JPS62109046A - Photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material having an excellent coating layer cured by electron rays by incorporating respectively at least one kind of a compd. curable by electron rays which contains polybutadiene chain in the molecular chain and specific compd. curable by electron rays into a compsn. curable by electron rays. CONSTITUTION:The compsn. curable by electron rays is coated on at least one face of a backing base material of a silver halide photographic sensitive material and the electron rays are irradiated thereto to cure the compsn., by which the cured coating layer is formed. The compsn. curable by electron rays preferably contains at least one kind respectively of the compd. (a) curable by electron rays which contains the polybutadiene chain in the molecular chain and the compd. (b) curable by electron rays expressed by the formula. A compd. (c) curable by electron rays which can react with the compds. (a) and (b) is preferably incorporated into the compsn. curable by electron rays. Any compds. which are the compds. curable by electron rays and can react with the compds. (a), (b) are usable as the compd. (c). The compd. (a) is preferably incorporated into the compsn. at 5-65wt% of the total weight of the components curable by electron rays. The compd. (d) is incorporated therein at >=15wt% of the total weight of the components curable by electron rays and further the compd. (c) is preferably incorporated therein at >=5wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photographic light-sensitive material, and more particularly to a photographic light-sensitive material in which a cured coating layer is formed by electron beam irradiation. This type of material is used, for example, as a light-sensitive material for photographic paper.

[Conventional technology and its problems]

Conventionally, this kind of material, for example, a photosensitive material for photographic paper whose support base material is paper, has been made by coating the surface of the paper base material with a polyolefin resin, which is useful for speeding up photographic processing, etc. It has been frequently used in recent years to accommodate.

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

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. A large amount of the above-mentioned inorganic white pigment cannot be added to such a high-temperature molten polyolefin resin.
Moreover, under such conditions, the dispersibility is also poor. For this reason, the sharpness of photographic images could not be sufficiently improved.

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

For example, JP-A-51-6531, JP-A No. 52-35625
No. 55-108658, No. 55-113039, No. 55-113040, etc. disclose techniques for coating the surfaces of titanium oxide particles with various compounds.

However, with these techniques, when polyolefin resin is melted at high temperatures, contamination from these additives occurs at the tie exit end of the extruder, and concave lines are formed on the surface of the molten film, which causes damage to the support. There is a problem in that surface grooves form and uneven coating of the emulsion occurs. Furthermore, in JP-A-57-151942, it is proposed to use an alkyl titanate instead of the above-mentioned additive (functioning as a type of dispersant); The problem will be remedied.

However, in this case, the alkyl titanate-treated pigment enters only about 10 to 20 wt% in the molten polyolefin resin, resulting in insufficient sharpness, and the free alkyl titanate that is not bonded to the pigment This tends to occur, causing problems such as thermal decomposition during melting, emitting smoke in the coating, and adhesion to the cooling roll, making it impossible to obtain a smooth film surface.

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

In order to solve the above problems, Japanese Patent Application Laid-Open No. 57-27257,
No. 57-49946 proposes a photographic support having a coating layer formed by coating a paper base material with a composition that can be cured by electron beam irradiation and curing the composition by irradiating it with electron beams. .

``Using such a support, the content of inorganic white pigment can be increased to 20-70 wt%, so that the sharpness is significantly improved compared to polyolefin resin coating.

However, the above technology still has the following problems. In other words, it has been found that photographic materials using a support having a coating layer cured by electron beams have a fog which increases to an extent that cannot be ignored as a product as the product is stored over time, and also easily break as a product, significantly reducing its commercial value. Furthermore, it was found that yellowing appeared on the image surface when the image was subjected to a development process.

As an improvement method for these, JP-A-59-124336 proposes a technique for providing a barrier layer between the paper of the support and a single layer of electron beam curable lacquer, but it is still not effective in suppressing fogging. This is not sufficient and requires a process to provide an additional barrier layer in the conventional product process, which is disadvantageous in terms of cost.

Furthermore, for the purpose of improving flexibility, especially against bending,
Although it has been proposed to mix monomers or polymers with flexibility, the effect is not always sufficient.

Moreover, there is a problem in that improving flexibility increases fogging, especially fogging over time.

Further, there is also the problem that yellowing tends to occur after the treatment process (this results in a decrease in commercial value).

As a technology to improve these, the applicant previously filed a patent application in 1983.
-251263, Japanese Patent Application No. 60-2656, Japanese Patent Application No. 1983
No. 0-112657 proposed the use of specific polymers and monomers, but it is desired to further improve the effect of suppressing fog. That is, in order to put into practical use a support having an electron beam-cured coating layer, it is desired to obtain a photosensitive material that can better solve the problems of fog and yellowing that are difficult to achieve at the same time as flexibility. ing.

[Purpose of the invention]

The purpose of the present invention is to impart excellent flexibility to the coating layer formed on the support, to significantly reduce the occurrence of peeling (particularly fogging over time), and to prevent yellowing after the treatment process. The object of the present invention is to provide a photographic material having an excellent electron beam-cured coating layer, which has excellent photographic performance.

[Structure and operation of the invention]

As a result of intensive research, the present inventors have found that at least one side of the support base material of a silver halide photographic light-sensitive material is coated with an electron beam curable composition, and the composition is cured by irradiation with an electron beam. The above object has been achieved by forming a layer and containing at least one of each of the following compounds (al and (b)) in the electron beam curable composition.

(An electron beam curable compound containing a polybutadiene chain in the a1 molecular chain.

(b) An electron beam curable compound represented by the following general formula.

AXY-X-A C In the formula, is a group having an ethylenically unsaturated group at the end.] The electron beam curable composition is composed of the above electron beam curable compound, an inorganic white pigment, and other additives as necessary.

When carrying out the present invention, the electron beam curable composition may further include (
c) It is preferable that an electron beam curable compound capable of reacting with the above-mentioned (al(bl) compound is contained).

