JPH09281709A - Photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive material low in tendency to curl even in the case of storing in a roll of film and good in dimensional stability by cooling a photosensitive layer, after coating and drying, from a specified temperature to a specified lower temperature above the glass transition point of a polyester support for a specified time. SOLUTION: This photoresist material has on the polyester support at least one transferrable or nontransferrable photosensitive layer and the photosensitive layer is cooled, after coating and drying it, from a temperature by 25 deg.C higher than the glass transition point of the polyester support down to a temperature by 5 deg.C higher than the glass transition point for >=20sec. This polyester of the support is not especially limited but it is preferred to use the polyester composed essentially of dicarboxylic acid and diol components and having film forming property. This photosensitive material is used for photosensitive materials for forming lithographic and letterpress printing plates and for color correction and the like.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to transferability or
More specifically, the present invention relates to a light-sensitive material to be transferred, which is hard to have a curl even when stored in a roll form and has good dimensional performance.

[0002]

2. Description of the Related Art A biaxially stretched polyethylene terephthalate film (hereinafter referred to as PET film) has excellent transparency,
It has mechanical strength and dimensional stability, and is used as a film for various photosensitive materials.

However, in recent years, since a large amount of light-sensitive materials have been used, the light-sensitive material which has been conventionally used in the form of a sheet is shipped in a roll and cut into a desired size on the user side, which is left unattended. The problem of Tsukuru Makise has become apparent. That is, PE placed in a rolled state for a long time
The T film sample has a problem that curling curls become large and jamming occurs during automatic transportation or transportation to the automatic processing machine. Therefore, it has been desired to reduce curling curl of a polyester film typified by a PET film.

[0004] From such a viewpoint, in the world of silver halide photographic light-sensitive materials, Japanese Patent Application Laid-Open No. S51-16358 discloses a method of reducing the curl of a polyester film by rolling a thermoplastic resin film at Tg-5 ° C. ~ Tg-30 ° C
(Hereinafter, the glass transition temperature of the thermoplastic resin film is referred to as Tg
It is said that the heat treatment is performed for 0.1 to 1500 hours. Further, JP-A-6-35118 proposes a method of subjecting a polyester film having a Tg of 90 ° C. to 200 ° C. to undercoating, and then heat-treating the film at 50 ° C. to Tg for 0.1 to 1500 hours.

[0005]

The thermoplastic resin film is heated at Tg-5 ° C to Tg-30 ° C for 0.1 to 1500 hours.
Heat treatment methods include PET film and polyethylene naphthalate film (hereinafter referred to as PEN film),
It was effective because it had the effect of reducing the curling curl of a crystalline or semi-crystalline thermoplastic resin. However, such a long-time heat treatment at a relatively low temperature has a problem that the quality of the photosensitive material is significantly impaired.

That is, the photosensitive material is 0.1 at 50 ° C. to Tg.
The method of heat treatment for up to 1500 hours is the same as the method described in JP-A-51-16358 in principle, but in order to sufficiently reduce curling curl by these methods, a film A heat treatment near Tg is required. The transferable photosensitive material has a plastic film as a base material, and a photosensitive layer or the like is laminated on the surface thereof on various functional layers such as an adhesive layer and an antistatic layer. Due to the nature of the photosensitive layer being peeled off from the support and transferred, applying heat to the front side and the back side causes the front side and the back side to stick together, and when unwound again, problems such as film peeling of the photosensitive layer occur. Further, since the curl becomes large to some extent, a deviation occurs when stacking documents, and the dimensional stability becomes worse as the curl increases. That is, when the heights of the four corners (called rising curls) when the convex portions are downward when the photosensitive material is rolled up and released are exceeded, the dimensional deviation becomes remarkable.

It is an object of the present invention to provide a light-sensitive material which does not have such a defect and which is hard to have a curling tendency and has good dimensional performance even when stored in a roll form.

[0008]

The above objects of the present invention have been attained by the following constitutions.

(1) In a photosensitive material having at least one transferable or transferable photosensitive layer on a polyester support, when the photosensitive layer is coated and dried and then cooled, the polyester support has a glass transition temperature of 25. A photosensitive material characterized by cooling from a temperature higher by 5 ° C to a temperature higher by 5 ° C over 20 seconds or more.

(2) A photosensitive material having a transferable or transferable photosensitive layer of at least one layer on a polyester support, wherein the rising curl of the polyester support is 30 mm or less.

The present invention will be described in more detail. The polyester (hereinafter referred to as polyester) constituting the support of the light-sensitive material of the present invention is not particularly limited, but is a polyester having a dicarboxylic acid component and a diol component as main components and having film-forming properties. It is preferable.

The main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2-6 naphthalene dicarboxylic acid, 2-7 naphthalene dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethane dicarboxylic acid. , Cyclohexanedicarboxylic acid, diphenyldicarboxylic acid,
Examples thereof include diphenylthioether dicarboxylic acid, diphenyl ketone dicarboxylic acid, and phenylindane dicarboxylic acid. As the diol component, ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2
-Bis (4-hydroxyphenyl) propane, 2,2-
Bis (4-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bisphenol fluorene hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like can be mentioned.

