods for preparing intentionally reduction-sensitized silver halide emulsions are described in European Patent Application Publication Nos. 0348934 A1 (Yamashita) and 0369491 (Yamashita),
No. 0371388 (Ohashi), No. 0396424 A1 (Takada), same
0404142A1 (Yamada) and 0435355A1 (Makino).

The photographic element of the present invention is a Research Disclosure, Item 38957,
Section I, September 1996, (Kenneth Mason Publicatio
ns, Ltd., Dudley Annex, 12a North Street, Emsworth,
Emulsions doped with Group VIII metals such as iridium, rhodium, osmium, and iron, as described in Hampshire PO 107DQ, England) can be used. For an overview of the use of iridium in the sensitization of silver halide emulsions, see Carrol's "Iridium
Sensitization ": Literature Summary" Photographic Science a
nd Engineering, "Vol. 24, No. 6, 1980. A method for preparing a silver halide emulsion by chemically sensitizing the emulsion in the presence of an iridium salt and a photographic spectral sensitizing dye is described in U.S. Pat. No. 4,693,965. In some cases, the incorporation of such dopants has resulted in the British Journal of Photography Annual, 1
The emulsion shows increased new fog and lower contrast sensitometry curves when processed with a color reversal E-6 process as described in 982, pages 201-203.

A typical multicolor photographic element of the present invention relates to a cyan dye image-forming unit comprising at least one red-sensitive silver halide emulsion layer having at least one cyan dye-forming coupler associated therewith. Magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer having at least one magenta dye-forming coupler, and at least one blue-sensitive having at least one yellow dye-forming coupler having It comprises a laminated support according to the invention carrying a yellow dye image-forming unit comprising a silver halide emulsion layer. The element can include additional layers, such as filter layers, interlayers, overcoat layers, subbing layers, and the like. The supports of the present invention can also be used in black and white photographic print elements.

The photographic element of the present invention is disclosed in US Pat.
It is also possible to have a transparent magnetic recording layer containing magnetic particles on the back side of a transparent support as described in JP-A-279,945 and JP-A-4,302,523. This element typically has a total thickness of 5 to 30 μm (excluding the support).

References in the following table are: (1) Research Disclosure, December 1978, Item 17643, (2) Research Disclosure, December 1989, Item 308119, (3) Research Disclosure, September 1996, Item 38957, (All Kenneth Mason Publications, Ltd., Dudley Anne
x, 12a North Street, Emsworth, Hampshire PO10 7DQ,
Published by England). The table and the references cited in the table are to be understood as describing particular components suitable for use in the photographic elements according to the present invention. Also, this table and the references cited in it describe methods suitable for exposing, processing and manipulating the elements and the images contained therein.

[0037] Reference No. Section Theme 1 I, II Particle composition, morphology and preparation; Hardening 2 XI, XII, XIV, XV Emulsion preparation 3 I, II , including agents, coating aids, additives, etc. , III, IX A & B 1 III, IV Chemical sensitization and spectral sensitization / desensitization 2 III, IV 3 IV, V 1V UV dye, Fluorescent brightener, 2V fluorescent dye 3 VI 1VI Antifoggant and stable Agents 2 VI 3 VII 1 VIII Absorbing and scattering materials; Antistatic layer 2 VIII, XIII, XVI; Matting agents 3 VIII, IX C & D 1 VII Image couplers and image-modified caps 2 VII colorants; Dye stabilizers and hues Revision 3 X Good agent 1 XVII support 2 XVII 3 XV 3 XI Specific layer arrangement 3 XII, XIII negative emulsion; direct positive emulsion 2 XVIII exposure 3 XVI 1 XIX, XX chemical treatment; developing agent 2 XIX, XX, XXII 3 XVIII, XIX, XX 3 XIV Scanning and digital processing method

The photographic elements of the present invention can be used in the ultraviolet, visible, and infrared regions of the electromagnetic spectrum, as well as various energy forms, including electron beams, beta rays, gamma rays, X-rays, alpha particles, neutron rays, and non-coherent ( Exposure can be made using particles in a (random phase) form or in a coherent (in-phase) form, such as that produced by a laser, and other forms of wave radiation energy. X
If a line is to be exposed, it can have features found in conventional radiographic elements.