Preferred structural formulas of compounds used as the compound (a) of the present invention are as follows, for example: (1) (P) - (W) n (2) CP) - (V) n (3) (P')-(,V) nIn the formula, (P) is a polybutadiene chain or a less than 70% hydrogenated polybutadiene chain, (P') is a hydrogenated polybutadiene chain of 70% or more, and (W) is an electron beam promoted A non-reactive group, (V) is an electron beam curable functional group, and n is an integer of 1 or more. Any compound that falls under this category can be preferably used. Furthermore, it is preferable that the average molecular weight of (P) and (P') is within the range of 300 to 4000. Further, preferable electron beam curable functional groups are vinyl groups and epoxy groups.

There are isocyanate groups, etc. W bonded to the polybutadiene chain of (P) includes a hydroxyl group, an alkyl group, a carboxyl group, a -COOR group (R: alkyl group), and the like. Also(
The polybutadiene chain of P) may have an added structure, for example, maleic acid is added to (P).

Next, specific examples of compounds that can be preferably used as the compound (al) of the present invention are shown. However, the compound (al) is not limited to these.

(a) Compound example: *-GHzGHz÷polybutadiene → CH, CH2-*
*-CH2CH2QCHC=CHz 110 C112CH□-CIl-C1+□÷Polybutadiene → *CI( lh *-CH2CHCHt CHz Ot+CHt CH C11□ *-C1r-elf□-CL 01(CH CH2 HOO CCHC112(-polybutadiene+CH2CH
C0OHThese compounds are for example Nl5SOPB TE
It is also available as a commercial product such as series TEA-1000, TE-2000 (Nippon Soda) Polybd series R45ACR (Idemitsu Petrochemical).

X in the general formula of the compound (b) of the present invention is, for example, a kylene group] II II +C-R-C± [R is a linear alkylene group having 8 or more carbon atoms] -(-RO-h (R is [R is an alkylene group having 2 to 4 carbon atoms, n is an integer of 1 or more, R' is an integer of 1 or more] -(-RO+-1co-R'-CO- Straight chain alkylene group having 1 or more carbon atoms] +RC-0+r (R is a straight chain alkylene group having 5 or more carbon atoms, n is an integer from 1 to 10), and the like.

Y is Oll )l
'O)lOHR011 (wherein, R is H or CH3).

Further, as A, for example, (-QROCCII = C11□) (R is a linear fullkylene group having 1 or more carbon atoms) 1,000CCII = C11□) (k is an integer from 1 to 20) -0-CHzCH-(CH2) kOccH= Cllt
OH (k is an integer of 1 or more), and the like.

Next, specific examples of compounds that can be preferably used as the compound (b) of the present invention are shown.

However, compound (b) is not limited to this.

(b) Compound example: *-CHzCHz QCCH= CI+2゜□to--
------4 (For compound example (10), it is clearly stated to which part the above X, Y, and A correspond.) HII *-QCC1l = CHz *-QCCII=CHz C11゜* -C1l=CHz *-(CHiCHzO)b 0CCH=CI12C1
1! *-CO-C1l zcHzOc -C)l = CI
l□*-CCII = C112 H *-(CHz)n Co CHzCHzOCCH=
CHz*-(COC5H100→]ccH=cIhHH H2 *-(C11□) *C0CHzcHcHt 0
CCII = C1l zl OH *-CHzCHz 0CCII = C)lzCHs
OH 1 (II *-QC-CIl = CI+□ *-QC-Cll = CH2 *-oc-cn=cuz The compound (b) of the present invention has a terminal hydroxyl group of bisphenol A, bisphenol F, or a hydrogenated type thereof. or a diisocyanate compound (D) to the terminal epoxy group of terminal epoxidized bisphenol A or bisphenol F;
A diisocyanate compound, a dicarboxylic acid-containing compound, a diol compound ( H), and then add an appropriate compound to the isocyanate, carboxylic acid, or hydroxyl residue of the intermediate reactant by selecting an appropriate compound from hydroxyalkyl acrylate (I), alkylglycidyl acrylate (J), acrylic acid, or isocyanate alkyl acrylate (K). Manufactured by

Specific diisocyanate compounds (D) include pentane diisocyanate, hexane diisocyanate, heptane diisocyanate, octane diisocyanate,
Examples include nonane diisocyanate and decane diisocyanate.

Examples of the dicarboxylic acid-containing compound (E) include malonic acid, succinic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, and sebacic acid.

Examples of the alkylene oxide (F) include ethylene oxide and propylene oxide.

Examples of the lactone (G) include T-butyrolactone, δ-valerolactone, and ε-caprolactone.

As the diol compound (H), ethylene glycol,
Examples include 1.2-propylene glycol, diethylene glycol, dipropylene glycol, 1.3-propylene glycol, 1,3-butylene glycol, neopentyl glycol, 4-butanediol, 1,6-hexanediol, etc. It will be done.

As hydroxyalkyl acrylate (1), 2
-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, 2-hydroxy-3-methoxypropyl (meth)acrylate, and the like.

Examples of the alkyl glycidyl acrylate (J) include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and the like.

As isocyanate alkyl acrylate (K),
Examples include isocyanate ethylene (meth)acrylate and isocyanate butylene (meth)acrylate.

When producing the compound (b) of the present invention, it is preferable to add a solvent, a catalyst, a polymerization inhibitor, etc.

Examples of the solvent used in the reaction between a hydroxyl group and an isocyanate group include organic solvents inert to the isocyanate group, such as acetone, methyl ethyl ketone, ethyl dioxanoate, butyl acetate, toluene, and dimethylformamide. Further, polymerizable monomers containing carbon-carbon double bonds that are inert to isocyanate M, such as trimethylolpropane triacrylate, ethylene glycol di(meth)acrylate, and styrene, can also be used as the solvent.

Examples of the catalyst include common urethanization catalysts, such as tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, stannath octoate, and dibutyltin diacetate, and tertiary amine catalysts such as triethylenediamine and N-ethylmorpholine.

Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-quinone, diethylhydroxylamine, and organic phosphine.

Further, in the case of the reaction between a hydroxyl group or an epoxy group, a carboxyl group, or an alkylene oxide lactone, examples of the solvent used include carbon-hydrogen solvents such as benzene, toluene, xylene, and cyclohexane.

As the catalyst, a conventional esterification catalyst or etherification catalyst is appropriately used. These include, for example, sulfuric acid, hydrochloric acid, phosphoric acid,
Examples include para-toluenesulfonic acid, benzenesulfonic acid, and boron fluoride.

Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, phenothiazine, copper salt, methylene blue, and benzoquinone.

Next, in addition to the compounds (a) and (b) of the present invention, (
Specific examples of the compound (c) that can react with the compound a) and (b) are shown below. However, it is of course not limited to this.

(c) Example of compound: Any electron beam curable compound that can react with the above compounds (a) and (b) can be used. Unsaturated polyesters having groups, modified unsaturated polyesters, acrylic polymers, and monomers having unsaturated bonds (seven polymers) can be used.

Particularly preferred among these monomers are acrylate and methacrylate monomers.

Representative examples of the compound (c) are illustrated below.

A) Polyester acrylate, polyester methacrylate Toagosei Chemical Industry Co., Ltd., trade name Aronix M61
00. Alonisox M6200. Aronisox M625
0. Aronix M6300.70 Nisox M6500
．． 70 Nix M7100° 70 Nix M, 8100 San Nopco Co., Ltd., product name Photomer 5007° Photomer 5018. Photomer 4149 Nippon Kayaku Co., Ltd.
, Product name Kayamar MAND (I) Kayarad HX22
0. Kayarad HX (b) Polyurethane acrylate, polyurethane methacrylate Osaka Organic Chemical Co., Ltd., product name Bismart 823 Toagosei Chemical Industry Co., Ltd., product name Aronix M1200. Alonisox MI100 Japan U-Pica Co., Ltd., product name AC
5801 Shin Nakamura Chemical Co., Ltd., product name NK Ester U-
108A, NK Ester U4HA Toshi Thiokol Co., Ltd., trade name Evisan 893 San Nopco Co., Ltd., trade name Photomer 5007° Photomer 60
08 (c) Epoxy acrylate, epoxy methacrylate Osaka Organic Chemical Co., Ltd., trade name Viscotro 00 Sannopco Co., Ltd., trade name Photomer 3016° Photomer 3
082 Nippon U-Pica Co., Ltd., product name AC3301, AC370
1, AC3702, EX9004. EX(ii) Silicone acrylate Compounds disclosed in Japanese Patent Publication No. 48-22172 and Japanese Patent Application Publication No. 48-59594 (e) Monofunctional upper methyl acrylate, ethyl acrylate, butyl acrylate-1., 2-ethylhexyl methacrylate, 2
-Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, n
-Hexyl acrylate, lauryl acrylate, etc.

Commercially available products include the product name Pbo.
tomer 4039 (Diamond Sham
Rock Inc.), etc.

(f) Bifunctional seven-mer 1,6-hexanediol diacrylate, ■, 6-hexanethiol dimethacrylate, neopentyl glycol, 1,4-butanediol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, penta Erythritol diacrylate, divinylbenzene, etc.

(g) Trimethylolpropane triacrylate, trimethylolpropane triacrylate, benquerythritol triacrylate, dipentaerythritol hexaacrylate, ethylenediamine acrylic acid amide, and the like.

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) Vinyl chloride copolymers: vinyl chloride-vinyl acetate copolymers, vinyl chloride-acetic acid and nyl-maleic acid copolymers, etc.

(4) Polyurethane resin (5) Unsaturated, saturated polyester resin (6) Polyamide resin The compound (a) of the present invention is preferably contained in an amount of 5 to 65% by weight in the total electron beam curing component, particularly 10 to 60% by weight. % is preferred. If it is less than 5% by weight, sufficient flexibility may not be obtained, and if it exceeds 65% by weight, a large amount of energy is required to cure and form a coating layer, which is disadvantageous in practice, and high fogging is desirable. There may be no.

Further, the content of the compound (b) is preferably 15% by weight or more, particularly preferably 25% by weight or more, in the total electron beam curable components. If it is less than 15% by weight, the fog reduction effect is not significant.

Furthermore, when the third component (c) compound is used in combination, it is preferably contained in an amount of 5% by weight or more, particularly preferably 15% by weight or more. If it is less than 5% by weight, the viscosity may be too high, resulting in poor coating workability, and curing reactivity may not improve.

In addition to the above-mentioned compounds, thermoplastic resins represented by the following may be mixed and used for the purpose of improving flexibility and adhesion of the support base material.

(I) Cellulose derivative nitrocellulose, cellulose acetate butyrate,
Ethyl cellulose, butyl cellulose, etc. (I) Polyvinyl alcohol resin Polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, etc. (III) Vinyl chloride copolymer Vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic acid copolymer (IV) Polyurethane resin (V) Unsaturated, saturated polyester resin ('l Polyamide resin, etc.) These thermoplastic resins may or may not have an acrylic modified double bond introduced therein.

These thermoplastic resins can be used in an amount of 20 parts by weight or less when the total amount of the electron beam curable resin composition of the present invention is 100 parts by weight.

Furthermore, the composition for coating a cured coating layer in the present invention includes:
A solvent can be added if necessary.

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

Solvents that can be suitably used in preparing the composition include methanol, ethanol, isopropanol, alcohols such as buknol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, ethyl butyrate. Examples include esters such as ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, glycol ethers such as dioxane, aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as hexane and heptane, and mixtures thereof.

