JPS61201250A - Photographic element having protective covering layer - Google Patents

Abstract

PURPOSE:To form a protective covering layer by coating a composition contg. an oligoacrylate and N-vinylpyrrolidone and by curing the composition by irradiation. CONSTITUTION:A composition contg. an oligoacrylate and N-vinylpyrrolidone is used. The oligoacrylate is a modified oligomer obtd. by reacting an oligomer having 300-10,000 number average mol.wt. with acrylic groups. The vinylpyrrolidone increases the strength and scratch resistance of a polymer film formed by the oligoacrylate. When the oligoacrylate is so viscous that it is not easily handled, the viscosity is lowered by adding N-vinylpyrrolidone. A photographic element is developed and dried, and the radiation-curable composition is coated and irradiated. The photographic element having a formed film is then cut.

Description

DETAILED DESCRIPTION OF THE INVENTION 1. Background Technical Field of the Invention The present invention relates to a photographic element having a protective coating layer. Generally, the uppermost layer of a silver halide photographic light-sensitive material has a surface condition that maintains hydrophilicity with ceratin as the main binder. They are susceptible to changes, stains, etc., which can reduce the attractiveness and longevity of the photo.

For this reason, many photographic material coatings have been developed, for example,
U.S. Patent Nos. 4,092,173 and 4,171
Radiation curable compositions containing acrylated urethanes, aliphatic ethylenically unsaturated carboxylic acids, and polyfunctional acrylates as described in US Pat. No. 4,333;
.

A composition that further contains a polycarbinol having a siloxy group in the above composition described in No. 998 can be mentioned.

Due to its hydrophobic nature, the acrylate and other layers obtained by polymerization with these radiations do not always have sufficient adhesion with the two-most layer of the silver halide photographic light-sensitive material that supports the gelatin-based image. Although it has scratch resistance, it has the disadvantage of being easily peeled off from the image-bearing layer.

Various means for solving these drawbacks have been proposed; for example, JP-A-53-57023 discloses the inclusion of unsaturated carboxylic acid in order to strengthen adhesive strength.

- In the case described above, an aliphatic ethylenically unsaturated carboxylic acid is used to improve adhesive strength, but there is a linear proportional relationship between the amount used and the improvement in adhesive strength in the composition. However, below a certain amount, there is no improvement in adhesion, and as the amount used increases, the gelatin film swells and the penetration effect increases, causing negative effects such as dissolving the internal image-forming dye and destroying the image. It's coming.

Furthermore, there are problems in terms of safety for living organisms and bad and irritating odors.

In addition, products containing polycarbinol with siloxy groups improve adhesion and prevent fingerprints from sticking.

It is not sufficiently effective in either improving the ease of wiping or reducing scratches.

In either case, when such a composition is used as a coating, the strength is insufficient and the scratch resistance is not satisfied.
Furthermore, the composition has the disadvantage that the viscosity of the composition increases during application, making application difficult.

Furthermore, as another example, U.S. Patent No. 4,426.43
A radiation-curable composition comprising a polymerizable epoxy according to No. 1, a cationic polymerization initiator for the epoxy, a polymerizable acrylic, a radical polymerization initiator that is a haloalkylated aromatic ketone, and a polymerizable organofunctional silane. , U.S. Pat. No. 4,156,046, a composition comprising a terminal epoxy silane, an aliphatic polyepoxy, a reaction product of an epoxy silane, a polymerizable monomer, and a UV absorber.

Abrasion resistant coatings containing epoxy-terminated silanes as described in U.S. Pat. No. 4,293,606, U.S. Pat. No. 4,262,0
Examples include compositions containing crosslinked polymers described in No. 72.

Even with these products, because they are cationic polymers, it is difficult to control the reaction, and the reactivity changes during storage, making it difficult to apply or not achieving the desired performance. It has many disadvantages, such as being difficult to do.

