JPS6067939A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a superior photographic printing paper by forming a layer of compsn. contg. an electron beam hardenable compd., a coupling agent having an ethylenically unsatd. double bond in the molecule, and an inorg. white pigment on the surface of a support, and forming a silver halide emulsion layer on this hardened compsn. layer. CONSTITUTION:At least one side of a supporting base is coated with a compsn. contg. an electron beam hardenable compd., a coupling agent having an ethylenically unsatd. double bond in the molecule, and an inorg. white pigment, hardened with electron beams to form a coating layer, and on this layer at least one silver halide emulsion layer is formed. The use of said coupling agent can reduce bleeding of precipitates on the surface or in the inside during a manufacturing process and a storing stage, and improves abrasion resistance. The silver halide photosensitive material using a support having such a coating layer is improved in dispersibility of the pigment, enhanced in sharpness of a photographic image, pigment fillability, and smoothness of the supporting surface, prevented from unevenness in emulsion coating, improved in adhesion of the coating layer to the base, and therefore, the coated support does not become brittle.

Description

Detailed Description of the Invention (1) Background of the Invention Technical Field The present invention relates to a silver halide photographic material. More specifically, the present invention relates to a silver halide photographic material having a support produced by electron beam irradiation and particularly suitable as photographic paper.

PRIOR ART AND THEIR PROBLEMS As supports for photographic paper, paper substrates whose surfaces are coated with polyolefin resins have recently been used in order to speed up photographic processing.

In order to improve the whiteness and hiding power of the support as well as the resolution and sharpness after coating the photographic emulsion, the polyolefin resin contains an inorganic white pigment such as titanium oxide or calcium carbonate.

By the way, when forming a polyolefin resin coating, it is necessary to melt the resin at a high temperature of about 280 to 340°C. Moreover, it is not possible to incorporate a large amount of inorganic white pigment into such a polyolefin resin melted at a high temperature, and furthermore, the dispersibility is poor. Therefore, there is a disadvantage that the sharpness of the photographic image cannot be changed to a sufficiently satisfactory level.

Under these circumstances, attempts have been made to disperse large amounts of inorganic pigments in polyolefin resins using dispersants.

For example, the technology of surface treating titanium oxide with hydrated alumina described in JP-A No. 51-8531,
Hydrous A (OH) described in No. 2-35825
2 or the technology of surface treating titanium oxide with hydrated Amon (OH) 2 and hydrated silicon dibutyride, and JP-A-55-108E1.
The technology of coating titanium oxide with a surfactant described in No. 58, the technology of coating the surface of titanium oxide particles with β-diketone chelate described in JP-A-55-113039, and the This includes the technique of coating the surface of titanium oxide particles with amines, which is described in Japanese Patent Publication No. 55-113040.

However, when using these techniques, when polyolefin resin is melted at high temperatures, contamination from these additives occurs at the goo exit end of the extruder, and concave lines are formed on the surface of the molten film. It has the disadvantage that it forms grooves on the surface of the body, causing uneven application of the emulsion.

Moreover, JP-A No. 57-1511142 proposes the use of an alkyl titanate in place of the above-mentioned additive (which functions as a type of dispersant), which improves the above-mentioned drawbacks.

However, in this case, the alkyl titanate-treated pigment enters the molten polyolefin resin at only about 10 to 20 wt %, which is insufficient in terms of sharpness. In addition, free alkyl titanates that are not bonded to pigments are likely to be generated, which may thermally decompose during melting and emit smoke in the coating.
There are drawbacks such as adhesion to the cooling roll and the ability to change the smooth film surface.

As described above, when pigments are incorporated into conventional polyolefin resin coatings, sufficient sharpness has not yet been achieved.

In view of this situation, Japanese Patent Application Laid-Open Nos. 57-27257 and 1987-49948-9 disclose a method in which a composition that can be cured by electron beam irradiation is coated on a paper base material, and then the paper is irradiated with the electron beam. Photographic supports have been proposed that have a coating layer that is cured.

Since such a support is coated at room temperature, the content of inorganic pigment can be increased to 20 to 70 wt%, and dispersion is easy. As a result, the sharpness is comparable to that of polyolefin resin coating. It is significantly improved in comparison.

