JP3190577B2 - Lithographic printing plate manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a lithographic printing plate. More specifically, the present invention relates to a method for producing a lithographic printing plate on which an ink receiving layer can be formed by a method including an image-wise thermal development step.

[0002]

BACKGROUND OF THE INVENTION Lithographic printing is a method of printing from a specially manufactured surface in which some areas can receive lithographic ink while others cannot receive the ink when wetted with water. The areas of the printing medium that receive ink from those plate areas that receive ink form the printed image area, while the areas of the printing medium that are in contact with those non-ink receiving printing plate areas are background areas. To form For the purposes of the present invention, the areas of the lithographic printing plate that are capable of receiving ink will be referred to as hydrophobic, and those areas which are not receptive to this ink after being pre-wetted with water will be referred to as hydrophilic.

In the negative-working lithographic technique, the image areas of the plate cannot be receptive to oily lithographic inks after being pre-wetted with water (hydrophilic), and the non-image areas can accept the ink (hydrophobic). A printing plate is manufactured. Two methods are possible depending on whether the surface of the plate is hydrophobic or hydrophilic before image-wise processing. In a method where the surface of the plate is hydrophobic before the image-wise treatment, the image-wise treatment renders the image area hydrophilic, whereas in a method where the surface of the plate before the image formation is hydrophilic, the image Processing according to the image corresponding to the negative renders the non-image areas hydrophobic.

In the technique of positive working lithographic printing, the printing plate has an image area which can accept oily lithographic ink (hydrophobic), and a non-image area cannot receive this ink after pre-wetting with water (hydrophilic). Is manufactured. Two methods are possible depending on whether the surface of the plate is hydrophobic or hydrophilic before image-wise processing. In a method in which the plate surface is hydrophobic before the image-wise treatment, the image-wise treatment corresponding to the negative of the image renders the non-image areas hydrophilic, while the surface of the plate before the image-wise treatment. In a method where is hydrophilic, image-wise processing renders the image area hydrophobic.

[0005] For the production of lithographic printing plates, image-wise treatment, or image-wise treatment, corresponding to the negative of the image, involves combining actinic radiation, ionizing radiation or heat or a combination thereof with appropriate treatment of the plate. Can be implemented using a combination of

[0006] The use of thermographic or photothermographic materials in the manufacture of lithographic printing plates opens the possibility of using dry development technology, which allows complete dry processing development without additional components and is applied externally It has advantages over conventional methods that require development with (wet) developers.

[0007] Thermal imaging or thermographic methods which utilize the reduction of a substantially light-insensitive organic heavy metal salt to heavy metal particles by the application of heat by an organic reducing agent are completely dry-processed without additional components. Development is possible. In addition, such systems can be made photosensitive by the incorporation of a photosensitizer that can catalyze the thermal reduction of the organic heavy metal salt by the reducing agent after exposure.

[0008] US Pat. No. 4,210,711 describes a method for forming an image which comprises image-wise exposure of a photosensitive imaging element composed of a layer of a thermoplastic photosensitive composition which is not adhesive at room temperature and a support. However, in this method, at least one surface of the exposed photosensitive material in close contact with a release developing carrier sheet composed of a thermoplastic material that is not adhesive at room temperature is heated to a temperature higher than the softening temperature of at least one photosensitive composition layer. And heating the release developing carrier sheet from the photosensitive imaging material at about or below that heating temperature, thereby supporting the exposed or unexposed areas of the photosensitive composition layer on the release developing sheet. The corresponding non-exposed or exposed areas are formed as separate images on the body. In this case, the photosensitive composition contains a photosensitive polyhalogen compound, a photosensitive quinone, a photosensitive polymer, silver halide or an organic silver salt.

[0009] US Pat. No. 3,689,993 discloses a thermographic composition comprising a complex of a hot-melt phenolic resin and a high molecular weight water-soluble poly-ether, -amine or -amide polymer, and an organic silver salt oxidizing agent for the resin. A lithographic printing plate is described, the composition of which undergoes a visible change upon heating to form an ink-receiving image area.

[0010] Differences in the ink receptive behavior of image and non-image areas in prior art thermographic methods for the production of lithographic printing plates are insufficient to produce high quality prints. Moreover, such lithographic printing plates have printing properties that are inferior to the best. For example, poor ink receptivity in the hydrophobic region of the lithographic printing plate and low printing durability.