Among the polyesters containing these as main constituents, terephthalic acid is used as the dicarboxylic acid component, ethylene glycol and / or 1-4 cyclohexane is used as the diol component from the viewpoints of transparency, mechanical strength and dimensional stability. Polyesters whose main constituent is dimethanol are preferred. Among them, polyester having polyethylene terephthalate as a main constituent, copolymerized polyester composed of terephthalic acid, 2-6 naphthalene dicarboxylic acid and ethylene glycol, and polyester having a mixture of two or more of these polyesters as main constituents Is preferred.

A polyester film having an ethylene terephthalate unit content of 70% by weight or more is excellent in transparency, mechanical strength, dimensional stability and the like, and is preferable.

The polyester constituting the biaxially stretched polyester film used in the present invention may be further copolymerized with another copolymerization component as long as the effect of the present invention is not impaired. May be mixed. Examples of these include the above-mentioned dicarboxylic acid component and diol component, and polyesters composed thereof.

The polyester used in the present invention may contain an antioxidant. The type of the antioxidant to be contained is not particularly limited, and various kinds of antioxidants can be used. Examples include antioxidants such as hindered phenol compounds, phosphite compounds, and thioether compounds. You can Above all, an antioxidant of a hindered phenol compound is preferable in terms of transparency.

The content of the antioxidant is usually 0.01 to 2% by weight, preferably 0.1 to 2% by weight with respect to the polyester.
0.5%. By setting the content of the antioxidant in this range, it is possible to prevent the so-called fog phenomenon in which the density of the unexposed portion of the photosensitive material becomes high, and the haze of the film can be suppressed to a low level, so that the photosensitive material having excellent transparency A support for use is obtained. Incidentally, these antioxidants may be used alone or in combination of two or more.

The method of synthesizing the polyester as the raw material of the biaxially stretched polyester film used in the present invention is not particularly limited, and the polyester can be produced by a conventionally known method for producing polyester. For example, a direct esterification method in which a dicarboxylic acid component is directly esterified with a diol component, first a dialkyl ester is used as a dicarboxylic acid component, and an ester exchange reaction is performed between this and the diol component, and this is heated under reduced pressure. A transesterification method in which the excess diol component is removed to perform polymerization can be used. At this time, if necessary, a transesterification catalyst or a polymerization reaction catalyst may be used, or a heat stabilizer may be added. In addition, in each process during synthesis, anti-coloring agent,
Add antioxidants, crystal nucleating agents, slip agents, stabilizers, antiblocking agents, UV absorbers, viscosity modifiers, defoamers, clarifiers, antistatic agents, pH adjusters, dyes, pigments, etc. Good.

The thickness of the biaxially stretched polyester film used in the present invention is not particularly limited. It may be set so as to have a required strength according to the purpose of use.
That is, when used in a photosensitive material, it is 50 to 300 μm.
m, particularly preferably 60 to 200 μm.

The biaxially stretched polyester film used in the present invention may be provided with slipperiness, if necessary. The means for imparting slipperiness is not particularly limited, but an external particle addition method of adding inert inorganic particles to polyester, an internal particle precipitation method of precipitating a catalyst added at the time of polyester synthesis, or a surfactant is used as a film. The method of applying on the surface is common. Among these, the internal particle deposition method in which the deposited particles can be controlled to be relatively small is preferable because slipperiness can be imparted without impairing the transparency of the film. As the catalyst, various known catalysts can be used, but Ca and Mn are particularly preferable because high transparency can be obtained. These catalysts may be used alone or in combination of two kinds.

The biaxially stretched polyester film used in the present invention preferably has a haze of 3% or less. More preferably, it is 1% or less. The haze is measured according to ASTM-D1003-52.

The Tg of the biaxially stretched polyester film used in the present invention is preferably 60 ° C. or higher. Tg is determined as an average value of a temperature measured by a differential scanning calorimeter at which a baseline starts to be shifted and a temperature at which the baseline returns to a new baseline. When Tg is not less than this value, the film is not deformed in the drying step of the developing processor, and a photosensitive material having a small curling curl after the developing processing can be obtained.

Next, a method for producing the polyester film used in the present invention will be described. A method for obtaining an unstretched sheet and a method for uniaxially stretching in the longitudinal direction can be performed by a conventionally known method. For example, the raw material polyester is molded into pellets, dried with hot air or vacuum dried, melt-extruded, extruded into a sheet from a T-die, adhered to a cooling drum by an electrostatic application method, cooled and solidified, and unstretched. Get the sheet. Then, the obtained unstretched sheet is subjected to a glass transition temperature (T) of polyester through a plurality of roll groups and / or a heating device such as an infrared heater.
This is a method of heating in the range of g) to Tg + 100 ° C. and performing single-stage or multi-stage longitudinal stretching. The stretching ratio is usually in the range of 2.5 to 6 times, and it is necessary to make the subsequent transverse stretching possible. When the sheet has a multilayer structure, the setting of the stretching temperature is preferably based on the Tg of the polyester of the thickest layer among the Tg of the polyester of each constituent layer.