As mentioned above, various attempts have been made as protective coatings, but each has its own drawbacks and improvements have been desired.

11 Purpose of the Invention The purpose of the present invention is to provide a material with excellent adhesiveness, scratch resistance and water resistance;
A photographic element having a protective coating layer consisting of a composition that prevents adhesion to other substances and fingerprints, is easy to wipe off, resulting in increased flatness, gives a high-quality image quality, and is easy to apply. Our goal is to provide the following.

■Disclosure of invention Such objects are achieved by the invention described below.

That is, the present invention provides a photographic element having at least one image-bearing layer and a protective coating layer on a support, coated with a composition comprising an oligoacrylate and a polymerizable vinyl monomer having a group that reacts with gelatin;
This composition is then cured by irradiation to form a protective coating layer, thereby providing a photographic element having a protective coating layer.

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

Photographic elements having a protective coating layer of the present invention are coated with a composition comprising an oligoacrylate and N-vinylpyrrolidone, and the composition is then cured by radiation to form the protective coating layer.

The oligoacrylate used in the present invention means an oligomer modified by reacting an acrylic group with various oligomers having a number average molecular weight of 300 to io, ooo, and has the following general formula (
A-1), (A-11) (A2m)t3J: bi(
A-IV) According to their general formula, these compounds are also called acrylated oligoesters, acrylated urethanes, acrylated alkylene oxide oligomers, and acrylated epoxy oligomers, respectively.

The radiation-curable fabric composition of the present invention has the general formula (ζlower♀) (
A-I), (A-11), (A-llI) and (A
-IV) At least ll! using oligoacrylate.

General formula % formula %) In the above general formulas (A-I) to (A -mV), A represents an acrylic group (CH2=cnccy-), E represents an n-valent oligomer containing an ester bond, and U represents urethane. P is an n-valent oligomer containing a bond, P is an n-valent oligomer containing an alkylene oxide group (e.g., ethylene, nitrogen oxide group, -propylene oxide group, etc.), and G
represent oligomers derived from compounds that give an epoxy group and have a valency of n, respectively.

Also, teeth Represents an integer greater than or equal to 1, especially It is preferable that it is 1-6.

The general formulas (A-I) to (A ■) in Specific examples of the compounds represented are shown★.

Kuniichi Engineering II Engineering II Total yen per day 1 Y Kuku1, :1:(0 Oligoacrylate is the main compound in the composition of the protective coating layer, and is photopolymerized by radiation irradiation to form a polymer film. It is something.

The oligoacrylate is 5 to 90 wt% in the case of acrylated oligoester, more preferably 8 to 70 wt%, and more preferably 3 to 90 wt% in the case of acrylated urethane, when the finished amount of the composition of the protective coating layer is 100 wt%. Preferably 5 to 60 wt%, 1-5-0 wt% for acrylated alkylene oxide oligomers, more preferably 3 to 30 wt%, 5 to 90 wt% for acrylated epoxy oligomers, more preferably 8 to 70 wt%. It is better to let

In addition, when using these items together, the total amount is 1 to 9.
5 wt%, more preferably 5 to 90 wt%.

N-vinylpyrrolidone is added to increase the strength and scratch resistance of the polymer film formed by oligoacrylates, and is also added when the oligoacrylates are too viscous to handle. - There is also a ``* knee v'' erute meruki.

1,, t: 4 and 1 N~bi=rupiroridoi, r taku, -q, island,, love p moon kan,
If the completed amount of vp-p composition is 100wt%, 1~
60 wt%, more preferably 5 to 40 wt%, +
! - Bow ij is better.

, Do? -; when forming the protective coating layer of the present invention! The I component includes a polymerizable compound having a group that reacts with gelatin, vinyl lumi--H
1) It is preferable to include a polymerizable vinyl monomer.

i-te-70,, knee 1 ・'-each-1 the following general formula (
B-I) and (n-u)
Preferably, ◆・(ζ) is used.