[0011]

SUMMARY OF THE INVENTION Therefore, the first aspect of the present invention is as follows.
It is an object of the present invention to provide a method for producing a lithographic printing plate having improved discrimination in the ink receiving behavior between image and non-image areas of the lithographic printing plate.

It is a further object of the present invention to provide a method for producing a lithographic printing plate having improved printing durability.

[0013]

[0014]

Further objects and advantages of the invention will become clear from the description hereinafter.

[0016]

The above objects are achieved by the specific features according to the present invention.

According to the present invention, there is provided a method for producing a lithographic printing plate, comprising the following steps: (i) a support, a hydrophobic thermosensitive layer, and a hydrophilic layer adjacent to the hydrophobic thermosensitive layer. A substantially light-insensitive thermographic material that can be used to produce a lithographic printing plate, including a hydrophobic surface, is thermally developed according to a positive or negative image (provided that the hydrophobic thermosensitive layer contains component A). The component A, when heated, directly reacts with at least one other component B which is in a thermal working relationship with the component A to form a portion that changes the adhesive force between the hydrophobic thermosensitive layer and the adjacent hydrophilic surface. Make, but component A
Or if one of B is an organometallic salt and the other of components A or B is a reducing agent for said organometallic salt, said reducing agent is selected from the group consisting of: Aromatic compounds having at least two hydroxy groups in the above ortho- or para-position; aminophenol; p-phenylenediamine; alkoxynaphthol;
Pyrazolidin-3-one; pyrazolin-5-one; indane-1,3-dione derivative; hydroxytetronic acid;
(Hydroxytetronimide; hydroxylamine derivative; hydrazine derivative; and reductone); and (ii) separating the hydrophobic thermosensitive layer from the adjacent hydrophilic surface according to a positive or negative image.

According to the present invention, there is also provided a method for producing a lithographic printing plate comprising the following steps: (i) a support, a hydrophobic thermosensitive layer and a layer adjacent to the hydrophobic thermosensitive layer. A thermographic material that can be used to produce a lithographic printing plate, including a hydrophilic surface, is exposed to actinic radiation according to a positive or negative image (provided that the hydrophobic thermosensitive layer comprises component A, A, when heated, directly reacts with at least one other component B, which is in thermal relationship with component A, creating a portion that alters the adhesion between the hydrophobic thermosensitive layer and the adjacent hydrophilic surface. When one of components A or B is an organometallic salt and the other of components A or B is a reducing agent for said organometallic salt, said reducing agent is selected from the group consisting of: Ortho- or para-position on the nucleus An aromatic compound having at least two hydroxy groups; aminophenol; p-phenylenediamine; alkoxynaphthol;
3-one; pyrazolin-5-one; indan-1,3-
Dione derivatives; hydroxytetronic acid; hydroxytetronimide; hydroxylamine derivatives; hydrazine derivatives; and reductone. Further, a photosensitive agent is present in the hydrophobic thermosensitive layer, and after exposure, the photosensitive agent catalyzes the reaction between the component A and the component B to cause the hydrophobic thermosensitive layer and the adjacent hydrophilic surface to be exposed. (Ii) thermally developing the imagewise exposed thermographic material; and (iii) the hydrophobic thermosensitive layer from the adjacent hydrophilic surface. Are separated according to a positive or negative image.

[0019]

[0020] Preferred embodiments of the invention are disclosed in the dependent claims.

[0021]

DETAILED DESCRIPTION OF THE INVENTION The present invention is described below in connection with a preferred embodiment thereof, but it will be apparent that the invention is not intended to be limited to that embodiment. On the contrary, the intention is to cover all alternatives, modifications and equivalents as falling within the scope and spirit of the invention as defined by the appended claims.

In the case of non-photosensitive thermographic materials, the image-wise thermal development step according to the invention comprises, for example, image-wise heating with a laser in heat mode or with a thermal head. In the case of photosensitive thermographic materials (i.e., photothermographic materials), the image-wise thermal development step comprises, after image-wise exposure with an actinic radiation source,
It consists of heating the entire photothermographic material.