Note that the support according to the present invention uses a white pigment in order to increase the reflectance since it is used as a reflective support, and the following inorganic white pigments are typically mentioned. That is, titanium oxide (anatase type, rutile type), barium sulfate, calcium carbonate, aluminum oxide, magnesium oxide, etc. can all be used. Preferred are titanium oxide, barium sulfate, and calcium carbonate. Further, the dispersibility of titanium oxide can be improved by treating the surface of the titanium oxide with a metal oxide such as a hydrous alumina oxide, a hydrous ferrite oxide, or a hydrous silicon oxide.

The amount of the inorganic white pigment is preferably 25 to 250 parts by weight based on 100 parts by weight of the electron beam curable composition. More preferably, it is 30 to 150 parts by weight.

In addition, the average particle diameter of the pigment is preferably 0.05 to 10 μm, more preferably 0.1 to 3 μm.

Furthermore, if necessary, blue tint can be added using pigments, dyes, antioxidants, and UV.
An absorbent or the like may be mixed into the electron beam curable composition.

As the support base material used in the present invention, commercially available medium-quality paper,
In addition to high-quality paper, various materials can be used, such as paper base materials made of natural pulp, synthetic pulp, or mixtures thereof, and known photographic base paper.

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

In addition, the basis weight of the paper base material is 60 to 250 g / +yf
, more preferably 80 to 200 g/%, and the surface may be smooth or rough.

The electron beam curable composition for coating in the present invention is prepared, for example, as follows.

That is, the above-mentioned components to form a composition are charged into a kneading machine either all at the same time or individually one after another. In this case, various types of kneading machines can be used to mix and disperse the coating composition, and usable kneading machines include, for example, a two-roll mill, a Miki roll mill, a pebble mill, a ball mill, a sand grinder, a high-speed stone mill, and a high-speed impact mill. There are mills, Nigu, homogenizers, etc.

Further, as the coating method, for example, air doctor coating, blade coating, squeeze coating, air knife coating, reverse roll coating, transfer roll coating, cast coating, etc. are used.

Before providing the electron beam-cured layer on the support, the support may be subjected to surface treatment such as corona discharge, or an adhesive layer may be provided in advance if necessary.

The coating thickness is 1 to 100 μm, preferably 5 μm.
It is preferable to set it to 50 micrometers.

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 side of the roll to harden it, thereby giving the surface a mirror finish. In addition, after preliminary irradiation is performed to partially harden the surface, it comes into contact with a mirror roll and peels off.
A method of performing secondary irradiation and completely curing may be used.

Further, when applying the pattern, a desired pattern such as a silky texture or a fine grain surface can be formed by using a patterning roll instead of a mirror-finished roll.

In addition, when irradiating the electron beam curable resin composition layer with an electron beam to form a cured resin layer, the electron beam is irradiated from the side of the electron beam curable resin composition layer, and this electron beam irradiation is carried out by the irradiated electrons. This can be done through an electron beam semi-transparent membrane (such as a metal plate or resin film) that absorbs the energy of the beam. In this case, the electron beam semi-transparent film may be in close contact with the electron beam or electron beam curable resin composition layer, or may not be in close contact with the electron beam or electron beam curable resin composition layer. In the case of close contact, the close contact surface of the electron beam semi-transparent film is made into a mirror surface, or regular or irregular irregularities are provided, so that the surface has a mirror surface or an uneven surface corresponding to this close contact surface. A photographic support can be obtained.

In addition, when using an electron beam semi-transparent film, it is used by adhering it to the electron beam curable resin composition layer in an inert gas (N2, cow, etc.) with an oxygen content of 500 ppm or less before electron beam irradiation. be able to. according to this,
Problems such as footpeg can also be prevented.

Others: Japanese Patent Application No. 1983-119176, Japanese Patent Application No. 1987-1
Curing may also be carried out by a curing method other than the above-mentioned methods described in Japanese Patent Application No. 19177 and Japanese Patent Application No. 119178/1983, or by a method described in Japanese Patent Application Laid-Open No. 144736/1983.

The electron beam accelerator used may be, for example, an electrocurtain system, a van de Graaf type scanning system, a double scanning system, or the like.

In addition, the electron beam characteristics are preferably 50 to 750 KV, more preferably 100 to 300 KV in terms of penetrating power.
Using an electron beam accelerator, the absorbed dose is 0.1 to 20 Mrad.
It is preferable to do so.

Note that when irradiating the electron beam, it is preferable to perform the irradiation in an atmosphere of an inert gas such as Nt, He, Co□, or the like.

Further, for the purpose of improving the adhesion with the photographic constituent layers, the coating layer may be subjected to surface treatment such as corona discharge treatment, or an undercoat layer may be separately applied to the surface of the coating layer.

Incidentally, the layer structure of the photographic emulsion layer and the photographic light-sensitive material formed on such a coating layer may be arbitrarily selected. As the photographic emulsion layer, monochrome and color emulsion layers can be provided. The cured coating layer of the photosensitive material of the present invention includes:
A color photographic emulsion layer can preferably be provided.

The photographic material of the present invention can be embodied as a silver halide photographic material, but it can also be applied to other photographic materials. For example, the present invention relates to a diffusion transfer type heat-developable photosensitive material, in which a color image is obtained by separating a silver image and a dye by releasing a diffusible dye by heat development and transferring this dye to an image-receiving layer, such as a special 1977-
No. 124339, No. 59-181345, No. 59-1
No. 59159, No. 59-166954, No. 57-17
No. 9840, No. 57-186744, No. 58-149
No. 046, No. 59-168439, No. 59-1748
No. 34, No. 59-17483.5, No. 5917483
No. 2, No. 59-174833, patent application No. 58-1092
No. 93, No. 59-181604, No. 59-18250
No. 7, No. 59-179657, No. 59-182506
No. 59-102813, JP-A-59-12432
No. 7, No. 59-124329, No. 59-154445
It is also effective for heat-developable photosensitive materials described in various publications such as No. 1, No. 59-166954, and the specifications thereof.