However, coating liquids containing pigments and resins that can be cured by electron beams have a disadvantage in that they have low storage stability and cannot be stored for long periods of time.

In addition, after coating and before electron beam irradiation, the coating material may aggregate and cause 1
, the filling properties after curing are poor, and the surface smoothness of the coating layer is extremely poor.

Furthermore, especially when the amount of pigment added is increased, the cured layer becomes brittle, prone to stress cracking, and has poor adhesion to the paper base material.

In this way, the electron beam-curable coating layer in the above proposal does not take into account the affinity or dispersibility between the electron beam-curable resin and the pigment, and also the coating layer when the amount of pigment added is increased. No consideration is given to the mechanical properties of the layer, which is insufficient for practical use.

Therefore, along with resin and pigment that can be cured by electron beam,
It is possible to improve the dispersibility of the pigment by adding various dispersion improvers.

However, ordinary dispersibility improvers such as surfactants do not have the effect of improving adhesion when the amount of pigment added is increased, nor do they have the effect of preventing embrittlement of the cured coating layer.

Furthermore, with conventional dispersibility improvers, when the amount added is increased, there is also the disadvantage that the coating layer becomes sticky.

11 Object of the Invention The object of the present invention is to produce a silver halide film using a support having a coating layer formed by disposing a composition containing a compound curable by electron beam and an inorganic white pigment and curing by electron beam. In photographic light-sensitive materials, the dispersibility of pigments is improved, the sharpness of photographic images is excellent, the filling property of pigments is improved, the smoothness of the support surface is excellent, there is no uneven coating of emulsion, and furthermore, The object of the present invention is to realize a material that has excellent adhesion between the base material and the coating layer, does not cause embrittlement of the cured coating layer, and does not cause stress cracks or cracks.

Such objects are achieved by the invention described below.

That is, the present invention provides a composition containing a compound curable by electron beam, a coupling agent having a C;C unsaturated double bond in the molecule, and an inorganic white pigment on at least one surface of a support base material. This is a silver halide photographic light-sensitive material characterized in that it has a coating layer formed by forming the silver halide emulsion layer and hardening it with an electron beam, and has at least one silver halide emulsion layer on the coating layer.

Note that the present inventors have previously proposed the use of silane or titanium coupling agents in a prior application to this application.

In the present invention, among these silanes or titanium camping agents, those having a C═C unsaturated double bond in the molecule are used, so the above-mentioned objective can be achieved with higher effectiveness, and the manufacturing process, storage process, etc. In this case, the phenomenon of forming precipitates on the surface or inside, that is, bleeding, is reduced, and the scratch resistance is also improved.

■Specific structure of the invention Hereinafter, a specific configuration of the present invention will be explained in detail.

The compound curable by electron beam used in the present invention includes a resin containing two or more unsaturated double bonds in its molecular chain, which is hardened by double polymerization or crosslinking by generating radicals etc. by electron beam irradiation. It is preferable that

Therefore, photographic supports having acrylic double bonds such as acrylic acid, methacrylic acid or their esters, allylic double bonds such as diallyl phthalate, unsaturated bonds such as maleic acid and maleic acid derivatives, etc. Any resin curable by electron beams that is known in the art or in various technical fields may be used.

However, especially when using paper base material as the support base material,
%: If the amount of white pigment added is increased, the hardened coating layer tends to become brittle, so the following are particularly suitable as those that do not impair the flexibility peculiar to paper.

(1) As urethane acrylate oligomer incyanate, 2.4-toluene diisocyanate, 2.6
-) Luene diisocyanate, 1.3-xylene diisocyanate, 1.4-xylene diisocyanate, 1.
5-Naphthalene diisocyanate.

m-phenylene diisocyanate, P-phenylene diisocyanate, 3.3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4.4'-diphenylmethane diisocyanate, 3.3'-dimethylbiphenylene diisocyanate), 4.4'- Various polyvalent incyanates such as biphenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate-1, Desmodur L, Desmodur N, and green forest saturated polyesters such as ethylene glycol,
Polyhydric alcohols such as diethylene glycol, glycerin, trimethylolpropane, 1,4-butanediol, 1,6-hexanediol, pentaerythritol, nrubitol, neopentyl glycol, 1,4-cyclohexanedimethanol, and phthalate. acid, isophthalic acid,
or by condensation polymerization with saturated polybasic acids such as terephthalic acid, maleic acid, succinic acid, adipic acid, and sebacic acid.