Preferably, the photographic element of the present invention comprises actinic radiation,
In particular, by exposing the visible region of the spectrum to form a latent image,
It is then processed (preferably other than heat treatment) to form a visible image. The treatment is preferably performed using a known RA-4 ^™ (Eastman K
odak Co.) process or other processing system suitable for the development of high chloride emulsions.

To make the water-resistant resin coating according to the invention, pellets containing pigments and other additives are subjected to hot melt coating on a running support made of paper or synthetic paper. If necessary, dilute the pellets with the polymer before hot melt coating. In the case of single layer coating, a resin layer is formed by lamination. In the case of multilayer coating, the resin layer is formed by sequential lamination or another lamination using a multilayer extrusion die (die using a feed block, die composed of a multi-slot type or a multi-manifold). The die is not limited to any type and can be any conventional die such as a T-slot or coat hanger die. The outlet orifice temperature in the hot melt extrusion of the water-resistant resin is 260 to 349 ° C (500 to 660 °).
F). Further, before coating the support with a resin, the support may be subjected to an activation treatment such as corona discharge, flame, ozone, plasma, or glow discharge.

On the image forming side, the total thickness of the single-layer water-resistant resin or the multilayer water-resistant resin applied to the base paper of the reflective support used in the present invention is preferably 5 to 100 μm,
Most preferably, it is 10 to 50 μm. When the water-resistant layer has a multilayer structure, the thickness of each layer is preferably in the range of 0.5 to 50 μm. For example, for a water-resistant resin coating having a two-layer structure, the thickness of each layer is in the range of 0.5 to 50 μm, and the total thickness is preferably 5 to 100 μm, and more preferably 10 to 50 μm.

The thickness of the resin layer applied to the base paper on the opposite side of the image forming element is preferably 5 to 100 μm,
0 μm is most preferred. The surface of the water-resistant resin coating on the image forming side can be a glossy surface, a fine surface, a silk surface, a granular surface, or a matte surface. The surface of the water resistant coating on the side not coated with the image forming layer can also be a glossy surface, a fine surface, a silk surface, or a matte surface. The preferred water resistant surface away from the imaging element is matte.

[0043]

EXAMPLE A pulp furnish consisting of 100% bleached hardwood kraft was purified in a double disc refiner and then in a Jordan conical refiner to produce a photographic paper support. To the obtained pulp furnish, on a dry basis, 0.8% of sodium stearate, 0.5% of aluminum chloride, 0.15% of stilbentriazine FWA,
0.2% polyamide epichlorohydrin, 0.7% anionic polyacrylamide and 0.6% TiO ₂ were added. About 152kg / 1000m ² (31.5lbs / 1000ft
² (ksf)) An absolutely dry base paper is made with a Ford Linier paper machine, wet-pressed to a solid content of 42%, and dried to a moisture content of 3% with a steam heating dryer to achieve an apparent density of 0.70 g / cc. did. And this paper base,
The surface was glued with a 16% hydroxyethylated corn starch solution using a vertical size press to achieve a starch loading of 4.2% by weight. The support having the surface glued thereon was dried with a steam heating dryer to a water content of 8.8%, and calendered to an apparent density of 1.08 g / cc.

Example 1 A blend of high and low density polyethylene was prepared at 316 ° C. (600 ° F.) and 29.2 g / m ^2.
At a coverage of (6.0 lbs / 1000 ft ² ), it was melt extruded on one side of the paper described above. On the other side of the paper, 0.22 μm rutile TiO ₂ 12% (manufactured by Dupont), zinc stearate 0.1%.
26.2 g / m ^{2 of} a low-density polyethylene resin containing 3%, a fluorescent whitening agent 0.05%, an antioxidant 0.1%, a blue coloring agent 0.6%, and a red coloring agent 0.002% ( 5.5lbs /
1000 ft ² ) at 316 ° C. (600 ° F.) and thickness 30 μm
And extrusion coated. The resulting resin-coated support was sensitized as described below.

An approximately equimolar amount of a solution of silver nitrate and sodium chloride was added to a reactor in which a gelatin peptizer and a thioether ripening agent were well mixed, and a blue-sensitive emulsion (blue EM-1) was added.
Was precipitated. Cesium pentachloronitrosyl osmate was added during manufacture and potassium iodide was added towards the end of the manufacture to form a silver iodide band in the grains. The obtained emulsion had cubic grains having a side length of 0.6 μm. The emulsion was added with glutaryl diaminophenyl disulfide, followed by the addition of a colloidal suspension of gold sulfide, and heating to 60 ° C with a ramp.
The blue sensitizing dye BSD-4, potassium hexachloroiridate, Lippman bromide and 1- (3-acetamidophenyl) -5-mercaptotetrazole were added for optimal sensitization.