Such diffusion transfer type heat-developable photosensitive materials (hereinafter simply referred to as heat-developable photosensitive materials) are also described in, for example, Japanese Patent Application Nos. 58-247986, 58-247989, and 59-2813. As shown in the figure, after exposure, a receiver/image receiving sheet having a dye fixing portion is superimposed on the heat-developable photosensitive material so that the photosensitive layer of the photosensitive material and the dye fixing layer are in close contact with each other, and the image receiving sheet is superimposed. 8 heat-developable photosensitive materials
Heat development is performed at 0°C to 250°C, preferably 120°C to 170°C, for 1.0 seconds to 180 seconds, preferably 1.5 seconds to 120 seconds, and the formed dye image is diffusely transferred to an image receiving sheet. By peeling the image receiving sheet from the photothermographic material,
A color image can be obtained.

The image-receiving sheet used in these applications is obtained by coating the support according to the present invention with a layer containing a mordant polymer for fixing the heat-transferable dye released from the heat-developable photosensitive material.

Preferred mordant polymers include Japanese Patent Application No. 58-9
7907, 58-128600, or vinylpyridine polymers such as those described in U.S. Pat. No. 2,548,564 or U.S. Pat. No. 3,709.
Examples include polymers containing a quaternary amino group described in , No. 690 of the present invention.

The support of the present invention can be used as an image-receiving sheet as it is, or by coating one layer of the mordant polymer on the support of the present invention.

When the photographic material according to the present invention is applied to a color photographic material, it usually has three types of light-sensitive silver halide emulsion layers having different spectral sensitivities, and each emulsion layer has a yellow coupler, a magenta coupler, and cyan coupler.

In such a case, the combination of a light-sensitive silver halide emulsion layer and a coupler is usually a cyan coupler in the red-sensitive silver halide emulsion layer, a magenta coupler in the green-sensitive silver halide emulsion layer, and a magenta coupler in the green-sensitive silver halide emulsion layer. A yellow coupler is associated with each blue-sensitive silver halide emulsion layer. There are no particular restrictions on the order in which the emulsion layers are stacked.

Any yellow, magenta and cyan couplers may be used as desired.

Preferred yellow couplers include benzoylacetanilide couplers and pivaloylacetanilide couplers. Preferred magenta couplers include 1-phenyl-3-anilino-5-pyrazolone couplers and pyrazolotriazole couplers. Preferred cyan couplers include phenolic couplers. Each of these couplers is present in the silver halide emulsion layer in amounts ranging from 0.05 to 1 mole of silver halide.
It is preferably contained in an amount of about 1 mol.

In addition to the above-mentioned silver halide emulsion layer, the color photographic light-sensitive material to which the present invention is applied includes, on the support, a non-photosensitive layer such as a protective layer, an intermediate layer, one filter layer, one scavenger layer, etc. in an appropriate layer order and number of layers. A sexual layer can be provided.

The silver halide contained in the silver halide emulsion layer used may be any of silver iodobromide, silver chlorobromide, silver bromide, silver chloroiodobromide, silver chloride, and silver chloroiodide. There may be,
A mixture of these may be used. These silver halides may be produced by any of the ammonia method, neutral method, acidic method, etc., and may be produced by any of the simultaneous mixing method, forward mixing method, back mixing method, conversion method, etc. Furthermore, silver halide grains with or without boundaries between different halogen compositions can be effectively used.

The binder that can be used in the constituent layers of the color photographic light-sensitive material used in the present invention is most commonly gelatin such as alkali-treated gelatin or acid-treated gelatin. Derivatives such as gelatin, albumin, agar, gum arabic, alginic acid, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone,
It can also be used in combination with a copolymer of these vinyl compounds.

The silver halide emulsion used is a salt of a noble metal such as ruthenium, rhodium, palladium, iridium, platinum, or gold (
For example, noble metal sensitization with ammonium chloroparadate, potassium chloroplatinate, potassium chloroaurate, potassium chloroaurate, etc.), active gelatin, sulfur sensitization with unstable sulfur compounds (e.g., sodium thiosulfate, etc.), selenium compounds. Chemical sensitization can be performed, such as selenium sensitization using stannous salts, polyamines, etc., and reduction sensitization under low 1) Ag conditions.

Further, these silver halide emulsions can be optically sensitized using various sensitizing dyes in order to impart photosensitivity in a desired wavelength range. Preferred sensitizing dyes that can be used at this time include, for example, US Pat.
No. 939,201, No. 2,072゜908, No. 2.7
No. 39.149, No. 2,213,995, No. 2,493
．． No. 748, No. 2,519,001, West German Patent No. 929
, 080, British Patent No. 505,979, etc., cyanine dyes, merocyanine dyes, or composite cyanine dyes can be used alone or in combination of two or more. These various optical sensitizers are used for purposes other than their original purpose, such as preventing fogging, preventing deterioration of photographic performance due to storage of color photographic materials, and adjusting development (for example, gradation control, etc.) It can also be used for this purpose.

Furthermore, various photographic additives such as ultraviolet absorbers (e.g.
(hensiphenone compounds and benzotriazole compounds), dye image stabilizers (e.g. phenolic compounds,
bisphenol compounds, hydroxychroman compounds, bisspirochroman compounds, hydantoin compounds, dialkoxybenzene compounds, etc.), stain inhibitors (e.g. hydroquinone derivatives, etc.), surfactants (
For example, sodium alkylnaphthalene sulfonate, sodium alkylbenzene sulfonate, sodium alkyl succinate sulfonate, polyalkylene compounds, etc.), water-soluble anti-irradiation dyes (for example, azo compounds, styryl compounds, oxonol compounds, triphenylmethane compounds, etc.), hardeners (e.g., halogen-substituted S−+-riazine compounds, active vinyl compounds, ethyleneimino compounds, epoxy compounds, water-soluble aluminum salts, etc.), film property improvers ( For example, glycerin, polyalkylene glycols, aqueous polymer dispersions [latexes], solid or liquid paraffins, etc.) can be added.