<l-1□,> General formula (2-[x R3
To=Zen
1, R2 and R3 are each a hydrogen atom, a halogen atom (e.g. F, C, Br, stirrup 1, etc.), or a substituted or arithmetic substituted lower (carbon number 1 to
4) Alkyl group (e.g. methyl group, =1-1・-j-
4) Represents an ethyl group, propyl group, butyl group, etc.), B, B
l and B2 are each substituted or unsubstituted linking group (
(described later), and B1. . and B2 may be the same or male, and x and Y each represent zeichireiwari °shiu-1 group'nmoni-)', and X and pa Y may be the same or different. Also, p is an integer from 1 to 3, and q
each represents an integer of 1 to 4, '', 1: Examples of the linking groups represented by B, B, and B2 include the following.

-R-;” -COO-R-NH- “S*g4-n- CONRs CONHCO ONR4 R-Co.

(Here, R4 represents a hydrogen atom or an alkyl group,
A hydrogen atom is preferred. Further, R represents an alkylene group. ) Examples of the groups represented by X and Y that can react with gelatin include the following.

CH=CH2 OD 0302 CH3 λX/ -(XN -CH-CH2D coo-ma0 -S02M (where, D is a halogen atom such as F, (11, Br, ■), E is S02 or CO, and M is an alkali metal ion (Na”
, K''), hydrogen ions (H+), ammonium ions (NH4''), and other cations. ) Specific examples of the compounds represented by the general formulas (B-I) and (B-II) are shown below.

(B CH2=CHCONHCH2CH2NHCH20H (B (B C look) (B CH2=CHCONHCH2CH2NHCH20H(B
H2 CH2=CHCONHCONHCOCH=C82(B (B H0H2CHNOCCH2=CH2CONHCH20H
(B CH2=CH Bi”c02502 CH=CH2 (B-ll) CH2=CH (B CH2 CH ^ (B CH2=CH =C=O) 02 CH2CH=CH2 CH2=CH CH=CH2 These polymerizable vinyl The additive is intended to improve the adhesion between the oligoacrylate polymer coating and the top layer of the predominantly gelatin image-bearing layer of the photosensitive element.

The amount of the polymerizable vinyl monomer added is preferably 1 to 50 wt%, more preferably 5 to 30 wt%, based on 100 wt% of the finished composition of the protective coating layer.

Preferably, the composition of the protective coating layer of the present invention includes one or more gelatin swelling solvents.

Such a solvent may be any solvent that swells gelatin, and specifically includes water, saturated aliphatic alcohols which may be substituted (for example, methanol, ethanol, isopropanol, ethylene glycol, glycerin, etc.), Unsaturated aliphatic alcohols (e.g. ali.

(alcohol, etc.), aromatic fucol (tlAc example yr).

1<beinlua, no1<co, nil, etc.)-, saturated fatty acids (e.g., formic acid, acetic acid, trichloroacetic acid, etc.), unsaturated fatty acids (e.g., acrylic acid, etc.), aromatic carboxylic acids (e.g., benzene, etc.) Acid tank), Ke? (e.g. Melke;
ton etc.-5, eagle-y-¥, 1. (vines (formaldehyde etc. if soaked), amides and amines (for example N,
N-dimethylformamide, etc.) -, y.

Sulfoxy group (e.g. di-3-tyl: female phoxite, etc.)
, Engineering? Examples include Shiro-(45, Eshi, 8' I-To-hee, Do2-Ya → Ran, Dioxane, etc.).

Among these, water, saturated aliphatic alkonyls, .-Japanese fatty acids, .
>-nie---''-1mins, 8, jho, 71:yJLr''111 are preferred, and water is particularly preferred.

The gelatin swelling solvent is oligoacrylate-f, l.
, -1\'s 6 towns ~ - Peiichi and - Kosen Kaname -' - *hat -, -< 7. -y-; -e, :II
, Ti is included in order to protect the surface and improve the adhesion between the layer and the layer 1.