At this time, even when polyester is laminated,
A conventionally known method may be used. For example, a co-extrusion method using a plurality of extruders and a feed block type die or a multi-manifold type die, a single layer film constituting a laminate or other resin constituting a laminate on the laminate film is melt extruded from the extruder and cooled. Examples thereof include an extrusion laminating method of cooling and solidifying on a drum, and a dry laminating method of laminating a monolayer film or a laminated film constituting a laminate with an anchor agent or an adhesive as required. Among them, a co-extrusion method that requires a small number of production steps and has good adhesion between the layers is preferable.

Next, the polyester film uniaxially stretched in the machine direction obtained as described above is treated with Tg to Tm-2.
Within the temperature range of 0 ° C. (the melting point of the polyester film is Tm), transverse stretching is performed, and then heat setting is performed. The transverse stretching ratio is usually 3 to 6 times, and the ratio of the longitudinal stretching ratio to the transverse stretching ratio is appropriately adjusted so that the obtained biaxially stretched film has physical properties measured and has desirable characteristics. In the case of the present invention, the elastic modulus in the width direction is made larger than the elastic modulus in the longitudinal direction.
It may be changed according to the purpose of use. At this time, it is preferable to laterally stretch while gradually increasing the temperature difference in the stretching region divided into two or more in the range of 1 to 50 ° C. because the distribution of the physical properties in the width direction can be reduced. Further, the film after the lateral stretching is 0.01 to below the final lateral stretching temperature in the range of Tg-40 ° C or higher.
Holding for 5 minutes is preferable because the distribution of physical properties in the width direction can be further reduced.

Heat setting is performed at a temperature higher than the final transverse stretching temperature,
Heat fixing is usually performed for 0.5 to 300 seconds within a temperature range of Tm-20 ° C or lower. At this time, it is preferable to heat-set while sequentially raising the temperature difference in the range of 1 to 100 ° C. in the two or more divided regions.

The heat-fixed film is usually cooled to Tg or less, and the clip gripping portions at both ends of the film are cut and wound up. At this time, within the temperature range not higher than the final heat setting temperature and not lower than Tg, 0.1 in the width direction and / or the longitudinal direction.
It is preferable to perform a relaxation treatment by 10%. Also, cooling is
100 ° C to 10 ° C per second from the final heat setting temperature to Tg
It is preferable to gradually cool at a cooling rate of. The means for cooling and relaxing treatment is not particularly limited and can be carried out by conventionally known means, but it is particularly preferable to perform these treatments while sequentially cooling in a plurality of temperature regions from the viewpoint of improving the dimensional stability of the film. The cooling rate is a value obtained by (T ₁ −Tg) / t, where T ₁ is the final heat setting temperature and t is the time required for the film to reach Tg.

The more optimum heat setting conditions, cooling conditions and relaxation treatment conditions differ depending on the polyester constituting the film. Therefore, the physical properties of the obtained biaxially stretched film are measured and appropriately adjusted so as to have the desired properties. It may be determined by

In the production of the above-mentioned film, a functional layer such as an antistatic layer, a slipping layer, an adhesive layer and a barrier layer may be coated before and / or after stretching. At this time, various surface treatments such as corona discharge treatment and chemical treatment can be applied as necessary. Further, for the purpose of improving the strength, stretching used for known stretched films such as multi-stage longitudinal stretching, re-longitudinal stretching, re-longitudinal-lateral stretching, and horizontal / longitudinal stretching can also be performed. Of course, the clip gripping parts on both ends of the cut film are used as raw materials for films of the same type or different types after being pulverized or after being subjected to granulation treatment, depolymerization / repolymerization, etc. as necessary. It may be reused as a raw material for the film.

Next, the photosensitive layer used in the present invention will be described. The photosensitive material of the present invention is a lithographic printing photosensitive material, a relief photosensitive material, a color proofing photosensitive material and the like.

Each of these is a photosensitive layer containing a photopolymerizable compound and a binder, a photosensitive layer containing an o-quinonediazide compound and a binder, a photosensitive layer containing a photoconductive compound and a binder, and a near infrared light absorber. It is composed of a photosensitive layer containing a binder and can be used as a non-silver salt photosensitive material by laminating the photosensitive layers. In addition to these photosensitive layers, it is generally known that a metal deposited layer of aluminum or the like, a hydrophilized layer, a colored layer, an image receiving layer, an antistatic layer and the like are laminated and used as required.

In the color proofing material, the photosensitive layer contains a near-infrared light absorbing agent and a binder, or the photosensitive layer containing a photopolymerizable compound and a binder and an o-quinonediazide compound and a binder is the support of the present invention and it. By being laminated on a resin layer to be laminated, it is generally widely used in the printing field as a color proof material.

As a color proofing material comprising a photosensitive layer containing a near-infrared absorber and a binder, a recording material and an image receiving material in which a heat-fusible coloring material layer or a coloring material layer containing a heat sublimable dye is provided on a support. A thermal transfer recording method is generally used in which a laser beam is used as a heat source, which are opposed to each other (JP-A-49-15437).
No. 49-17743, No. 57-87399, No. 59-1439659, No. 61-112665, etc.).

Typical recording materials and image receiving materials will be described below. The ink layer laminated on the resin layer of the present invention as a recording material may be a transfer layer composed of a color material, a photothermal conversion agent and a binder, and a transfer layer composed of the color material and the binder, and a non-transfer layer composed of the photothermal conversion material and a binder. It may have a two-layer structure of a transferable photothermal conversion layer.