Linear saturated polyethers, such as polyethylene glycol, polypropylene glycol.

Polyurethane elastomers and prepolymers made of polycondensates of polytetraethylene glycol, etc., and various polyesters such as caprolactam, hydroxy-containing acrylic esters, and hydroxy-containing methacrylic esters.

Telomer is effective.

It is also possible to use a urethane elastomer modified by reacting the terminal incyanate group or hydroxyl group with a monomer having an acrylic double bond or an allylic double bond to react with the incyanate group or hydroxyl group.

Note that the molecular weight is preferably about 500 to 20,000.

(2) Spirane ring-containing acrylic oligomer A compound that has a spirane ring in its molecule, has an acrylic double bond at both ends of the molecule, has a molecular weight of usually 500 to 20,000, preferably 2,000 or less, and is liquid at room temperature. .

A typical example is 1 mole of tetramethylolmethane reacted with 2 moles of vinyl aldehyde to form an acetal.

Next, a spiran ring-containing oligomer represented by the following general formula (wherein R is an alkylene group and n is an integer) is synthesized by reacting a polyhydric alcohol to the vinyl groups at both ends, and Examples include those obtained by subjecting a hydroxyl group to an esterification reaction with an acrylic unsaturated acid such as acrylic acid or methacrylic acid.

Commercial products of such spiran ring-containing acrylic oligomers include Subi-5-/Ri-T-5 manufactured by Showa Kobunshi Co., Ltd.
00,T-510X-7,N, T-502X-
4, υ-3000. U-3150. υ−3151,E−
4000 etc.

(3) Butadiene oligomer 1.2-polybutadiene glycol N manufactured by Nippon Soda Co., Ltd.
l5SO-LeB G-1000, 2000, 3000,
A compound in which an acrylic unsaturated double bond is added to an oligomer having 10H groups at both ends, such as PolyBD Liquid Resin R-15 manufactured by Sinclair Petrochemical.

Cyclized polybutadiene such as CBR-MEIOl manufactured by Japan Synthetic Rubber Co., Ltd.

The molecular weight of these is preferably 500 to 20,000.

Specific examples of these compounds that can be cured by electron beams are listed below, but the invention is not limited to these.

-cIJ Zeng These electron beam curable compounds may be used as a mixture of two or more types.

Also, for the purpose of adjusting hardenability and flexibility.

It is preferable to mix one or more kinds of electron beam curable compounds, such as the following oligomers or hematinants, which accelerate the curing speed of these compounds with electron beams, into these preferred compounds. is 20-6
0ffi amount% is preferred.

Suitable compounds include the following.

(1) (CH-CCH2CH3)3C-C2H5(2
) (CH-CCH2CH3)3C-CI(20H(3
) (CH-CHCo-(OC3H8)-0(J2)3
-CCH2CH3(4) CH2-CHCOO(OH2
80COCR-CH2(5) CM “CHCOO(C
H2), 0COCH-CH2 (n is 1 to 14.) (7) CH=CH-C0-0+CH2-CH,,O+
nCo-CH-tl:)12 (n is 4 to 14.) Among the compounds curable by electron beam, the ratio of monomer to oligomer is not particularly limited, but is 60/40 to 20/
A range of 80% by weight is preferred.

Furthermore, for the purpose of improving flexibility and adhesion of the support base material, thermoplastic resins represented by the following may be mixed and used.

(1) Cellulose derivative nitrocellulose, cellulose acetate butyrate,
Ethyl cellulose, butyl cellulose, etc. (2) Polyvinyl alcohol resins Polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, etc. (3) Polybutadiene and butadiene copolymers Polybutadiene, acrylonitrile butadiene copolymer, styrene-butadiene 8m polymer, etc. (4) Vinyl chloride copolymers, vinyl chloride-vinyl acetate copolymers, vinyl 41-vinyl acetate-maleic copolymers, etc. (5) polyurethane resins (6) unsaturated and saturated polyester resins (7) polyamide resins, etc.

These thermoplastic resins may or may not have an acrylic modified double bond introduced therein.