The amount of the solvent is maintained;
Parrot i#-:4 0;O wt%:-0,z
,, ---t H- 3 0 HwK% = (1 j preferred) or -i '';

The composition of the protective coating layer of the present invention includes polyfunctional acrylic acid, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chloride, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, chlorine, etc.; 7
．． I,, (7J, 4., species. It is preferable to include the above, or 7. see.

A polyfunctional acrylate is an acrylic monomer having at least two acrylic ester groups, and the polyfunctional acrylate preferably used in the present invention is represented by the following formula.

R. OR5 Riso 1 In the formula, each R5 is a hydrogen atom and a carbon atom number of 1
-2 alkyl groups, and each R6 is independently selected from an alkyl group having 1 to 6 carbon atoms and a radical represented by the following formula.

In the above formula, R7 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.

Specific compounds are illustrated below.

Neopentyl glycol diacrylate Pentaerythritol triacrylate 1,6-hexanediol diacrylate Trimethypropane triacrylate I tetraethylene glycol diacrylate 1
．． 3-Butylene glycol diacrylate trimethylolpropane trimethacrylate 1. 3-butylene glycol diacrylate trimethylolpropane trimethacrylate 1. 3-butylene glycol dimethacrylide ethylene glycol dimethacrylate pentaerythritol tetraacrylate 1. 6-Hexanediol・Ethylene glycol dimethacrylate・Diethylene glycol diacrylate・Glycerol diacrylate・
Diacrylate glycerol ● Triacrylate 1.3-Propanediol diacrylate 1.3-Propanediol dimethacrylate 1.2.4-Butanetriol trimethacrylate 14-Cyclohexanediol diacrylate Pentaerythritol diacrylate 1.5 -Pentanediol dimethacrylate polyfunctional acrylate is
In addition to increasing the strength of the polymer film and improving its scratch resistance, it also increases the rate of photopolymerization.

The amount of the polyfunctional acrylate added is preferably 5 to 95 wt%, more preferably 10 to 90 wt%, based on 100 wt% of the finished composition of the protective coating layer.

The composition of the protective coating layer of the present invention preferably contains one or more silicone compounds.

As a silicone compound, U.S. Patent No. 3゜042.5
No. 22, No. 3,080,317, No. 3,489,
Dimethyl silicone described in Japanese Patent Publication No. 53292 and liquid organopolysiloxane described in Japanese Patent Publication No. 53292 can be preferably used.

preferred < Examples of compounds used are shown below. vinegar.

i,, 7", 10g"l2・彊:: CH3-i -CH3 H3211 H3 H3 Hibiki H3 H3 ■ H3 H3 ■ H3 H3 Kure H3 ■ After the polymer film is formed, the silicone compound is It prevents the polymer coating surface from adhering to other substances and improves the lubricity and scratch resistance of the polymer coating surface.

The amount of the silicone compound added is preferably 0.1001 to 2 t%, more preferably 0.003 to 0.5 wt%, based on 100 wt% of the finished composition of the protective coating layer.

The composition of the protective coating layer of the present invention preferably contains one or more fluorinated photopolymerizable vinyl monomers.

The fluorine-containing photopolymerizable vinyl monomer has the following general formula (
Those represented by C-I) and (C-II) are used.

General formula % Formula %) In the above general formulas (C-I) and (C-It), R
+, "R2R3,B, B1.B2, p and q are the general formulas (B-I) and (B
-II) are used synonymously with each other. Further, xF and R each represent an alkyl group, alkenyl group, aryl group or aralkyl group partially substituted with a fluorine atom, and X and RF may be the same or different.

Specific examples of preferably used compounds are shown below.