First, the case where the ink layer is a transfer layer capable of converting light into heat will be described.

Examples of the coloring material include pigments such as inorganic pigments and organic pigments and dyes. Examples of the inorganic pigments include titanium dioxide, carbon black, zinc oxide, Prussian blue, cadmium sulfide, iron oxide and chromates of lead, zinc, barium and calcium. Examples of organic pigments include azo-based, thioindigo-based, anthraquinone-based, anthanthrone-based, triphendioxazine-based pigments, vat dye pigments, phthalocyanine pigments (eg, copper phthalocyanine) and their derivatives, and quinacridone pigments. Examples of the organic dyes include acid dyes, direct dyes, disperse dyes, oil-soluble dyes, metal-containing oil-soluble dyes, and sublimable dyes.

As a coloring material, for example, Lionol Blue FG-
7330, Lionol Yellow No. 1206, No.
1406G, Lionol Red 6BFG-4219X
Pigments such as (all manufactured by Toyo Ink) can be used.

The content of the coloring material in the ink layer is not particularly limited, but is usually in the range of 5 to 70% by weight, preferably 10 to 60% by weight.

As the light-heat converting agent, any conventionally known one can be used. In a preferred embodiment of the present invention, heat is generated by irradiation with a semiconductor laser beam. Therefore, when a color image is formed, a near-infrared light absorbing agent showing an absorption maximum in a wavelength band of 700 to 3000 nm and having no or small absorption in a visible region is used. preferable. When a monochrome image is formed, carbon black or the like having absorption in the visible to near infrared region is preferable.

As the near-infrared light absorber, organic compounds such as cyanine-based, polymethine-based, azurenium-based, squalium-based, thiopyrylium-based, naphthoquinone-based, anthraquinone-based dyes, phthalocyanine-based, azo-based, and thioamide-based organometallic complexes And the like, and specifically, JP-A-63-139191, JP-A-64-33547, JP-A-1-160683, 1-280750 and 1
-293342, 2-2074, 3-2659
No. 3, No. 3-30991, No. 3-34891, No. 3
-36093, 3-36094 and 3-3609
No. 5, 3-42281, 3-97589, 3
And the compounds described in JP-A-103476.

These can be used alone or in combination of two or more.

Examples of the binder for the ink layer include a heat-melting substance, a heat-softening substance, and a thermoplastic resin. The heat-fusible substance is generally a solid or semi-solid substance having a melting point in the range of 40 to 150 ° C. measured using Yanagimoto MJP-2. Specifically, carnauba wax, wood wax,
Vegetable waxes such as ouricure wax and Espal wax; animal waxes such as beeswax, insect wax, shellac wax, spermaceti wax; petroleum waxes such as paraffin wax, microcrystal wax, polyethylene wax, ester wax, acid wax; Waxes such as mineral waxes such as ozokerite and ceresin; and besides these waxes and the like, higher fatty acids such as palmitic acid, stearic acid, margaric acid and behenic acid; palmityl alcohol;
Higher alcohols such as stearyl alcohol, behenyl alcohol, marganyl alcohol, myricyl alcohol, and eicosanol; higher fatty acid esters such as cetyl palmitate, myricyl palmitate, cetyl stearate, and myricyl stearate; acetamide, propionamide, palmitamide; Amides such as stearic acid amide and amide wax; and stearylamine;
And higher amines such as behenylamine and palmitylamine.

As the thermoplastic resin, an ethylene copolymer, a polyamide resin, a polyester resin, a polyurethane resin, a polyolefin resin, an acrylic resin, a vinyl chloride resin, a cellulose resin, a rosin resin, Resins such as polyvinyl alcohol resins, polyvinyl acetal resins, ionomer resins, petroleum resins;
Natural rubber, styrene butadiene rubber, isoprene rubber,
Elastomers such as chloroprene rubber and diene copolymer; rosin derivatives such as ester gum, rosin maleic acid resin, rosin phenol resin and hydrogenated rosin; and phenol resin, terpene resin, cyclopentadiene resin, aromatic hydrocarbon resin and the like High molecular compounds and the like can be mentioned.

The thermal transfer layer having a desired heat softening point or heat melting point can be formed by appropriately selecting the above-mentioned heat-meltable substance and thermoplastic substance.

Next, the case where the ink layer has a two-layer structure of a transferable color material layer and a photothermal conversion layer will be described. By having a two-layer structure of a color material layer and a light-to-heat conversion layer, a light-to-heat conversion agent having absorption in the visible region can be used, which is advantageous in color reproduction especially when a color image is formed.

As the photothermal conversion agent in the photothermal conversion layer,
The above-mentioned light-to-heat convertible ink layers can be used. However, the photothermal conversion layer has a thickness of 700 to 1000 nm.
In the near-infrared light region, the absorption for the wavelength of the light source is at least 0.25 or more, preferably 0.5 or more. When an infrared absorbing dye is used, it has an absorption coefficient per unit weight as compared with a pigment such as carbon black, so that the thickness of the light-to-heat conversion layer can be reduced, and high sensitivity can be achieved.