These thermoplastic resins are mixed at a mixing ratio of 80/20 to 40/60% by weight based on the total amount of the above-mentioned electron beam curable compound and 1TL-f-ray curable compound for improving curing speed. It is preferable.

Next, the coupling agent in the present invention is a compound having two or more different reactive groups in its molecule, and one of these reactive groups is one that chemically bonds with the inorganic white pigment (
methoxy group, I-oxy group, silanol group, etc.),
The other is a reactive group that chemically bonds with a compound that can be cured by an electron beam (in the present invention, a C═C unsaturated double bond).
It is.

Such a coupling agent has the function of acting as a bridge between the electron beam curable compound and the inorganic white pigment by forming a strong chemical bond.

As a result, the following excellent effects are produced.

(1) Dispersibility and filling properties of the inorganic white pigment.

Since the surface smoothness of the coating layer is sufficiently improved, the surface smoothness of the coating layer becomes good.

(2) [411] Workability is significantly improved by increasing the content of the white pigment at a high concentration.

(3) The interface of the inorganic white pigment can be effectively reinforced, and there is an advantage that the type of compound curable by electron beam can be selected from a wide range.

In this case, the coupling agent is preferably a silane coupling agent or a titanium coupling agent, which is added so as to coat the surface of the inorganic white pigment.

That is, the coupling agent chemically bonds with the hydroxyl groups of the inorganic white face I') and the hydroxyl groups in the metal oxide layer partially covering the surface thereof.

That is, since the silane coupling agent has a group forming a silanol group and/or a silanol group, it is in the form of a silanol group.

It reacts with the hydroxyl groups of the inorganic white pigment and the hydroxyl groups on the surface of the metal oxide that partially covers the surface, forming a chemical bond with the inorganic white pigment.

In addition, titanium coupling agents strongly react with the hydroxyl groups of the inorganic white pigment and the hydroxyl groups on the surface of the metal oxide that partially coats the surface, breaking the chemical bonds of ether bonds or ester bonds. form.

In addition to these, the silane or titanium coupling agent of the present invention has a C═C double bond, and therefore, upon curing, it forms a strong chemical bond with a compound that can be cured by electron beams.

Because it has an unsaturated double bond that hardens by radiation,
This double bond and radicals generated from the compound that can be cured by electron beams cause a radical polymerization reaction, forming a crosslinked structure and curing.

The above compounds thus bond strongly with the inorganic white pigment on the one hand and with the compound curable by electron beams on the other hand.

On the other hand, coupling agents that do not have double bonds in their molecules have reactive groups (
methoxy group, ethoxy group, silanol group),
The bond between the inorganic white pigment and the compound curable by electron beams is not necessarily sufficient.

The reason is that it does not chemically bond with the compound that can be cured by the electron beam, but only has good compatibility with it, and does not form a bond with the cured/<-ingu.

Therefore, a strong bond between the inorganic white pigment and the hardened/heingu is not formed, and these effects are low.1 As a result, 1. According to the present invention, when using a coupling agent that does not have a C=C double bond, In particular, the bleeding of the cured coating layer is significantly reduced and the scratch resistance is significantly improved compared to the above.

In addition, the inorganic white pigment can be effectively reinforced at the interface, the filling properties are further improved, and the surface smoothness is further improved.

Specific examples of the coupling agent of the present invention are listed below.

■ Silane coupling agent with unsaturated double bond in the molecule (1) CH=C'H5i(QC2H5)3(2) C
H2=CH5i(DC2H40CH3')3(3)OH
2 DaiCCH3C02CH2CH2Si(OCH3)3(
4) CH=CHC02C12CH2Si(OCH3)
3(5) CH=CCHCOCHC)l 5i(OCH
2CH3)32 3222 (6) CH=CHC02G)12CH2Si(OCR
2CH3)3(7) CH=CCHCo C)I CH
CH5t(OCH3)32 32222 (8) CH=CHCD2CH2CH2CH2Si(O
CH3)3(9)CH2=CCH3C02CH2CH2
CH2Si(OCH2CH3), I(10) CH2-
CCH3C02CH2CH2CH2CH2SiCOCH
3)3(11) CH=CHC0CHCHcHCH5i
(OCH3)32 22222 (12) CH=CHC0C)I CHCHcH3+(
OCH2c)+3)32 22222 (13) CH=CHCHNHCHcHcH5i(QC
)+3)32223 (14)CH2=CHCH2NHCH2CH2NHCH
2CH2CH2S i (OCH3)3II Titanium coupling agent having a double bond in the molecule (15) ' CH2-0-IJ2-CH=CH2(1
8) CH3 CH3-C-0-Ti-f-C0O-CH= CH2)
3(+7) cH3 (CH2-C-0-) 2 Ti(-C0O-CH=
CH2) The following methods can be used to incorporate such a coupling agent into the coating layer.