B2 (C Ca F, 7so2 milk: l:, c)1. ．． ooccm=
cH2(C-2) C6F17CH2CH200CCH=CH2(C-3) H+CF2u CH200CCH=CH2010, F2
ICH2CH200CCH=CH2(C 3H7 ca F, 7302 N+CH2CH20u-OCCH
=CH2(C (C CH3 (C-9) H-C-CF2←CONH-0-CH=CH2 The fluorine-containing photopolymerizable vinyl monomer improves the water repellency of the surface of the polymer film and allows other substances to This prevents them from adhering.

The addition amount of the fluorinated photopolymerizable vinyl monomer is 0.01 to 0.01 when the finished acid of the composition of the protective coating layer is 100 wt%.
The content is preferably 0.1-10 wt%, more preferably 0.1-10 wt%.

The composition of the protective coating layer of the present invention preferably contains one or more photopolymerization initiators.

Any known photopolymerization initiators can be used in the present invention, but those with little coloring are preferred.

For example, benzophenone or an aromatic ketone compound derived from benzophenone such as alkylbenzophenone as described in JP-A-5691233; or l-hydroxycyclohexylferketone;
2-Hydroxy-2-methyl-1-phenylpropane-
l-one, 1-(4-4sopropylphenyl)-2-hydroxy-2methylpropan-1-one, and the like.

The photopolymerization initiator promotes the photopolymerization reaction when the oligoacrylate forms a polymer film.

The amount of the photopolymerization initiator added is preferably 1 to 20 wt%, more preferably 2 to 10 wt%, assuming that the finished amount of the composition of the protective coating layer is 100 wt%.

The protective coating layer consisting of the polymer film of the present invention is preferably provided on the top layer on the image-bearing layer side of the support, but may be provided on the top layer (back layer) on the opposite side of the support. .

Supports, photosensitive silver halide emulsions, antifoggants, stabilizers, chemical sensitizers, spectral sensitizing dyes, color couplers, DIR compounds used in image-bearing layers, etc. in photographic elements having protective coating layers of the present invention. , surfactant, binder,
There are no particular restrictions on the curing agent, polymer latex, antifading agent, dye, matting agent, plasticizer, and the manufacturing method, exposure, and development processing method of the photosensitive element.
Day Closure, Vol. 176, pp. 22-31 (1978
(December 2013) can be referred to.

A photographic element having a protective coating layer of the present invention may be treated to form a visible image prior to coating the image-bearing side thereof with a radiation curable composition; such treatment may be carried out by any suitable method. You may go. For example, black-and-white photographic elements typically involve a sequence of development, fixing, and washing, while color prints typically include color development, bleaching, and fixing (
or a sequence of steps consisting of bleach-fix bonding and stabilization, and for color reversal photographic elements, black-and-white development, reversal exposure or chemical fog, color development, bleaching, fixing (or bleach-fix bonding) and stabilization. Each is processed through a series of steps. A preferred method for carrying out the invention is to dry the photographic element in a conventional photographic processing operation followed by coating and curing as a final step to form a protective coating layer.
This coating and curing can be carried out in a batch, semi-continuous or continuous manner.

The radiation curable composition may be applied to the photographic element according to conventional methods. For example, dip coating, air knife coating, roll coating, gravure coating, extrusion coating, bead coating,
Curtain coating and wired coating rod usage can be used. Also, air knife,
The thickness can be made constant and uniform by using a doctor blade or the like made of a suitable material.

Typically, the amount applied on the photographic element is sufficient to form a very thin coating, with a surface m2 of wet coating.
Approximately 2 to 20 cm3. More typically about 3 per m2
~about 10cm3. The viscosity of the applied composition, which is preferably about 5 cm3 per m2, can vary within a wide range depending on the application method employed. Generally, about 25 to about 1000 centivoids, more preferably about 75 to about 20
Satisfactory coatings can be formed on photographic elements by using coating compositions with a viscosity of 0 centipoise.