According to the present invention, there is provided a hydrophobic thermosensitive layer having reduced adhesion to an adjacent hydrophilic surface of said portion of said hydrophilic layer having reduced adhesion to an adjacent hydrophobic thermosensitive layer. Separation of the portions can be achieved by any technique known to those skilled in the art. It does not adversely affect the quality of the lithographic printing plate thus obtained, for example, after lamination at room temperature, peeling (with adhesive tape, etc.), rubbing, wiping with a non-aggregating liquid such as 2-propanol, After lamination, it is peeled off.

According to the present invention, the component A is a substantially non-photosensitive organic silver salt, and the component B having a thermal action relationship with the component A is formed between the hydrophobic thermosensitive layer and the adjacent hydrophilic surface. There is provided a method of making a lithographic printing plate that is a reducing agent that can reduce substantially non-photosensitive organic salts when heated to create a hydrophobic moiety that reduces adhesion.

Further, according to the present invention, after the photosensitive agent is exposed,
The method of making a lithographic printing plate present in a hydrophobic thermosensitive layer that can catalyze the reaction of component A and component B to create a portion that alters the adhesion between the hydrophobic thermosensitive layer and the adjacent hydrophilic surface is described. Provided.

According to a particular example of the invention, a hydrophobic thermosensitive layer is coated on a hydrophilic surface. The hydrophilic surface may be the surface of a hydrophilic layer, or may be the surface of a support.

According to another embodiment of the present invention, the hydrophobic thermosensitive layer is the outermost layer. In this case, according to the invention, it is coated on a hydrophilic surface and image-wise thermal development will cause a change in the adhesion between the hydrophobic thermosensitive layer and this hydrophilic surface. In the method of making a lithographic printing plate according to this example, the portion of the hydrophobic thermosensitive layer that is removed depends on whether the thermal imaging results in a decrease or increase in the adhesion of the hydrophobic thermosensitive layer to the adjacent hydrophilic surface. May correspond to the imaged or non-thermally imaged portion.

In another embodiment of the invention, the hydrophilic layer is the outermost layer providing a hydrophilic surface adjacent to the hydrophobic thermosensitive layer. In this case, according to the present invention, image-wise thermal development will cause a change in the adhesion between the hydrophilic surface adjacent to the hydrophobic thermosensitive layer and the hydrophobic thermosensitive layer itself. In the method of manufacturing a lithographic printing plate according to this example, the removed portion of the hydrophilic layer depends on whether the adhesive force between the hydrophilic surface of the hydrophilic layer adjacent to the hydrophobic layer and the hydrophobic thermosensitive layer decreases or increases. It may correspond to a thermally imaged portion or a non-thermally imaged portion. According to this example, the hydrophobic thermosensitive layer may be coated on the hydrophilic surface provided that no delamination of the thermosensitive layer from this hydrophilic surface occurs during the image-wise thermal development step.

The heat-sensitive layer may be composed of one or more materials, wherein the one or more materials include at least one of component A, component B,
It includes a binder layer containing a photosensitizer, a spectral sensitizing dye, an acutance dye, or other components that are active in the imagewise thermal development step. However, it is required that the components included in the reaction between the component B and the component A, which are generated during the thermal development at a portion where the adhesive force between the heat-sensitive layer and the adjacent hydrophilic surface is strongly changed, have a thermal action relationship with each other.

The component A in the thermosensitive layer and the component B which is in a thermal working relationship with the component A form a reactive bond, which according to the present invention, adheres between the hydrophobic thermosensitive layer and the adjacent hydrophilic surface upon application of heat. It can create a part that can change the force.
Examples of such reactive linkages are organic heavy metal salts and reducing agents therefor; organic reducing agents and oxidizing agents therefor; thermally polymerizable monomers and imagewise thermal development to produce a reduced or increased adhesion polymer. For example, 4,4'-azobis (4-
Thermally active sources of free radicals, such as azo compounds such as cyanovaleric acid), 1,1'-azobis (cyclohexanecarbonitrile), α, α'-azobisisobutyronitrile; Thermally diffusible hydrophilic parts (non-diffusible in the form of a mask) which can remove the mask by the action of such a mask and such a substrate which produces increased adhesion with image-wise thermal development; Masked thermally diffusible hydrophobic parts (non-diffusible in the form of a mask) from which the mask can be removed in a combined action and such a substrate which produces reduced adhesion with image-wise thermal development; acid and heat A masked thermally diffusible hydrophilic portion (non-diffusible in mask form) from which the mask can be removed by the combined action of and an acid which produces increased adhesion with image-wise thermal development;
Masked thermally diffusible hydrophobic parts (non-diffusible in the form of a mask) from which the mask can be removed by the combined action of acid and heat and such an acid which produces reduced adhesion with image-wise thermal development And so on.