In other words, the first method is to use the above-mentioned one or a mixture of the two.
A method in which an inorganic white pigment and the above-mentioned coupling agent dissolved in a solvent are simultaneously added to a compound that can be cured by an electron beam or more, and after being dispersed and mixed, the mixture is coated on a support base material and cured. be.

In the second method, a coupling agent is dissolved in a suitable solvent, an inorganic white pigment is immersed in this solution, the surface is treated in advance, and the inorganic white pigment is dried. This is a method in which a composition liquid is prepared by dispersing and mixing the composition in a compound that can be cured by electron beams, and then it is applied onto a support base material and cured.

The third method is to dissolve one or more of the above-mentioned compounds that can be cured by electron beams in a suitable organic solvent, and then disperse and mix the inorganic white pigment that has been surface-treated with a coupling agent and dried. After that, it is applied onto a support base material and cured.

Furthermore, a fourth method involves dispersing a coupling agent with an inorganic white pigment in an organic solvent before adding a compound curable by electron beams, and then adding a compound curable by electron beams to disperse the coupling agent. In this method, after mixing to prepare a composition liquid, it is applied onto a support base material and cured.

Among these, a method using an inorganic white pigment that has been previously treated with a coupling agent and dried is preferred.

In addition, when using an organic solvent in these, 1
1 The viscosity of the composition liquid is lowered, the filling property of the inorganic white pigment is improved, and the surface smoothness of the coating layer is further improved.

The amount of these coupling agents used is preferably in the range of 0.1 to 20% by weight based on the inorganic white pigment.

If it is less than 0.1% by weight, the desired effect cannot be obtained;
If it exceeds % by weight, there is a risk of bleeding over time.

In this case, the coupling agent is more preferably 0.5 to
It is preferable to use it in a range of 10% by weight.

As the inorganic white pigment in the present invention, any of titanium oxide (anatase type, rutile type), sulfuric acid/<lium, calcium carbonate, aluminum oxide, magnesium oxide, etc. can be used, but in particular, titanium oxide, barium sulfate,
Calcium carbonate is preferred.

Further, the surface of titanium oxide may be partially coated with a metal oxide containing water, such as a metal oxide such as water-containing alumina oxide or water-containing ferrite oxide.

The inorganic white pigment is the electron beam curable compound 1
It is preferable that the amount is in the range of 20 to 200 parts by weight per 1% by weight.

If it is less than 20 parts by weight, the sharpness will not be sufficient, and if it exceeds 200 parts by weight, the adhesiveness and surface smoothness will not be sufficient.

In this case, 30 to 150 parts by weight is more preferable.

The average particle diameter of the pigment is 0.1 to 10. The composition for coating the coating layer in the present invention consists of these electron beam curable compounds, a coupling agent, and an inorganic white pigment. A solvent can be added to.

In this case, especially when an organic solvent is used, the viscosity of the coating composition becomes lower, so that the filling properties of the inorganic white pigment are further improved and the surface smoothness is further improved.

The solvent to be used is not particularly limited and is appropriately selected in consideration of the solubility, compatibility, etc. of the compound curable by the electron beam and the coupling agent to be used.

Solvents that can be suitably used in preparing the composition include methanol, ethanol, impropatol, butanol alcohol acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, butyl ethyl acetate, etc. Examples include glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol 7-ethyl ether, and dioxane; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and heptane; and mixtures thereof.

As the support base material used in the present invention, commercially available medium-quality paper,
In addition to wood-free paper, paper substrates consisting of natural pulp, synthetic pulp or mixtures thereof can be used.

Alternatively, a film may be used in which an inorganic white pigment is dispersed, if necessary, on a base of polyesters or polyolefins.