Equipment and methods used to cure radiation curable compositions by exposing them to suitable radiation are well known, and any suitable radiation curing process may be used in the practice of the present invention, e.g. , and can be cured by UV irradiation with appropriate intensity. High energy ionizing radiation such as X-rays, gamma rays, beta rays and accelerated electrons may also be used; generally the radiation should be of sufficient intensity to penetrate substantially the entire thickness of the coating layer; The total dose must be sufficient to cure the radiation curable composition to form a solid plastic.

Typically, the dose is about 0.2 to about 5.0 megarads.

In particular, from about 0.5 to about 20 megarads, the coating compositions used in this invention convert substantially completely to a solid product.

Preferably, the photographic element kit is formed before the photographic element is cut to final size. Thus, after the photographic element has been processed and dried, it is coated with a radiation curable composition, irradiated, and cut. If it becomes.

It is sufficient that the radiation curable composition is applied only to the image-containing layer mating side of the photographic element or only to the support side; in other cases, it is preferred that the radiation curable composition be applied to both sides of the photographic element. For double-sided coating, depending on the coating method, either a method in which both surfaces are coated simultaneously or a method in which one side is sequentially coated can be adopted.

Radiation curable! II compositions adhere strongly to both the image-bearing side and the support side of the photographic element.

Adheres to materials that are normally difficult to adhere to, such as cellulose triacetate and polyethylene terephthalate, commonly used as supports in photographic elements, and gelatin/silver halide emulsion layers or gelatin protective layers, commonly used on the image-bearing side of photographic elements. It is effective for radiation-curing the composition to form a transparent, flexible and scratch-resistant 1L crosslinked polymer layer, even in color photographic elements where the image is a dye image. There will be no adverse effect on the

(2) Specific effects of the invention According to the invention, a composition containing oligoacrylate and N-vinylpyrrolidone is coated, and then this composition is cured by radiation irradiation to form a protective coating layer.

The result is a photographic element with a protective coating layer that has excellent adhesion, scratch resistance and water resistance, prevents adhesion to other materials and fingerprints, and is easy to remove, resulting in an increased flatness and a high-grade This makes it possible to provide a pleasing image quality.

Further, when forming the protective coating layer, since the above-mentioned composition is used, the viscosity is reduced and coating becomes easy.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown, and the effects of the present invention will be explained in further detail.

Example 1 A color paper photographic material having a silver halide emulsion layer and a gelatin layer on a paper support laminated on both sides with polyethylene was exposed and developed in a conventional manner, and dried to produce a processed paper having a single color image. got color paper,
The silver halide emulsion layer side of this light-sensitive material was coated with a radiation-curable coating composition having the composition shown in Table 1 to a film thickness of 30 mm, and then 80 W/c coatings were placed at intervals of 20 cm. A color paper photographic material coated with a cured film was prepared by irradiating it with a high-pressure mercury lamp for about 20 seconds.

Samples 101-104 of the photosensitive materials produced in this way
(Table 1).

Also. As a comparative sample, a treated color paper not coated with a radiation-curable coating composition was used.

This is sample 1 (comparison) and Ru.

taste 0c1) -+!　　　　　　　　− 1:=Kaku IJCQ ;l-, hi-pa and 11:7 112, ・-i;j, 7 taste taste size of of ,,C 0J G1 1 < χN K size ” ζ ko 1.

1 eye 1 114I n<tumor~^ 1 taste cloud day sun 1 toku, Bv mouth 18c11I Σ ■ ni agonyhesaku 11'' mouth shouting dimension) λ -%%-mu8 mo5- Δ The following tests were conducted on the cured films of Samples 101-105 of sJ+1 ll and -L.

<T) flit scratch test A sample was pasted on a horizontal plate that was driven by a motor and moved linearly in the horizontal direction over a length of 10 cm at a constant speed, with the cured film facing upward. The radius of the needle tip is 0-05m on this cured film.
A sapphire needle with a fixed horizontal direction of m was applied vertically. The design is such that when the horizontal plate is moved, a load that linearly and continuously increases from 0g to 200g is applied to this needle while moving 10cm.