In order to coat each constituent layer of the color photographic light-sensitive material on the support of the light-sensitive material of the present invention, a commonly known coating method is used.
For example, the coating is applied by dip coating, roller coating, bead coating, curtain flow coating, etc., and then dried. In order to obtain a dye image using a color photographic light-sensitive material, after imagewise exposure, a color development process is performed if necessary. The processing steps basically include color development and bleach-fixing steps. In this case, each step may be independent, or two or more of the steps may be performed using processing liquids that have the respective functions, resulting in a single treatment. Further, each step can be divided into two or more times as necessary. In addition, during the processing process, in addition to the above, a pre-hardening bath, a neutralization tower, a first development (black and white development)
, an image stabilizing bath, washing with water, etc. are combined. The processing temperature is set within a preferable range depending on the photosensitive material and processing prescription. Generally, the temperature is 20 to 60°C, but the above-mentioned color photographic materials are particularly suitable for processing at 30°C or higher.

Color developing agents used in color development include a variety of agents that are widely used in various color photographic processes. Color developing agents useful for and (are N,
It is an N-dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, particularly useful compounds include N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, 2-amino- 5-(-N-ethyl-N-
dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline sulfate, 4-amino-3 -methyl-N,
N-diethylaniline sulfate, N-ethyl-N-β-hydroxyethyl-3-methyl-4-aminoaniline sulfate, 4-amino-N-(β-methoxyethyl)-N-ethyl-3-methylaniline -p-toluenesulfonate, N,N-diethyl-4-amino-3-(β-methanesulfonamidoethyl)aniline sulfate, and the like. Among these exemplified compounds, those more preferably used include N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, 4-amino-3-methyl-N,N- Diethylaniline hydrochloride, and 4-amino-N-(β-methoxyethyl)-N-ethyl-3-methylaniline-p-1-luenesulfonate, N,N-diethyl-4-amino-3
-(β-methanesulfonamidoethyl)aniline sulfate.

Various additives can be added to the color developing solution as necessary. For example, alkali metal hydroxides and carbonates, alkaline agents such as tertiary phosphates, buffers such as boric acid and acetic acid, thioethers, 1-aryl-3-pyrazolidones, N-methyl-p-aminophenols, Development accelerators such as polyalkylene glycol, benzyl alcohol,
Organic solvents such as ethylene glycol, diethylene glycol, methanol, and acetone, development inhibitors such as potassium bromide and nitrobenzimidazoles, preservatives such as sulfites, hydroxylamine, glucose, and alkanolamines, polyphosphoric acid compounds, and nitrilotriacetic acid. There are water softeners such as

〔Example〕

Examples of the present invention will be described below.

First, an example of manufacturing a product for obtaining an electron beam curable composition according to this example will be described, and then a detailed explanation of the present invention will be given. A comparative example will also be described. It should be noted that, as a matter of course, the present invention is not limited to the following production examples and examples.

Production Example 1 228 parts of bisphenol A and 168 parts of hexane diisocyanate were mixed, and further 0 parts of dibutyltin dilaurate were added.
．． 4 parts and 0.3 parts of p-quinone as a thermal polymerization inhibitor were added, and the mixture was reacted with stirring at 65°C for 4 hours.

Next, in this, 2-hydroxyethyl acrylate 232
was added dropwise, and stirring was continued until the presence of isocyanate groups in the reaction system was no longer recognized by IR spectrum.

After 2 hours, a product with an isocyanate distillation degree of 0% was obtained. The obtained product corresponds to the above-mentioned exemplified compound (10).

Production Example 2 182 parts of heptane diisocyanate was used in place of hexane diisocyanate. A product was obtained in the same manner as in Production Example 1 except for this. This product is the same as the above-mentioned exemplified compound (2
7) applies.

Production Example 3 Bisphenol F200 was placed in a reaction vessel equipped with a stirrer.
1 part, 320 parts of pimelic acid, 6 parts of para-toluenesulfonic acid, 0.5 part of phenothiazine, and 60 parts of cyclohexane, and heated at 80 to 100°C while blowing air for about 1 part.
The reaction was stirred for 0 hours.

Next, in this, 2-hydroxyethyl acrylate 232
1 part was charged and the reaction was carried out in the same manner to obtain a product.

This product corresponds to the above-mentioned exemplified compound (29).

Production Example 4 348 parts of superic acid was used in place of pimelic acid. A product was obtained in the same manner as in Production Example 4 except for this. This product corresponds to the above-mentioned exemplified compound (28).

Production Example 5 200 parts of bisphenol F and 2 parts of sodium hydroxide were placed in an autoclave equipped with a thermometer, a nitrogen gas introduction device, an alkylene oxide introduction device, and a stirring device, and the system was replaced with nitrogen gas while stirring, and the temperature was 5 kg at 160°C.
/ctA or less, 528 parts of ethylene oxide is gradually introduced and reacted. After the reaction is completed, the gauge pressure is 0. l kg
Stirring was continued until the temperature was below /cr&, and the reaction required 30 minutes. 728 parts of the obtained adduct, 144 parts of acrylic acid, 9 parts of para-toluenesulfonic acid, 0.9 parts of hydroquinone, and 90 parts of cyclohexane were placed in a four-bottle flask equipped with a stirrer and reacted at 80 to 100°C for 15 hours while blowing air. Since the acid value became 5.1 or less, the solvent was removed and pumped out to obtain a product. This product corresponds to the above-mentioned exemplified compound (14).

Production Example 6 228 parts of bisphenol A, 34 parts of propylene oxide
8 parts and 2 parts of sodium hydroxide were reacted in the same manner as in Production Example 5. 576 parts of the obtained adduct, 144 parts of acrylic acid,
6 parts of paratoluenesulfonic acid, 0.6 parts of hydroquinone, and 60 parts of cyclohexane were reacted in the same manner as in Production Example 5,
The product was obtained.

This product corresponds to the above-mentioned exemplified compound (15).