The paper base material preferably has a basis weight of 60 to 250 g/rn', more preferably 80 to 190 g/rn', and its surface may be smooth or rough.

The composition for coating in the present invention is prepared as follows.

In other words, all of the above-mentioned components at the same time.

Alternatively, they can be put into a kneading machine one after another.

Various crosstalk machines are used for crosstalk dispersion of the coating composition. Usable mixers include Ninigi roll mill, Miki roll mill, pebble mill, ball mill, sand grinder, high-speed stone mill, high-speed impact mill, and kneader.
, homogenizer, etc.

Application methods include air doctor coating, blade coating, squeeze coating, air knife coating, and reverse roll coating.

Methods such as cast coating are used.

The coating thickness is preferably 1 to 100 iLa+, more preferably 5 to 50 pLm.

If the layer is less than 1JL, the desired purpose cannot be achieved;
If it exceeds Op-, the cost will increase.

Such a coating composition is coated on the silver halide emulsion-coated side of the support substrate, and then coated.

It is cured by electron beam irradiation to form a coating layer.

In this case, the opposite side of the support base material is coated with a compound that can be cured by electron beams as described above.

If necessary, a back coat layer is provided by applying a composition comprising the above-mentioned curing speed improving compound and a thermoplastic resin, preferably containing the above-mentioned solvent, and curing it by electron beam irradiation. is preferred.

An inorganic white pigment may be added to this back coat layer, and in this case, it is preferable to include the above-mentioned coupling agent having a C═C double bond or other coupling agent.

To apply a coating composition onto a support base material, use a two-stage coater head to simultaneously coat the emulsion-coated side and the opposite side, and immediately heat and dry to remove some or all of the solvent. After removal, the coating layer may be cured by electron beam irradiation and then wound onto a roll.

Alternatively, immediately after coating, electron beam irradiation may be performed to cure the i-layer, followed by heat drying to remove the solvent in the cured layer, and then winding up onto a roll.

If you do not have a two-stage coater head, first apply the emulsion to the surface to be coated, dry and harden it in the same manner as above, then wind it up onto a base roll, unite it, and coat the opposite side.
It may be dried and cured in the same manner as above and then wound onto a roll.

When applying and winding according to each of the above methods, after the composition liquid is prepared, it is stable without being affected by changes in temperature and humidity or the concentration of the material used, and there is no aggregation or gel formation when applied. , allowing stable coating operation for long periods of time.

In addition, when the coating layer that is first applied and cured on the support material is overlapped, or when the layer that is applied and cured on the opposite side is overlapped, the coupling agent bleeds out. Since blocking due to etc. does not occur,
There is no reduction in coating operability or deterioration of the surface condition of the coating layer.

Even if the composition liquid according to the present invention contains a large amount of inorganic white pigment, it does not cause aggregation or gel formation even when applied after long-term storage, and has good application operability. No blocking occurs.

The coating layer of the present invention can be smoothed to have a mirror finish, and can also be patterned if necessary.

To achieve a mirror finish, the surface to be treated can be brought into contact with a mirror roll, and an electron beam is irradiated from the back of the roll to harden it, thereby giving the surface a mirror finish.

Alternatively, a method may be used in which preliminary irradiation is performed in advance to partially cure the surface, and then the surface is brought into contact with a mirror-finished roll, peeled off, and secondary irradiation is performed to completely cure the surface.

Examples of mirror-finished rolls include chlorine-plated rolls and stainless steel rolls.

In addition, when molding is performed, instead of mirror-finished rolls, rolls such as stainless steel rolls and chrome-plated rolls are coated with surface polishing, vapor deposition, etching, plating, etc. A roll formed with a desired pattern can be used.

For mirror finishing and molding, apply one composition solution,
The application may be performed after removing part or all of the organic solvent, or the organic solvent may be removed after molding.

The drying temperature of the coating layer is preferably about 50 to 120°C, preferably 70 to 100°C, particularly preferably 80 to 90°C.

The drying time is approximately 10 seconds to 10 minutes, preferably 20 minutes.
It is about seconds to 5 minutes.

The electron beam accelerator used may be any one of an electrocurtain system, a van de Graaf type scanning system, a double scanning system, and the like.

In addition, the electron beam characteristics are 100 to 7 in terms of penetrating power.
It is preferable to use an electron beam accelerator of 50 KV, preferably 150 to 300 KV, so that the absorption line Ji is 0.5 to 20 Mrad.