An approximately equimolar amount of silver nitrate and sodium chloride solution was added to a reactor in which a gelatin peptizer and a thioether ripening agent were well mixed, and a green-sensitive emulsion (green EM-1) was added.
Was precipitated. Cesium pentachloronitrosyl osmate was added during most of the manufacturing. The obtained emulsion had cubic grains having a side length of 0.3 μm. The emulsion was optimally sensitized by adding a colloidal suspension of gold sulfide and heating to 55 ° C. The following were added: potassium hexachloroiridate, Lippman bromide and green sensitizing dye GSD-1. The completed emulsion was then cooled and 1- (3-acetamidophenyl) -5-mercaptotetrazole was added a few seconds after the cooling started.

About equimolar amounts of silver nitrate and sodium chloride solutions were added to a reactor in which a gelatin peptizer and a thioether ripening agent were well mixed, and a green-sensitive emulsion (green EM-2) was obtained.
Was precipitated. Cesium pentachloronitrosyl osmate was added during most of the preparation and potassium iodide was added towards the end of the preparation to form a silver iodide band in the grains. In addition, pentachlorothiazole iridate (I
II) The potassium salt was added towards the end of the production. The resulting emulsion had cubic shaped grains with a side length of 0.22 μm. The emulsion was added with glutaryl diaminophenyl disulfide, followed by the addition of a colloidal suspension of gold sulfide, and heating to 60 ° C. with gradient while the green sensitizing dye GSD-4, potassium hexachloroiridate. , Lippman bromide and 1- (3-acetamidophenyl) -5-mercaptotetrazole were added for optimal sensitization.

An approximately equimolar amount of a solution of silver nitrate and sodium chloride was added to a reactor containing a gelatin peptizer and a thioether ripening agent, and the mixture was added to a red-sensitive emulsion (red EM-1).
Was precipitated. The obtained emulsion had cubic grains having a side length of 0.4 μm. This emulsion was treated with bis (1,4,5-
Trimethyl-1,2,4-triazolium-3-thiolate) gold (I) fluoroborate and sodium thiosulfate were added, followed by heat aging at 65 ° C. for optimal sensitization. Then the following were added: 1- (3-acetamidophenyl) -5-mercaptotetrazole, potassium hexachloroiridate and potassium bromide. The emulsion was cooled to 40 ° C and the red sensitizing dye RSD-1 was added.

The coupler dispersion is emulsified in a manner well known in the art to provide a polyethylene resin coated support (sized to the size described in US Pat. No. 4,994,147;
(PH adjusted as described in U.S. Pat. No. 4,917,994) was coated with the following layers. The polyethylene layer coated on the emulsion layer side of the support contained 0.1% of 4,4'-
Containing bis (5-methyl-2-benzoxazolyl) stilbene and 4,4'-bis (2-benzoxazolyl) stilbene, 12.5% TiO _2, and 3% of a mixture of ZnO white pigment did. 1.95% by weight of total gelatin
In%, these layers were hardened with bis (vinylsulfonylmethyl) ether.

Layer 1: Blue-sensitive layer Gelatin 1.133 g / m ² Blue-sensitive silver (blue EM-1) 0.186 gAg / m ² Y-4 0.420 g / m ² ST-23 0.420 g / m ² Phthal Dibutyl acid 0.186 g / m ² ST-16 0.010 g / m ²

Layer 2: Intermediate layer Gelatin 0.650 g / m ² Di-t-octylhydroquinone 0.056 g / m ² Dibutyl phthalate 0.163 g / m ²

Layer 3: Green-sensitive layer Gelatin 1.087 g / m ² Green-sensitive silver (green EM-1) 0.067 gAg / m ² M-7 0.280 g / m ² Dibutyl phthalate 0.076 g / m ² Phthal Diundecyl acid 0.033 g / m ² ST-8 0.019 g / m ² ST-21 0.167 g / m ² ST-22 0.530 g / m ²