As the binder in the photothermal conversion layer,
Resins with high glass transition temperature and high thermal conductivity, such as gelatin, polyvinylpyrrolidone, polyester, polyparabanic acid, polymethylmethacrylate, polycarbonate,
Polystyrene, ethyl cellulose, nitrocellulose,
Polyvinyl alcohol, polyvinyl chloride, polyamide,
A general heat resistant resin such as polyimide, polyether imide, polysulfone, polyether sulfone, or aramid can be used.

The film thickness of this photothermal conversion layer is preferably 0.1 to 3 μm, and the content of the photothermal conversion material in the photothermal conversion layer is
Usually, the absorbance at the wavelength of the light source used for image recording is 0.3
It can be determined to be 3.0.

The photothermal conversion layer may be formed as a vapor deposition film in addition to the above. Carbon black, gold, silver, aluminum, chromium, nickel, antimony and tellurium described in JP-A-52-20842. Examples include vapor-deposited layers of metal black such as bismuth and selenium. The photothermal conversion material may be the color material itself of the ink layer, and is not limited to the above, and various substances can be used.

Next, the image receiving material will be described. The image receiving material forms an image by receiving the ink layer that is imagewise peeled from the recording material. Usually, the image receiving material has a support and an image receiving layer, and may be formed of only the support.

The image-receiving layer is composed of a binder and various additives and mat materials which are added as necessary. In some cases, it is formed only with a binder. As the image-receiving layer binder having a good image-receiving property, polyvinyl acetate emulsion-based adhesives, chloroprene-based adhesives, epoxy resin-based adhesives and other adhesives, natural rubber, chloroprene rubber-based, butyl rubber-based, polyacrylic acid ester-based, nitrile Adhesive materials such as rubber type, polysulfide type, silicone rubber type, rosin type, vinyl chloride type, petroleum type resin and ionomer resin,
Recycled rubber, SBR, polyisoprene, polyvinyl ether and the like can be mentioned.

When the image formed on the image receiving layer is retransferred to another recording medium by further heating and / or pressing, a resin having a relatively small polarity (small SP value) is used as the image receiving layer. Is particularly preferable. For example, polyethylene, polypropylene, ethylene-vinyl chloride copolymer, polybutadiene resin, ethylene-acrylic copolymer, vinyl chloride resin, various modified olefins, and the like.

The thickness of the image receiving layer is usually 10 to 100 μm, but this is not the case when the support of the present invention is used as an image receiving material. As the cushion layer, a cushioning intermediate layer described in the recording material can be used. Further, the film thickness when re-transferring to another recording medium is preferably 30 to 50 μm. Other undercoat layer, back coat layer,
In some cases, an antistatic layer or the like may be provided.

When the photosensitive layer contains an o-quinonediazide compound, any one can be used as long as it can function as a photosensitizer.

Specifically, for example, 1,2-benzoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-
Naphthoquinonediazide-5-sulfonyl chloride,
A compound obtained by condensing 1,2-naphthoquinonediazide-6-sulfonyl chloride with a compound containing a hydroxyl group and / or an amino group is preferably used. Preferably, it is a compound having a sulfonyl chloride group at the 4-position, and is a condensed compound with 1,2-naphthoquinonediazido-4-sulfonyl chloride.

Examples of the hydroxyl group-containing compound include trihydroxybenzophenone, dihydroxyanthraquinone, bisphenol A, phenol novolac resin, resorcin benzaldehyde condensation resin and pyrogallol acetone condensation resin. Examples of the amino group-containing compound include aniline, p-aminodiphenylamine,
Examples include p-aminobenzophenone, 4,4'-diaminodiphenylamine, and 4,4'-diaminobenzophenone.

With regard to the quinonediazide compounds, including the ones mentioned here, further reference is made to J. Koser (J. Kosa)
r) "Light Sensitive System" (Light
Sensitive System (New York City, John Wiley and Sons, Inc., 1965), and Nagamatsu and Inui, "Photosensitive Polymer" (Kodansha, 1
1977).

When the photosensitive layer contains a photopolymerizable compound, specifically, for example, as the photopolymerizable compound, any one generally used can be arbitrarily used.
For example, at least one compound arbitrarily selected from the compound group consisting of acrylic acid, methacrylic acid, acrylic acid ester and methacrylic acid ester can be used. Examples include, but are not limited to, ethylene glycol diacrylate, glycerin triacrylate, polyacrylate, ethylene glycol dimethacrylate, and the like.

The photosensitive layer may contain a photopolymerization initiator. The photopolymerization initiator in this case is optional,
It is more preferable that the absorption in the visible region is small, and examples of such a substance include the following compounds.
However, it is not limited to these. That is, benzophenone, Michler's ketone [4 ', 4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone,
Aromatic ketones such as phenanthraquinone and other aromatic ketones, benzoin ethers, methyl benzoin, ethyl benzoin and other benzoins,
And 2- (o-chlorophenyl) -4,5-diphenylimidazole duplex, 2- (o-chlorophenyl)
-4,5- (m-methoxyphenyl) imidazole duplex, 2- (o-fluorophenyl) -4,5-diphenylimidazole duplex, 2- (o-methoxyphenyl)
-4,5-diphenylimidazole dimer, 2- (p-
Methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer Weight,
2- (p-methylmercaptophenyl) -4,5-diphenylimidazole duplex and U.S. Pat.
185, 2,4,5-triacrylimidazole duplexes, such as similar duplexes described in GB 1,047,569 and U.S. Pat. No. 3,784,557. .