The distance traveled by the sample until a scratch appeared on the surface of the cured film was measured, and the load applied to the needle when the scratch occurred was determined, and this was used as a measure of the scratch strength of the sample. The larger the load, the better the scratch resistance of the sample.

(Water-based ink sampling test: One drop of black water-based ink was dropped on the cured film of a sample that had been developed without exposure. After 3 minutes, it was removed with a damp cloth. v) was measured using a self-recording densitometer.

(■Adhesion test) Make 25 squares by making 6 cuts (■) at intervals of 5 mm horizontally on the cured film of the photosensitive material coated with the cured coating composition. Adhesive tape (Sumitomo 3M, Scotch Mending Tape) was applied to the film and quickly peeled off in a 180° direction, whereby the adhesion of the cured film to the gelatin layer was evaluated by the number of squares that peeled off. The smaller the number of peeled squares, the stronger the adhesive force.

The results are shown in Table 2.

adultery stm In a gourd Tomoaki general IAj book Like Harvest Sakaki Weir・− Scarcity 0.

A141 ,J=,・,8) ☆　 That S Tsukuda Hyozuka.

ts s㇉1item 亦 纺 類 連 8 bul ze 昶田 ：tl?侃11 Hatake λ Gourd mo de 1h Reki Momme C Soe 111 So L1 v WII! 1,0 1S #Hyopo-Ki 11 table + 1 moan! IS gourd P is j measured gourd-,,8,{,1- j-,-? +ζ1\ is considered with respect to the results in Table 2. It is clear that Samples 101-104 are superior in both # polarization and water-based ink sampling tests compared to Test Sample 4105 (uncoated photosensitive material). Compared to samples 103 and 104, samples lot and 102 (in the IIIJ scratch test) showed an increased load at the time of scratch occurrence, indicating that the scratch resistance was greatly improved by using N-vinyl 2-pyrrolidone. It is clear that

Applicant Fuji Photo Film Co., Ltd. Agent Patent Attorney Nozomu Watanabe Minoru Patent Attorney Yo Ishii Proceedings WITE (spontaneous) July 17, 1985 [1 1985 Patent Application No. 42396 2, Protection of the name of the invention Relationship with the Case of Person Correcting Photographic Elements Having a Covering Layer Patent Applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. 4, Agent Address 101 Telephone 864-4498 Tokyo 3-2-2 Iwamoto-cho, Chiyo 11-ku, Column 6 of [Detailed description of the invention] of the specification (11BlIMii) $6, line 13, line F# - line 15 @
cF) [vinyl monomer that reacts with gelatin]
is corrected to [N-vinylpyrrolidone].

(2) Replace pages 11, 12, and 13 of the specification as shown in the attached sheet.

(3) Structural formula on page 19, line 5 and correct it.

(4) Structural formula on page 22 (8-8) %formula% and correct it.

(5) Delete [1,3-butylene gelicol diacrylate] on page 27, line 6.

(6) [Trimethylolpropane, page 27, line 7]
Remove "Trimethacrylate".

(7) On page 28, lines 1 and 2, after [1゜4-cyclohexanediol diacrylate], add a line break and start the line the same as the other compound examples, and add ``1,4-cyclohexanediol''.・Insert "dimethacrylate".

(8) “Sampling” on page 41, line 11 of the same page means “wiping off”
and correct it.

(9) "Sampling test" on page 45, line 17 is corrected to "wiping test."

(10) Correct the word "extract" at the beginning of page 45, line 20 to "wipe off".

υ Engineering ■ Automatic procedure correction writing 1986 9th day

Claims (1)

[Claims] In a photographic element having at least one image-bearing layer and a protective coating layer on a support, a composition comprising an oligoacrylate and N-vinylpyrrolidone is coated and the composition is then cured by radiation to form the protective coating layer. A photographic element having a protective coating layer formed thereon.