[0053] layer 4: UV intermediate layer Gelatin ^{0.630g / m 2 UV-1 0.028g} / m 2 UV-2 0.158g / m 2 di -t- octylhydroquinone 0.046 g / m ² 1,4 Cyclohexylene dimethylene bis- (2-ethylhexanoate) 0.032 g / m ² Dibutyl phthalate 0.032 g / m ²

Layer 5: Red-sensitive layer Gelatin 1.170 g / m ² Red-sensitive silver (Red EM-1) 0.160 g Ag / m ² C-3 0.365 g / m ² Dibutyl phthalate 0.362 g / m ² UV -2 0.230 g / m ² 2- (2-butoxyethoxy) ethyl acetate 0.028 g / m ² di -t- octylhydroquinone 0.003 g / m ² potassium tolylthiosulfonate acid 0.0023 g / m ² tolyl sulfinate Potassium 0.0002 g / m ²

Layer 6: UV overcoat Gelatin 0.446 g / m ² UV-1 0.019 g / m ² UV-2 0.111 g / m ² Di-t-octylhydroquinone 0.033 g / m ² 1,4- Cyclohexylene dimethylene bis- (2-ethylhexanoate) 0.022 g / m ² Dibutyl phthalate 0.022 g / m ²

[0056] layer 7: SOC Gelatin 0.557 g / m ² di -t- octylhydroquinone 0.019 g / m ² Silica 0.204 g / m ² polydimethyl siloxane ^{0.017g / m 2 SF-2 0.002g} / m ² Tergitol 15-S-5 0.002g / m ²

Example 2 A blend of high and low density polyethylene was prepared at 316 ° C. (600 ° F.) and 29.2 g / m ^2.
At a coverage of (6.0 lbs / 1000 ft ² ), it was melt extruded on one side of the above paper. On the other side of the bleached hardwood kraft paper, 12% by weight of 0.22 μm rutile-type TiO ₂ , 0.3% by weight of sodium stearate, and 0.05 of fluorescent whitening agent
26.2 g / m ² (5.5 lbs / 1000 ft ² ) of a polyethylene resin containing 0.1% by weight of an antioxidant, 0.6% by weight of a blue colorant, and 0.002% by weight of a red colorant. 3
Extrusion coated onto photographic paper at 16 ° C (600 ° F). The resulting resin-coated support was sensitized as described in Example 1.

Example 3 A blend of high and low density polyethylene was prepared at 316 ° C. (600 ° F.) and 29.2 g / m ^2.
At a coverage of (6.0 lbs / 1000 ft ² ), it was melt extruded on one side of the paper described above. On the other side of the bleached hardwood kraft paper, 12% by weight of 0.22 μm rutile TiO ₂ , Kema
ide w40 Contains 0.3% by weight of fatty acid bisamide, 0.05% by weight of optical brightener, 0.1% by weight of antioxidant, 0.6% by weight of blue colorant, and 0.002% by weight of red colorant. Polyethylene resin 26.2 g / m ² (5.5 lbs / 1000
ft ² ) was extrusion coated on photographic paper at 316 ° C. (600 ° F.). The resulting resin-coated support was sensitized as described in Example 1.

Comparative Example 1 A blend of high density polyethylene and low density polyethylene was prepared at 316 ° C. (600 ° F.) and 29.2 g / m ^2.
At a coverage of (6.0 lbs / 1000 ft ² ), it was melt extruded on one side of the paper described above. On the other side of the bleached hardwood kraft paper, 14.5% by weight of 0.18 μm anatase TiO ₂ , 0.5% by weight of calcium stearate, 0.05% by weight of fluorescent whitening agent, 0.1% of antioxidant 26.2 g / m ² (5.5 lbs / 1000) of a polyethylene resin containing, by weight, 0.6% by weight of blue colorant and 0.002% by weight of red colorant.
ft ² ) was extrusion coated on photographic paper at 316 ° C. (600 ° F.). The resulting resin-coated support was sensitized as described in Example 1.