Production Example 7 200 parts of bisphenol F, 352 parts of ethylene oxide
1 part and 2 parts of sodium hydroxide were reacted in the same manner as in Production Example 5. 552 parts of the obtained adduct, 90 parts of succinic acid, 6 parts of paratoluenesulfonic acid, 0.5 part of phenothiazine, and 60 parts of cyclohexane were charged, and the mixture was heated to 80 parts while blowing air.
The reaction was stirred at ~100°C for about 10 hours. Next, 144 parts of acrylic acid was charged and reacted in the same manner, followed by neutralization washing and removal of the solvent to obtain a product. This product corresponds to the above-mentioned exemplified compound (16).

Next, examples will be described. First, the formation of the coating layer in each example will be explained, and various tests (
The results of folding durability tests and fog measurements will be summarized later.

Example 1 After coating 30 g/rrf of the following mixture on one side of photographic base paper with a weight part of 160 g/%, energy rays @0.5
Cured using a M rad electron beam. The composition of the mixture is as follows.

Exemplified compound (1) 60 parts by weight Production example 1
Product (Exemplary Compound (10)) 25 parts by weight Propylene glycol diacrylate 15 parts by weight Titanium dioxide (rutile type, average particle size 0.2 μm) 40 parts by weight Example 2 Example using a mixture having the following composition A support was prepared in the same manner as in 1.

Exemplified Compound (1) 30 parts by weight Product of Production Example 1 30 parts by weight Propylene glycol diacrylate 40 parts by weight Titanium dioxide (rutile type average particle size 0.2 μm) 40 parts by weight Example 3 A mixture consisting of the following composition A support was prepared by carrying out the same operation as in Example 1.

Exemplified Compound (1) 10 parts by weight Product of Production Example 1 50 parts by weight Propylene glycol diacrylate 40 parts by weight Titanium dioxide (rutile type average particle size 0.2 μm) 40 parts by weight Example 4 A mixture consisting of the following composition was used. The same operation as in Example 1 was carried out to prepare a support.

Exemplified Compound (1) 30 parts by weight Product of Production Example 2 (Exemplified Compound (27)) 30 parts by weight Kayamer HDDA manufactured by Nippon Kayaku Co., Ltd. 40 parts by weight Titanium dioxide (anatase type average particle size 0.15 μm) 4
0 parts by weight Example 5 A support was prepared in the same manner as in Example 1 using a mixture having the following composition.

Exemplified Compound (1) 30 parts by weight Product of Production Example 3 (Exemplified Compound (29)) 30 parts by weight Propylene glycol diacrylate 40 parts by weight Titanium dioxide (anatase type average particle size 0.15 μm) 4
0 parts by weight Example 6 A support was prepared in the same manner as in Example 1 using a mixture having the following composition.

Exemplified Compound (1) 30 parts by weight Product of Production Example 4 (Exemplified Compound (2B)) 30 parts by weight Kayamer HDDA manufactured by Nippon Kayaku Co., Ltd. Titanium dioxide (anatase type average particle size 0.15 μm) 4
0 parts by weight Example 7 A support was prepared in the same manner as in Example 1 using a mixture having the following composition.

Exemplified compound (1) 30 parts by weight Production example 5
Product (Exemplary Compound (14)) 30 parts by weight Propylene glycol diacrylate 40 parts by weight Titanium dioxide (anatase type average particle size 0.20 μm) 4
0 parts by weight Example 8 A support was prepared in the same manner as in Example 1 using a mixture having the following composition.

Exemplified compound (1) 30 parts by weight Production example 6
Product (Exemplary Compound (15)) 30 parts by weight Kayamer HDDA titanium dioxide (rutile type average particle size 0.25 μm) manufactured by Nippon Kayaku Co., Ltd.
40f! Amount Example 9 A support was prepared in the same manner as in Example 1 using a mixture having the following composition.

Exemplified Compound (1) 30 parts by weight Product of Production Example 7 (Exemplified Compound (16)) 30 parts by weight Propylene glycol diacrylate 40 parts by weight Titanium dioxide (rutile type average particle size 0.25 μm) 40 parts by weight Example 10 A support was prepared in the same manner as in Example 1 using a mixture having the following composition.

Exemplary Compound (1) 60 parts by weight Product of Production Example 1 40 parts by weight Titanium dioxide (anatase type average particle size 0.3 μm) 40 parts by weight Example 11 The same procedure as in Example 1 was carried out using a mixture having the following composition. The operation was performed to create a support.

Exemplary compound (1) 60 parts by weight Product of Production Example 3 40 parts by weight Titanium dioxide (anatase type average particle size 0.3 μm) 40 parts by weight Example 12 The same procedure as in Example 1 was carried out using a mixture having the following composition. The operation was performed to create a support.

Exemplified compound (3) 60 parts by weight Production example 5
Product: 40 parts by weight Titanium dioxide (rutile type average particle size 0.23 μm) 40 parts by weight Example 13 A support was prepared in the same manner as in Example 1 using a mixture having the following composition.

Exemplified compound (3) 60 parts by weight Production example 7
Product: 40 parts by weight Titanium dioxide (rutile type, average particle size 0523 μm) 40 parts by weight Comparative Example 1
A support was prepared in the same manner as in Example 1 except that Mrad was used.

Exemplary Compound (1) to parts by weight EPM800 manufactured by Shin-Nakamura Chemical Industry Co., Ltd. 50 parts by weight Propylene glycol diacrylate 40 parts by weight Titanium dioxide (rutile type average particle size 0.2 μm) 40 parts by weight Comparative Example 2 Consists of the following composition A support was prepared using the mixture in the same manner as in Example 1.

Exemplary compound (3) 30 parts by weight M210 manufactured by Toagosei Chemical Industry Co., Ltd. 30 parts by weight Propylene glycol diacrylate 40 parts by weight Titanium dioxide (anatase type average particle size 0.3 μm) 40
Parts by Weight Comparative Example 3 A support was prepared in the same manner as in Example 1 using a mixture having the following composition.