Note that N2. It is desirable to irradiate in an inert gas atmosphere such as He, 002, etc.

A lubricant, an abrasive, an antistatic agent, etc. may be added to the coating composition liquid of the present invention, if necessary.

Further, for the purpose of improving the adhesion with the photosensitive silver halide emulsion layer, surface treatment such as corona treatment may be performed, or an undercoat layer may be separately applied to the surface of the coating layer.

In addition, the layer structure of the silver rhodanide emulsion layer and the silver halide photographic light-sensitive material formed on such a coating layer is as follows.
It may be any known one.

(2) Specific effects of the invention According to the invention, the dispersibility of the inorganic white pigment is significantly improved, and the sharpness of photographic images is extremely improved.

Furthermore, the filling properties of the inorganic white pigment are greatly improved, the smoothness of the support surface is improved, and the uneven coating of the emulsion is extremely reduced.

Furthermore, the hardened coating layer has excellent flexibility and is almost free from stress cracking and stress cracking.

Furthermore, the adhesion of the coating layer is also extremely high.

The charging characteristics of the coating layer are also sufficiently small for practical use.

Furthermore, bleeding of the coating layer after storage is extremely low.

In this case, as compared to the case of using a conventional coupling agent as previously proposed by the present inventors, bleeding is extremely reduced and scratch resistance is improved.

The present inventors conducted various experiments to confirm the effects of the present invention.

An example is shown below.

Experimental example (1) Preparation of sample 1 Terminal acrylic-modified polybutadiene (average molecular weight 1000, TEA-1000 manufactured by Nippon Soda Co., Ltd.) 70 parts by weight C
)I=C:HJl:0O-(CH)-00C-CH=
220 parts by weight of CH2 26 parts by weight of trimethylolpropane triacrylate 10 parts by weight of titanium oxide (rutile type, average particle size 0.2 l+e) 50 parts by weight Car 2 pulling agent for exemplary compound (8) of the present invention 5 parts by weight of methyl ethyl ketone/toluene ( A composition liquid consisting of 30 parts by weight (1:1 mixing) was mixed and dispersed in a ball mill for 48 hours, and then coated on one side of high-quality paper with a weight of 150 g/rrf to a thickness of 30 p, va using a curtain coater. .

Next, after removing the solvent of this coating by drying (100°C for 1 minute), it was dried under a nitrogen gas atmosphere using an electron beam accelerator.
The coating was irradiated with an electron beam at an irradiation intensity of 50 KV and 5 Mrad.

The cured coating layer was once wound up, and the above composition was coated on the opposite side to the coating layer to a thickness of 30 μm, dried and cured in the same manner, and then wound up.

This sample is designated as No.1.

(2) Sample breakdown of the present invention, preparation of 2 Titanium oxide (anatase type) i average particle diameter 0°21Lm
) 100g was washed with acetone and dried,
Methanol 5 in which 3 g of the exemplary compound (2) of the present invention was dissolved
00+'L, mixed and stirred for 2 hours, and then left to stand for about 6 hours. The solvent was removed under reduced pressure, the titanium oxide was air-dried, and then heat-treated at 130° C. for 10 minutes.

Next, 60 parts by weight of the surface-treated titanium oxide CH2=CH
-Coo-(H2CH2-E-NHcO-(C:H2)
4-C0NH--C:H,,-CH2-) 800G
-'GH=CH2 acrylate oligomer
80 parts by weight of trimethylolpropane triacrylate 20 parts by weight of methyl ethyl ketone/cyclohexanone (1:1 mixture) After mixing and dispersing a composition solution consisting of 30 parts by weight in a ball mill for 36 hours, the mixture was coated on both sides of a high-quality paper with a basis weight of 180 g/rn'. Then, each layer was coated with a curtain coater to a thickness of 30 JAll.

Next, after removing the solvent of this coating layer by drying (100'C! 1 minute), using two electron beam accelerators, under a nitrogen gas atmosphere, with an irradiation dose of 1 50 KV 7 Mrad (7),
After curing by irradiating the coating layer with electron beam.

I rolled it up.

This sample is designated as positive and 2.