Other photopolymerizable compounds include 2,4-
Thioxanthones such as diethylthioxanthone can also be used. In this case, known compounds such as p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, N-methyldiethanolamine, and bisdiethylaminobenzophenone can be used as the photopolymerization accelerator.

As the binder, a known polymer compound,
It is possible to contain a synthetic resin, and it is preferable to contain, for example, a polymer compound having a carboxylic acid vinyl ester polymerization unit represented by the following general formula in its molecular structure.

[0062]

Embedded image

In the formula, R ₁₀ represents an alkyl group which may have a substituent.

Any polymer compound having the above-mentioned structure can be optionally used. Examples of the vinyl carboxylate ester monomer for forming the polymerized unit represented by the above general formula include vinyl acetate and propionic acid. vinyl,
Examples thereof include vinyl butyrate, vinyl laurate, vinyl versatate (shown in Chemical Formula 2) and the like.

[0065]

Embedded image

In the formula, R ₁₁ and R ₁₂ are alkyl groups, and the sum of their carbon numbers is 7. That is, R ₁₁ + R ₁₂ = C ₇ H ₁₆ .

The polymer compound may be a polymer obtained by polymerizing one kind of carboxylic acid vinyl ester, or a polymer obtained by copolymerizing two or more kinds of carboxylic acid vinyl ester, or a carboxylic acid vinyl ester and a copolymer thereof. It may be a copolymer in any component ratio with other possible monomers.

Examples of the monomer unit that can be used in combination with the polymer unit represented by the above general formula include ethylenically unsaturated olefins such as ethylene and propylene, styrenes, acrylic acid such as acrylic acid and methacrylic acid. Unsaturated aliphatic dicarboxylic acids such as maleic acid and maleic anhydride, diesters of unsaturated dicarboxylic acids such as diethyl maleate, α-methylene aliphatic monocarboxylic acid esters such as methyl acrylate, nitriles such as acrylonitrile , Amides such as acrylamide, anilides such as acrylanilide, vinyl ethers such as methyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, for example, 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1, Two
Vinyl monomers such as ethylene derivatives such as dimethoxyethylene, 1,1-dimethoxycarbonylethylene and 1-methyl-1-nitroethylene, N-vinyl compounds such as N-vinylpyrrole and N-vinylcarbazole There is. These monomer units have a structure in which the unsaturated double bond is cleaved and are present in the polymer compound.

The polymer compound to be used is particularly preferably one having a vinyl acetate polymer unit in the molecular structure. Among them, those having 40 to 95% by weight of vinyl acetate polymerized units and having a number average molecular weight (MN) of 1,000
~ 60,000, weight average molecular weight (MW) of 50
Those having 0 to 150,000 are preferred.

More preferably, a polymer compound having a vinyl acetate polymer unit (particularly 40 to 95% by weight) and a carboxylic acid vinyl ester polymer unit having a longer chain than vinyl acetate is preferable, and particularly a number average molecular weight (MN). Is 2,000
0-60,000, weight average molecular weight (MW) of 10,000
It is preferably from 00 to 150,000.

In this case, the monomer constituting the polymer compound having vinyl acetate polymerized units by copolymerization with vinyl acetate may be any monomer as long as it can form a copolymer, such as vinyl acetate-ethylene. Vinyl acetate-vinyl chloride, vinyl acetate-vinyl stearate, vinyl acetate-
It can be arbitrarily selected from the above-mentioned monomers such as vinyl versatate, vinyl propionate-vinyl versatate and the like.

Dyes and / or pigments are added as colorants in the photosensitive layer. Especially when used for color proofing,
Pigments and dyes having the same colors as those required for ordinary colors, that is, yellow, magenta, cyan, and black are required, but other metal powders, white pigments, and fluorescent pigments are also used.

When a colorant is used, the ratio of the colorant / a component other than the colorant in the colored photosensitive layer is determined by a method known to those skilled in the art in consideration of the target optical density and the removability of the colored photosensitive layer from a developer. Can be determined by For example, in the case of a dye, the content is preferably 5% to 75% by weight, and in the case of a pigment, the content is preferably 5% to 90% by weight.

The thickness of the colored photosensitive layer is determined by a method known to those skilled in the art according to the target optical density, the kind of the coloring agent used in the colored photosensitive layer (dye, pigment, carbon black) and its content. However, if the thickness of the colored photosensitive layer is as thin as possible within the allowable range, the resolution is higher and the image quality is better. Thus, the membrane thickness is preferably usually being used in the range of ^{0.1g / m 2 ~5g / m 2} .

In addition, if necessary, a plasticizer, a coatability improver and the like may be added to the layer structure of the transfer material and the image receiving material.

As the plasticizer, various low molecular weight compounds such as phthalic acid esters, triphenyl phosphates,
Examples of the maleic acid esters and the coatability improver include surfactants such as fluorine surfactants and nonionic surfactants represented by ethylcellulose polyalkylene ether.