40 parts by weight of aliphatic polyurethane acrylate 30 parts by weight of trimethylolpropane triacrylate 30 parts by weight of diethylene glycol diacrylate 40 parts by weight of titanium dioxide (rutile type average particle size 0.2 μm) (folding durability test of support) To determine the folding resistance of the support, each sample was
Humidity was controlled at 3°C and relative humidity 55% for 10 days, and the sample length was 15%.
It was cut into a size of x200 (mm") and measured using a MAT folding durability tester (manufactured by Unishima Co., Ltd.) under a load of 1.0 kg. The results are shown in Table-1.

Table 1 Measurement results of folding durability (fogging test of photographic layer) In order to measure the effect on fog of each obtained support, the following layers were sequentially coated on the cured coating layer, and five different colors were coated. A photographic paper sample was prepared (the amount added is shown per 1 unless otherwise specified, and the silver halide emulsion is shown in terms of silver).

Layer 1: 2 g gelatin, 0.042 g blue-sensitive silver chlorobromide emulsion (silver chloride 10 mole %), and 0.83 g yellow coupler (Y-1'), 0.01 g H
A blue-sensitive emulsion layer containing 0.6 g of dioctyl phthalate in which Q-1 was dissolved.

Layer 2: 1.2g gelatin and 0.05g HQ
A first intermediate layer containing 0.2 g of dioctyl phthalate dissolved in -1.

Layer 11.9 g of gelatin, 0.040 g of green-sensitive silver chlorobromide emulsion (silver chloride 50 mol %), and 0.42 g of the following magenta coupler (M-1), 0.015 g of H
A green-sensitive silver chlorobromide emulsion layer containing 0.36 g of dioctyl phthalate in which Q-1 was dissolved.

Layer 4: 1.9g gelatin and 0.02g HQ-
1 and 0 in which 0.7g of ultraviolet absorber (UV-1) was dissolved.
, a second intermediate layer containing 5 g of dioctyl phthalate.

1 s: t, sg of gelatin, 0.027 g of red-sensitive silver chlorobromide emulsion (silver chloride 50 mol%), and 0.4.
g of the following cyan coupler (C-1), 0.01 g of H
A red-sensitive emulsion layer containing 0.35 g of dioctyl phthalate in which Q-1 and 0.3 g of UV-1 were dissolved.

Layer 6: Protective layer containing 1.4 g of gelatin.

HQ-1 UV-1 ~ Each sample thus obtained was heated at 30°C and relative humidity 60%.
After being stored for several months and subjected to light pattern exposure, it was subjected to color development using the processing steps and processing solution shown below. A portion of each sample was coated, dried 10 days later, exposed and developed, and was used as data on the same day.

Processing process (33℃) Color development 3 minutes 30 seconds drift fixing
Wash with water for 1 minute and 30 seconds
Dry for 3 minutes
60-80℃ (color developer) Pure water 800I
IIIl Ethylene glycol 15Il
lI! Benzyl alcohol 15...1W
hitex B Bcone
Lg (fluorescent bleach manufactured by Sumitomo Chemical Co., Ltd.) Hydroxylamine sulfate 3g3-methyl-4-
Amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate
4.5g Potassium carbonate (anhydrous) 30g
Potassium sulfite (anhydrous) 2.0 g Potassium bromide 0.65 g 60% aqueous solution of hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 2 ml water was added to make the solution 11, and the pH was adjusted to 10 with sulfuric acid or potassium hydroxide. Adjust to 1.

(Bleach-fix solution) Pure water 600mj
! Ethylenediaminetetraacetic acid-2-sodium・2Hz0 25g ammonium sulfite (40% aqueous solution) 35mj! Ammonium thiosulfate (70% aqueous solution) 50mg Ethylenediamine iron(II) tetraacetate ammonium 95g Aqueous ammonia (28%
) 25mj? Add water to make 11, and adjust the pH to 6.9 with aqueous ammonia or glacial acetic acid.

The fog density of the developed sample was measured using a Sakura color densitometer model PDA-60 (manufactured by Konishiroku Photo Industry Co., Ltd.). The results are shown in Table-2.

Furthermore, yellowing of the support itself was compared with samples after development.

As is clear from Table 1, samples (sample fish 1 to 13) of supports (Examples 1 to 13) constituting the photosensitive material of the present invention
is the sample of the support of Comparative Examples 1 to 4 (sample 11m14 to 1
Compared to 6), the performance against bending is significantly improved.

In addition, as is clear from Table 2, compared to the comparative example, the folding durability and fogging, which were difficult to achieve in the past, were improved while improving the folding durability without deteriorating the fogging over time. It can be significantly reduced. Further, there was no problem with yellowing of the support itself after development.

Furthermore, the sharpness of the image, the smoothness of the support, the heat resistance, the weather resistance, and the adhesion between the paper and the layer to be cured were also sufficiently satisfactory.

〔Effect of the invention〕

As mentioned above, in the silver halide photographic light-sensitive material of the present invention, the coating layer of the support has excellent flexibility, and furthermore, fog, which has conventionally been difficult to achieve at the same time as flexibility, especially fog over time, deteriorates flexibility. It has good photographic performance, such as being able to reduce the amount of photosensitive material while still improving it, and also prevent yellowing after the processing process, and solve the problems of conventional photosensitive materials having an electron beam-cured coating layer.

Claims (1)

[Scope of Claims] 1. A photographic light-sensitive material having at least one photosensitive layer provided on a support, wherein the support has an electron beam curable composition coated on at least one side of the support base material. A cured coating layer is formed by curing the composition by irradiating it with an electron beam, and the electron beam curable composition contains the following compounds (a) and (b).
) A photographic material comprising at least one of each of the following. (a) An electron beam curable compound containing a polybutadiene chain in its molecular chain. (b) An electron beam curable compound represented by the following general formula. A-X-Y-X-A [In the formula, , tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R is H or CH_3) Any of the following; A is an ethylenically unsaturated group at the terminal a group having