(3) Preparation of sample cap, 3 * Q 11 (7) Example conversion. Object, □5) (7) Cuff 7
．． 2. Place the sample in a 5% methanol solution of the agent. Using calcium carbonate that had been surface-treated in the same manner as in 2, prepare 100 parts by weight of calcium carbonate and 60 parts by weight of spiran ring-containing acrylic oligomer (Spirac U-3000 manufactured by Showa Kobunshi Co., Ltd.). Polyurethane resin (B, F, Goodrich Estane 57
02)6 20 parts by weightC)1. , -CH-C00-(CO2)8-00G-(
H=CH220 parts by weight methyl ethyl ketone/toluene
A composition liquid consisting of 50 ffit parts was milled in a ball mill for 72 hours.
After mixing and dispersing for a period of time, one side of a high-quality paper with a basis weight of 150 gorr+' was coated with a thickness of 30 gorr using a curtain coater.

Next, after drying (100°C for 1 minute) the solvent on this coating, it was heated at 150K under a nitrogen gas atmosphere using an electron beam accelerator from the other side while contacting it with a mirror roll.
After curing and mirror finishing were performed at the same time with an irradiation dose of V 5 Mrad, the film was wound up.

This composition, minus the calcium carbonate, was then coated to a thickness of 30 pm. Thereafter, drying, curing, and mirror finishing were performed according to the same operations as above, and the film was wound up.

This sample is designated as 3.

(4) Preparation of Comparative Sample, Sample 4 In Sample 3, calcium carbonate without any surface treatment was used instead of surface-treated calcium carbonate, and sample was prepared in the same manner as in Sample 3. was created.

This sample is designated as sample 4.

(5) Comparative sample breakdown, between samples prepared in 5, in 1, tetrastearyl titanate [Ti(OC18H
Except for using the same amount of 3□)4].

A sample was prepared in the same manner as in 1.

(6) Preparation of comparative sample 6.

Sample No. 1, except that γ-glycidoxyprobyltrimethoxysilane (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the coupling agent of the present invention.
A sample was prepared in the same manner.

The following measurements were performed using these samples Nos. 1 to 6.

(1) Stability of inorganic white pigment after composition liquid preparation After composition liquid preparation, the composition liquid was weighed for each sample, and the sedimentation state of the inorganic white pigment after 48 hours was evaluated according to the following three-stage criteria. evaluated.

O No precipitate at all Δ Some precipitate present

O Very good smoothness Δ Good smoothness
was applied, and the state of the coating film was evaluated on a 3-level scale, when the tape was removed instantly.

0 No abnormality Δ Partial peeling (4) Flexibility (bending test) Using a bending tester, check the film condition at one bend with a curvature radius of 2 m + s and a bending angle of 180'' with the coating layer surface on the emulsion layer side outside. , evaluated using the following 3-level criteria (repeated 5 times).

0 No abnormality Δ Partial cracking X Cracking throughout (5) Sharpness To measure sharpness (resolution), apply a color photographic emulsion to each obtained sample, and then apply a color chart for resolution measurement. was burned and visually observed and determined.

(6) Bleed when left at high temperature (A) The sample was left at 23° C. and 90% RH for one month, and the surface was observed with the naked eye under white light.

(B) The sample was left under conditions of 40° C. and 80% RH for 14 days, and the surface was observed with the naked eye under white light.

Both (A) and CB) were evaluated using the following three-level criteria.

ONo change observed〇 Partial stickiness occurs × Significant stickiness occurs (7) Scratch resistance test A static load is applied to a sapphire IT with a curve radius of 0.15 mm, and the sample is moved over the sample at a constant speed (5, Oc 2/5ee), and the amount of load at which scratches began to appear on the sample was determined.

These results are shown in Table-1.

From the results shown in Table 1, the effects of the present invention are clear.

Applicant: Konishiroku Photo Industry Co., Ltd. Agent Patent Attorney Yo Ishii -

Claims (1)

[Claims] (1) A composition containing a compound curable by electron beam, a coupling agent having a C═C unsaturated dim bond in the molecule, and an inorganic white pigment is provided on at least one surface of the support base material. 1. A silver halide photographic light-sensitive material, characterized in that it has a coating layer formed by layering and curing with an electron beam, and has at least one silver halide emulsion layer on the coating layer.