Component A can be, for example, a substantially light-insensitive organic heavy metal salt. Particularly suitable organic heavy metal salts for use in the thermographic materials according to the invention are organic silver, iron and nickel salts, preferably organic silver salts. Preferred organic silver salts according to the present invention are silver salts of aliphatic carboxylic acids, known as fatty acids whose aliphatic carbon chain preferably has at least 12 C atoms, such as silver laurate, silver palmitate, silver stearate, Silver oleate and silver behenate (these silver salts are called "silver soap")
And a silver salt having a hydrogen atom or a hydroxyl on the aliphatic carboxylic acid, for example, silver hydroxystearate. Silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds (including silver benzoate), 3,5
Silver-substituted benzoates such as silver dihydroxybenzoate, silver gallate and the like; silver phenyl acetate; 3-carboxymethyl-4-methyl-4-thiazoline-2-thione described in US Pat. No. 3,785,830; GB-P1111492; Silver salts of aliphatic carboxylic acids containing thioether groups as described; US-P45
Silver dodecylsulfonate described in No. 04575 and E
The di- (2-ethylhexyl) -sulfosuccinates described in P-A 227 141 can likewise be used for producing thermally developable silver images.

Silver salts of compounds containing a mercapto or thione group and derivatives thereof can also be used. Preferred examples of these compounds include silver salts of 3-mercapto-4-phenyl-1,2,4-triazole, silver salts of 2-mercaptobenzimidazole, silver salts of 2-mercapto-5-aminothiadiazole, -(Ethyl-glycolamide) silver salt of benzothiazole, silver salt of thioglycolic acid, silver salt of dithiocarboxylic acid; US Pat.
Silver salts and U.S. Pat.
3- (2-carboxyethyl) -4 as described in
Silver salts of thione compounds such as -methyl-4-thiazoline-2-thione.

Further, a silver salt of a compound containing an amino group can also be used. Preferred examples of these compounds include silver salts of benzotriazole and its derivatives; silver salts of halogen-substituted benzotriazole; silver salts of carbimidobenzotriazole; 1-H-tetrazole or 1-H-tetrazole as described in US-P 4,220,709. Silver salts of imidazole and imidazole derivatives; and other organic silver salts as described in GB-P1439478, for example, phthalazinone. In addition, silver imidazolate and US-P 4,260,067
Substantially non-photosensitive inorganic or organic silver salt complexes described in No. 7;

Useful substantially light-insensitive organic silver salts are, for example, iron salts of organic acids, such as the iron salts described in EP-A 520 404, in particular iron o-benzoylbenzoate.

Useful substantially light-insensitive organic nickel salts, nickel stearate, are described in CA-P 763903.

Component B is preferably a reducing agent. Suitable organic reducing agents for the reduction of substantially light-insensitive organic heavy metal salts are aromatic di- and tri-hydroxy compounds; aminophenols; METOL®; P-phenylenediamine; alkoxynaphthols, such as US -P3
4-methoxy-1-naphthol; pyrazolidin-3-one type reducing agents, for example PHEN
IDONE®; pyrazolin-5-one; indane-1,3-dione derivative; hydroxytetronic acid; hydroxytetronimide; for example US-P408290
Hydroxylamine derivatives as described in No. 1; hydrazine derivatives; and reductones such as ascorbic acid (US Pat. No. 3,074,809, 3080254, 3094).
Organic compounds containing at least one active hydrogen atom bonded to O, N or C (see also 417 and 3887378).