The photosensitive layer can be divided into two layers, a colored layer containing a colorant and a binder and a photosensitive layer containing a photosensitive composition. In this case, either layer may be arranged on the support side.

Any known protective layer may be used, but its gas permeability is preferably selected appropriately depending on the type of the photosensitive composition used. That is, it is preferable to provide a protective layer having a high gas permeability in the case of a photosensitive composition which generates a gas at the time of exposure to o-quinonediazide or the like, and in the case of using a photopolymerizable photosensitive composition, it is preferable to provide a protective layer. It is preferable to provide a protective layer having low permeability. Further, those which are soluble in a developing solution during development, in particular, a water-soluble polymer such as polyvinyl alcohol and cellulose, having a thickness of about 0.01 to 5 μm, particularly 0.0
It is preferably about 3 to 1 μm.

The materials used for these photosensitive layers and other layer constitutions are not only color proof materials but also lithographic printing photosensitive materials and letterpress printing photosensitive materials with binders of novolac resins and vinyl-based materials having phenolic hydroxyl groups. It can also be widely used by changing it to a polymer.

As a color proofing material containing a photopolymerizable compound and a binder and an o-quinonediazide compound and a binder, there is a method of forming a multicolor transfer image using a color sheet, for example, as described in JP-A-47-41830. Direct method of transferring the colored image of the above directly to the final image receiving paper
97140 and 61-189535, JP-A-3-13-1
No. 07852, an indirect transfer system for temporarily transferring a colored image onto a temporary image receiving sheet.
Generally, a method of transferring the colored photosensitive layer described in No. 7 to an image receiving paper and thereafter forming an image is repeated.

The photosensitive layer as described above is coated on a biaxially stretched polyester film, but Tg + 30 is obtained by coating and drying.
Since a temperature of not less than 0 ° C. is applied, the curling curl tends to be attached, so the curl curling reduction treatment of the present invention is performed.

In the winding curl formation, the amorphous portion of the polyester begins to agglomerate for a long period of time to form a fibrillar ribbon which is a spherulite constituent element (P.
H. Gel et al. J. Macromol. Sc
i. Phys. , B1, 235, 251 (1967))
It is considered that the shape is left as it is and is stabilized. In other words, if it is flat, the shape will be stable in the unwound state and in the unwound state. This phenomenon can also be understood from the fact that, when measuring DSC, an endothermic peak, which was not observed immediately after film formation, was observed to increase with standing time and the size of the endothermic peak made it difficult to curl. In this case, if the temperature is not higher than Tg, the higher the temperature, the shorter the treatment time and the same effect can be obtained, and the peak top of the endothermic peak shifts to the higher temperature side with the treated temperature.

However, such microfibrils are
It seems to be formed only in the amorphous part, and it is more than Tg, especially Tc.
When exposed to a temperature above (cold crystallization temperature), the shape returns to a flat state where the crystal part remembers during film formation.

In the heat treatment of the present invention, the formation of such microfibrils is not observed, but the winding curl is improved. That is, if the temperature is gradually cooled between Tg + 25 ° C. and Tg + 5 ° C. for 20 seconds or more, it is mysteriously difficult to wind. In order to accelerate the curling effect,
It is advisable to perform heat treatment at 130 ° C. ± 20 ° C. for 1 second or more and 30 minutes or less during drying. From the viewpoint of continuous production, it is preferable that such heat treatment time is short, so that it is more preferably 5 seconds or more and less than 6 minutes.

The method of applying the heat treatment of the present invention is not particularly limited, but the feature of the present invention is that the effect of reducing the curl curl can be obtained by performing the heat treatment in a much shorter time than the conventional curl curl reduction method. Therefore, for example, even if the film is heat-treated in a state where the films are stacked one on top of another or wound in a roll, the film is not uniformly heated, so that the effect of the present invention is difficult to obtain. Therefore, a method that can uniformly heat the film in a short time is preferable. As such a method, for example, the film is continuously transported by gripping the both ends of the film with pins or clips, or transporting the roll by a plurality of rolls or air transport that blows air onto the film and floats the film. Heat treatment by spraying heated air from one or more slits on one or both sides of the film surface, using radiant heat from an infrared heater, or contacting with multiple heated rolls. Method.

The method for holding the film in a flat state is as follows.
Although not particularly limited, examples thereof include the above-described pin and clip transfer method, air transfer method, and roll transfer method. The roll transport method is not perfectly flat because the roll is transported with a film holding angle.
The film can be considered to be substantially flat because the front and back of the film alternately contact the roll and the winding direction of the film is not one direction.

The above heat treatment step may be any step from the production of the film to the cutting and packaging into the final product form. 3 at temperatures above ℃
If it is heated for more than 0 minutes, its effect will fade. Especially T
If c or more, the effect will disappear in a very short time, so be careful. Of course, even if the effect disappears once,
By performing the heat treatment again, the original curling curl reducing effect can be obtained.

The heat treatment may be performed in one step, or may be performed in two or more zones with a temperature difference. After coating and drying the photosensitive layer, it is preferable to subsequently perform heat treatment.