Example 4 12% by weight of 0.22 μm rutile type TiO ₂ , 0.5% by weight of zinc stearate and 0.0% of a fluorescent whitening agent from Example 1
Extruding a polyethylene resin containing 5% by weight, 0.1% by weight of antioxidant, 0.6% by weight of blue colorant and 0.002% by weight of red colorant onto a 1.5 "Egan extruder The die line tendency was tested by drying (−22).
° C (-7.5 ° F dew point) hot air (82 ° C (180 °
F)) The resin was dried in a dryer for 17 hours. 308
At 587 ° F., about 23-27 kg (50-60 l)
The resin was extruded at a rate of b) / hour. The resin was extruded at 130 RPM in a sagging manner (no coating, just put in cooling bath). 29.2 g / m ²
A (6.0 lbs / 1000 ft ² ) resin blend was coated on standard photographic great paper every 30 minutes. The criterion used to determine the time to die line was the time it took for the first die line to be visible on the resin coated sheet.

Example 5 12% by weight of 0.22 μm rutile type TiO _2, 0.3% by weight of Kemamide w40 fatty bisamide, 0.05% by weight of optical brightener, 0.1% by weight of antioxidant from Example 3 A polyethylene resin containing 0.6% by weight of blue colorant and 0.002% by weight of red colorant was tested for die line tendency by extruding the resin onto a 1.5 "Egan extruder. Dry (-22 ° C). Dew point: 17 hours with hot air (82 ° C) dryer
The resin was dried. At 308 ° C., about 23 to 27 kg /
The resin was extruded at the current speed. The resin was extruded at 130 RPM in a sagging manner (no coating, just put in cooling bath). 29.2 g / m ² (6.0 lb
s / 1000 ft ² ) of the resin blend was coated on standard photographic great paper every 30 minutes. The criterion used to determine the time to die line was the time it took for the first die line to be visible on the resin coated sheet.

Comparative Example 2 The resin formulation from Comparative Example 1 was tested for die line tendency by extruding the resin onto a 1.5 "Egan extruder. Dry (-22 ° C dew point) hot air (82 ° C) dryer. 17
Over time, the resin was dried. At 308 ° C, about 23-27
The resin was extruded with a 0.03 mm (30 mil) die gap at a rate of kg / hr. The resin was extruded at 130 RPM in a sagging manner (no coating, just put in cooling bath). 29.2 g / m ² (6.0 lbs / 10
00ft ² ) Resin blend on standard photographic great paper
Coated every 0 minutes. The criterion used to determine the time to die line was the time it took for the first die line to be visible on the resin coated sheet.

The samples of Examples 1 to 3 and Comparative Example 1 were chemically photographic processed (no exposure) to obtain samples having the minimum dye concentration.
Samples with the lowest dye concentration should be
) Color tests were performed using a colorimeter (Table I).

[Table 1]

L^*Is the brightness of the support, a^*Is red
Degree, b^*Is blueness. L^*The higher the value, the brighter
A^*The higher the value, the redder, b^*The lower the value, the more
blue. The brighter and bluer the support, the better the support appearance
White. In photography, L^*Is b^*Is a function of Support
More blue colorant to make the
However, the whiteness decreases. UVO measurement is tongue
Equivalent to stainless illumination, UVI is equivalent to fluorescent illumination. same
L^*In UVO measurements by value, the rutile-type support was ~ 0.
7b units blue, but with UVI the support is essentially b^*Is the same
The same. 0.4b ^*The value of
It is so blue that it draws. Therefore, in typical room light, rutile
The type support looks whiter than the anatase type support,
In the Ming, rutile and anatase supports are equally
Will look white.

The samples were evaluated visually under different types of illumination (D5500, fluorescent and tungsten). Visual evaluation correlated well with the spectroguard data. The present invention is the same as or superior to the comparative examples.

[0066]

[Table 2]

DMT sharpness is directly proportional to the concentration of anatase or rutile TiO ₂ . The example of rutile TiO ₂ contains 17% less TiO ₂ , but the sharpness of the inventive example is better than the comparative example.

[0068]

[Table 3]

The two examples of the present invention both took more than twice as long as the anatase comparative example.

Other preferred embodiments of the present invention are described below in connection with the claims. (Aspect 1) At a concentration of at least 10% by weight and a particle size of 0.1
An image forming resin comprising: a polyolefin in which rutile-type TiO _{2 of about} 0.26 μm is dispersed; and a dispersant. (Aspect 2) The image forming resin according to aspect 1, wherein the polyolefin is selected from the group consisting of polyethylene, polypropylene, polymethylpentene, polystyrene, and polybutylene. (Aspect 3) The rutile TiO ₂ is treated with aluminum hydroxide, silicon hydroxide, phosphate, zinc oxide, ZrO ₂ , polyhydric alcohol, polyamine, metal soap, alkyl titanate, or polysiloxane. The resin for image formation according to aspect 1, which has a roughened surface.