Among the aromatic di- and tri-hydroxy compounds having at least two hydroxy groups in the ortho- or para-position on the same aromatic nucleus, for example the benzene nucleus, suitable reducing agents are hydroquinone and substituted hydroquinones, catechol and Pyrogallol and substituted pyrogallol such as substituted catechols, gallic acid and gallic esters. Particularly useful are polyhydroxy-spiro-bis-
Indane compounds, especially those corresponding to the following general formula (I):

Embedded image Wherein R represents hydrogen or alkyl, for example methyl or ethyl, each of R ⁵ and R ⁶ may be the same or different and represents an alkyl group, preferably a methyl group or a cycloalkyl group, for example a cyclohexyl group. And R
Each of ⁷ and R ⁸ may be the same or different and represents an alkyl group, preferably a methyl group or a cycloalkyl group, for example a cyclohexyl group, Z ¹ and Z ²
Each may be the same or different, and
Or necessary to close an aromatic ring or ring system (eg, a benzene ring) substituted in the para-position with at least two hydroxyl groups and optionally substituted with at least one hydrocarbon group (eg, an alkyl or aryl group). Represents an atom.

In particular, US-P such as photographic tanning agents
Polyhydroxy-spiro- described in 3440049
Bis-indane compounds are 3,3,3 ', 3'-tetramethyl-5,6,5', 6'-tetrahydroxy-1,
1'-spiro-bis-indane and 3,3,3 ', 3'
-Tetramethyl-4,6,7,4 ', 6', 7'-hexahydroxy-1,1'-spiro-bis-indane. Indane is also known as Hydlinden.

At the ortho-position, two hydroxy groups (--O
Among the catechol-type reducing agents, which mean a reducing agent containing at least one benzene nucleus having H), catechol, 3- (3,4-dihydroxyphenyl) propionic acid, 1,2-dihydroxybenzoic acid, gallic acid And esters thereof, such as methyl gallate, ethyl gallate, propyl gallate, tannic acid, and 3,4-dihydroxy-benzoate. A particularly preferred catechol-type reducing agent described in the unpublished European Patent Application No. EP 9420154 is one in which the benzene nucleus is replaced by two hydroxy groups present at the 3,4-position on the nucleus.
Benzene compounds having a substituent attached to the nucleus by a carbonyl group at the -position.

During the image-wise thermal development step, the reducing agent is capable of diffusing into the substantially light-insensitive organic heavy metal salt particles to enable the reduction of the substantially light-insensitive organic heavy metal salt. Must exist.

The above reducing agents, which are regarded as main reducing agents, can be used in combination with so-called auxiliary reducing agents. Such co-reducing agents are sterically hindered phenols which become reactive partners when heated in the reduction of substantially light-insensitive organic silver salts, such as silver behenate, for example as described in U.S. Pat. For example, it is of the type described in US Pat. No. 3,547,648. The auxiliary reducing agent can be present in the imaging layer in thermal relation thereto or in the polymeric binder layer.

A preferred auxiliary developer is a sulfonamidophenol corresponding to the general formula: aryl-SO ₂ -NH-arylene-OH, where aryl represents a monovalent aromatic radical and arylene is preferably para - -OH to -SO ₂ -NH- group in position
Represents a divalent aromatic group having a group.

The sulfonamide phenol represented by the above general formula was obtained from Research Disclosure published in February 1979.
17842, US-P4360581, US-P47
82004, and EP-A 42 38 91, in which these reducing agents are used in photothermographic materials in which the photosensitive silver halide is present in catalytic proximity to a substantially light-insensitive silver salt of an organic acid. It is stated as for use.

Other auxiliary reducing agents which can be used in combination with the above-mentioned main reducing agents are organic reducing metal salts such as US-P
Stannous stearate described in 3460946 and 3547648.

The thermographic material can be made photothermographic (ie, exposing a species capable of catalyzing the reduction of silver ions of organic silver salts to silver by a heat-reducing agent in the application of heat to silver). The photosensitizer (which can sometimes be formed) should be in intimate contact with the organic silver salt.
This produces the sensitizer "ex situ" and then adds it to the organic silver salt or produces the sensitizer "in situ" in the presence of the organic silver salt Can be achieved by: Suitable photosensitizers therefor include metal diazosulfonate salts, preferably heavy metal organic or inorganic salts of the 1b metal group of the periodic table; chlorides,
A salt of a hydrogen halide such as bromide or iodide; or a salt of nitric acid or nitric acid. Suitable metals include silver, copper, chromium, cobalt, platinum and gold, with silver being preferred. Mixtures of the above can also be used.