The heat treatment base thus obtained is
Since it is at least Tg, it must be cooled to room temperature. The cooling at this time is preferably as fast as possible in terms of planarity, and is preferably at least 10 ° C./second or more.

[0090]

Next, the present invention will be described based on examples, but embodiments of the present invention are not limited to these examples.

Example 1 An ethylene-vinyl acetate copolymer resin layer (manufactured by Mitsui DuPont Polychemical Co., Ltd.) having a thickness of 25 μm and a thickness of 25 μm on a biaxially stretched PET (intrinsic viscosity: melt viscosity 0.62) having a film thickness of 100 μm. EVAFLEX P-1405, vinyl acetate 1
4 wt%) was applied by an extrusion laminating method while applying an anchor agent (urethane oligomer, isocyanate compound). After the corona discharge was applied to the opposite surface, an antistatic layer having the following formulation was applied.

Water-soluble acrylic resin (Jurimer ET-410; 2 wt% manufactured by Nippon Pure Chemical Co., Ltd.) 1.6 parts by weight Antimony-doped crystalline tin oxide (SN-88: manufactured by Ishihara Sangyo) 1.8 parts by weight Fluorine-based activator (Eftoptop EF-102: manufactured by Mitsubishi Materials) 0.15 parts by weight 2-hydroxy-4,6-dichloro-1,3,5-triazine soda 0.2 parts by weight Drying after finishing to 100 parts by weight with pure water Film thickness is 0.2μ
It was dried at 130 ° C. to obtain m.

Further, the following photosensitive layer was coated on the ethylene-vinyl acetate resin layer side.

(Photosensitive Solution) o-Naphthoquinonediazide-4-sulfonic acid ester of p-cresol / formalin novolac resin (polymerization average molecular weight = 2000) 60 g 50% methanol solution of vinyl acetate / versa vinylate copolymer (charged weight) Ratio = 70: 30, weight average molecular weight; 45000) 878.4 g Carbon black MA-100 99 g Glutaric acid 2 g Fluorosurfactant (FC-430 <3M company>) 1 g MEK 100 g The working fluid is applied and 130 ° C. And dried for 1 minute to obtain a photosensitive layer having a dry film thickness of 1 μm.

Subsequently, an overcoat solution having the following formulation was applied on the upper surface of the photosensitive layer.

(Overcoat Liquid) Cellulose derivative (carboxymethylcellulose) 10 g Water 300 g of a processing liquid was applied to a dry film thickness of 0.4 μm, and 1
It was dried at 30 ° C. for 1.5 minutes and gradually cooled from 100 ° C. to 80 ° C. as shown in the table of Example to obtain a transferable photosensitive material.

This original is wound around a 3-inch core,
It was stored at 40 ° C. for the period shown in Table 1. The transferable photosensitive material and an A-2 size plate-making original (an original having register marks at four corners) were superposed with a pin bar and exposed to ultraviolet rays, and developed with the following developing solution.

(Developer) Potassium silicate 40 g Perex NBL (manufactured by Kao Atlas) 80 g Water 2000 g Next, the photosensitive layer side of the transfer material on which the developed image is formed and the art paper (manufactured by Mitsubishi Paper Mills, Tokubishi Art) ) Are brought into close contact with each other, they are overlapped with each other using a pin bar, and a heated laminator (temperature 100 ° C., nip pressure 3 kg, feed speed 45 mm / min) is passed through to transfer the formed image to paper. It was

Here, the reticulated positive film used at the time of exposure and the register mark position of the image transferred on the paper are overlapped with each other by using a pin bar, and each of them is measured to obtain a dimensional deviation (register mark deviation).
Was measured. In addition, the positions A, B at which the dimensional deviation is measured,
C and D are shown in FIG.

[0100]

[Table 1]

From Table 1, when the slow cooling time is 20 seconds or more, it is difficult to wind and the dimensional deviation is small. Further, when the rising curl exceeds 30 mm, the size is greatly deviated, but by taking the annealing time of 20 seconds or more, the rising curl is saturated at 30 mm or less and there is no problem.

From the above studies, it has been found that a storage treatment at 40 ° C. for 3 days gives a curling habit similar to that after 2 years, and even if it is wound on a 3 inch core for 2 years, the core portion can be used without any problem. I understand.

The curl just after the production is due to the asymmetric support and the result of anti-curl due to the solvent coating.

[0104]

According to the present invention, even when stored in a roll form,
A light-sensitive material having less winding tendency and good dimensional performance was obtained.

[Brief description of drawings]

FIG. 1 is a diagram showing positions where dimensional deviations of the present invention are measured.

[Explanation of symbols]

 1 position of life pin 2 position of free pin 3 position A 4 position B 5 position C 6 position D

Claims (2)

[Claims] 1. A photosensitive material having at least one transferable or transferable photosensitive layer on a polyester support, when the photosensitive layer is coated and dried and then cooled, the temperature is 25 ° C. above the glass transition temperature of the polyester support. High temperature to 5 ℃
A photosensitive material characterized by being cooled to a high temperature in 20 seconds or more. 2. A photosensitive material having at least one transferable or transferable photosensitive layer on a polyester support, wherein the rising curl of the polyester support is 3
A photosensitive material having a length of 0 mm or less.