(Embodiment 4) The resin for image formation according to claim 1, wherein the resin further comprises a coloring agent, a slip agent, a fluorescent whitening agent or an antioxidant. (Aspect 5) A support having a front surface and a rear surface, at least one
At a concentration of 0% by weight, dispersed particle size 0.1-0.2
An image forming substrate comprising a polyolefin resin disposed on at least one side of the support, the rutile type TiO ₂ having a thickness of 6 μm, and a dispersant. (Aspect 6) The image forming substrate according to Aspect 5, wherein the polyolefin is selected from the group consisting of polyethylene, polypropylene, polymethylpentene, polystyrene, and polybutylene.

(Embodiment 7) The above rutile type TiO ₂ is composed of aluminum hydroxide, silicon hydroxide, phosphate, zinc oxide,
The image forming substrate according to embodiment 5, which has a surface treated with ZrO ₂ , polyhydric alcohol, polyamine, metal soap, alkyl titanate, or polysiloxane. (Aspect 8) The image forming substrate according to claim 5, wherein the resin further comprises a coloring agent, a slip agent, a fluorescent whitening agent or an antioxidant. (Aspect 9) The image forming substrate according to claim 5, wherein the support comprises paper, woven fabric, woven polymer fiber, or a laminate thereof.

(Embodiment 10) The above-mentioned support having a support having a front surface and a rear surface, rutile-type TiO ₂ having a particle size of 0.1 to 0.26 μm dispersed at a concentration of at least 10% by weight, and a dispersant. An imaging element comprising a polyolefin resin disposed on at least one side of the body, and an imaging layer disposed on said polyolefin resin. (Embodiment 11) The image forming element according to embodiment 10, wherein the polyolefin is selected from the group consisting of polyethylene, polypropylene, polymethylpentene, polystyrene and polybutylene. (Aspect 12) When the rutile TiO ₂ is aluminum hydroxide, silicon hydroxide, phosphate, zinc oxide, ZrO ₂ ,
The imaging element of embodiment 10 having a surface that has been treated with a polyhydric alcohol, polyamine, metal soap, alkyl titanate, or polysiloxane.

(Aspect 13) The image forming element according to claim 10, wherein the resin further comprises a colorant, a slip agent, a fluorescent whitening agent or an antioxidant. (Aspect 14) The support comprises paper, woven fabric, woven polymer fiber, or a laminate thereof.
4. The image forming element according to claim 1. (Embodiment 15) A support having a front surface and a rear surface, dispersed at a concentration of at least 10% by weight and having a particle size of 0.1 to 0.1%.
An imaging element comprising a polyolefin resin disposed on at least one side of the support, having 26 μm rutile TiO ₂ , and a dispersant, and a silver halide emulsion layer disposed on the polyolefin resin .

(Embodiment 16) The image forming element according to embodiment 15, wherein said polyolefin is selected from the group consisting of polyethylene, polypropylene, polymethylpentene, polystyrene and polybutylene. (Aspect 17) The rutile TiO ₂ is aluminum hydroxide, silicon hydroxide, phosphate, zinc oxide, ZrO ₂ ,
Embodiment 16. The imaging element of embodiment 15 having a surface treated with a polyhydric alcohol, polyamine, metal soap, alkyl titanate, or polysiloxane. (Aspect 18) The resin further comprises a colorant, a slip agent, an optical brightener or an antioxidant.
4. The image forming element according to claim 1. (Aspect 19) The support comprises paper, woven fabric, woven polymer fiber, or a laminate thereof.
4. The image forming element according to claim 1.

Claims (2)

[Claims] 1. An image forming resin comprising a polyolefin in which rutile TiO ₂ having a particle size of 0.1 to 0.26 μm is dispersed at a concentration of at least 10% by weight and a dispersant. 2. A support according to claim 1, comprising a support having a front surface and a rear surface, rutile-type TiO ₂ having a particle size of 0.1 to 0.26 μm dispersed at a concentration of at least 10% by weight, and a dispersant. An imaging substrate comprising a polyolefin resin disposed on at least one side.