The individual metal salts photogenerate a catalyst (free metal) for the reduction of the silver oxidant with the reducing agent.
A simple test that can be used to determine whether it is possible is described in US-P 3,152,904. First, a freshly prepared sample (50 mg) of the metal salt in question is mixed with an aqueous or alcoholic suspension or dispersion (5 ml) of silver behenate (0.5 g). This dispersion is coated on filter paper and dried. The coated paper is then treated with a 0.5% aqueous or alcoholic solution of a reducing agent, preferably hydroquinone (5%).
ml) and dried again. The reaction should not take place immediately in the absence of light. The coated filter paper is then exposed (approximately 5-10 seconds-6 inches with an RS sun lamp) and heated to approximately 90-100 ° C for 5 seconds. If the exposed paper darkens faster than a similar paper sample under the same conditions without the metal salt, the salt is suitable as a photosensitive generator for the catalyst.

The preferred sensitizer is silver halide, and silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide and mixtures thereof are particularly preferred. Very fine grain photographic silver halide is particularly useful. Photographic silver halides can be prepared by any of the known methods of photographic technology. Methods for forming such photographic silver halide and forms of photographic silver halide are described, for example, in Research Disclosur
e, December 1978, Item No. 17029 and Resea
rch Disclosure, June 1978, Item No. 1764
3. Tabular grain photosensitive silver halides are also useful, for example, as described in U.S. Pat. No. 4,435,499. The photographic silver halide must be unwashed or washed, chemically sensitized, protected against fog formation and stabilized against loss of sensitivity while kept as described in the Research Disclosure publication above. Can be. Silver halides can be prepared in situ, for example as described in U.S. Pat. No. 4,457,075, or elsewhere by methods known in the photographic art. In the case of ex situ production, it may be present during the production of the organic heavy metal salt, for example as described in U.S. Pat. No. 3,389,049, or may be mixed with the organic heavy metal salt after its production.

The photosensitizer can be spectrally sensitized in the visible spectrum and in the infrared region of the spectrum using various known dyes, including cyanine, merocyanine, styryl, hemicyanine, oxonol, hemioxonol, and xanthene dyes. Useful cyanine dyes include those having a basic nucleus such as a thiazoline nucleus, oxazoline nucleus, pyrroline nucleus, pyridine nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus and imidazole nucleus. Preferred useful merocyanine dyes include not only the above basic nuclei, but also thiohydantoin nuclei, rhodanine nuclei, oxazolidinedione nuclei, thiazolidinedione nuclei, barbituric acid nuclei,
Also included are those having an acidic nucleus such as a thiazolinone nucleus, a malononitrile nucleus and a pyrazolone nucleus. Among the cyanine and merocyanine dyes, those having an imino group or a carboxyl group are particularly effective. The sensitizing power of these spectral sensitizers is described, for example, in EP-A-559228, US-P5.
It may be increased by the use of so-called supersensitizers as described for IR spectral sensitizers in 258282 and JN 63/23145.

Thermographic materials sensitized by the presence of a sensitizer are disclosed in US Pat. No. 3,515,559, DE-A.
P1927412, US-P40333948, US-P
4197131, EP-A12020, CA-P113
9149, US-P4271263, EP-B1016
46, EP-B102781, US-P475255.
9, EP-A3777961, US-P5300420,
EP-A627660, EP-A652473, US-
As described in US Pat. No. 5,382,504 and US Pat. No. 5,395,747, it may contain antihalation or acutance dyes which absorb light transmitted through the photosensitive layer and thereby prevent its reflection.

The film-forming binder of the photosensitive layer containing components (A) and (B) may be any kind of natural, modified natural or synthetic resin or a mixture of such resins, including organic heavy metal salts. Can be homogeneously dispersed. Polymers derived from α, β-ethylenically unsaturated compounds such as cellulose derivatives such as ethyl cellulose, cellulose esters, for example cellulose nitrate, carboxymethyl cellulose, starch ether, galactomannan, polyvinyl chloride, post-chlorinated polyvinyl chloride , A copolymer of vinyl chloride and vinylidene chloride,
Copolymers of vinyl chloride and vinyl acetate, polyvinyl acetate and partially hydrolyzed polyvinyl acetate, polyvinyl alcohol, polyvinyl acetate made from polyvinyl alcohol as starting material (repeatedly only some of the vinyl alcohol units react with aldehydes) ), Preferably polyvinyl butyral, copolymers of acrylonitrile and acrylamide, polyacrylates, polymethacrylates, polystyrene and polyethylene or mixtures thereof.

A particularly preferred polyvinyl butyral containing a small amount of vinyl alcohol units is that sold under the trademark BUTVAR B79 by MONSANTO USA, which gives good adhesion to paper and properly primed polyester supports. .

The above binders and their mixtures are known as "heat solvents, thermal solvents or thermosols" which improve the rate of redox reactions at elevated temperatures.
vents) "or in combination with waxes.

In the present invention, the term “thermal solvent” is 5
A liquid solvent for at least one of the redox reactants, such as a reducing agent for the organic silver salt, which becomes solid in the recording layer at a temperature of 0 ° C. or less, but is substantially non-photosensitive at a temperature of 60 ° C. or more; A non-hydrolyzable organic material that becomes a plasticizer for the thermally heated recording layer. Useful for that purpose are 15 as described in US-P 3,347,675.
It is a polyethylene glycol having an average molecular weight in the range of 2000 to 20000. Another suitable thermal solvent is US-P3
Compounds such as urea, methylsulfonamide and ethylene carbonate as described in US Pat.
Research Disclosure 150 issued in December 2006
27. Tetrahydro-thiophene-1,1 as described in 27.
Compounds such as dioxide, methyl anisate and 1,10-decanediol; and US Pat.
6, US-P4740446, US-P536897
9, EP-A0119615, EP-A122512 and DE-A3339810.

To achieve improved shelf life and reduced fog, stabilizers and antifoggants may be incorporated into the thermographic materials of the present invention. Examples of suitable stabilizers and antifoggants which can be used alone or in combination and their precursors include US-
Thiazolium salts described in P2131038 and 2694716; US-P2886437 and 244460
Azaindene described in US Pat. No. 5,287,135;
Urosol described in US Pat. No. 3,235,652; Oximes described in GB-P623448; Tiuronium described in US-P3220839; US-P2566263 and 2597.
915, palladium, platinum and gold salts;
Tetrazolyl-thio-compounds described in S-P3700457; 1,1 described in GB-P1547326
2,4-triazole compounds; US Pat. No. 4,404,390
, 1,2,4 described in US Pat.
-Triazolium-3-thiolate stabilizer precursor; tribromomethyl ketone compound described in EP-A600587; combination of isocyanate and halogen compound described in EP-A600586; EP-A6
Vinylsulfone and β-halosulfone compounds described in No. 00589; and “Imaging Processes and Mate
rials, Neblette's Eighth Edition, Chapter 9, D. Kloosterboe
r, edited by J. Sturge, V. Walworth and A. Shepp, 2
79, Van Nostrand (1989); Research Dis
closure 17029, published June 1978; and all of these references are cited in the references cited therein.

The thermographic and photothermographic materials used in the method for producing a lithographic printing plate according to the invention can contain one or more toning agents. The toning agent should be in thermal working relationship with the substantially light-insensitive organic heavy metal salt and reducing agent during the heat treatment. Any toning agent known in thermography or photothermography can be used.

Suitable toning agents are phthalimides and phthalazinones of the general formula described in US Pat. No. 4,082,901 and US Pat. No. 3,074,809, US Pat.
48 and US-P 3,844,797. Particularly useful toning agents are heterocyclic toner compounds of the benzoxazinedione or naphthooxazinedione type, especially benzo [e] [1,3] oxazine-, in the general formula described in GB-P 1,439,478 and US Pat. No. 3,951,660. 2,4-dione.

In addition to these components, the free fatty acid of the recording layer, a surfactant, and an antistatic agent, for example, a nonionic antistatic agent containing a fluorocarbon group (eg, F ₃ C (CF ₂ ) ₆ CO)
NH (CH ₂ CH ₂ O) -H); silicone oil (eg, BAYSILONE OE1A (BAYER A
G)); it may also contain other additives such as ultraviolet light absorbing compounds and / or silica.

The support for the thermographic material used in the method of preparing a lithographic printing plate according to the invention may be transparent, translucent or opaque, for example paper, polyethylene coated paper, metal (eg aluminum), aluminum containing Preference is given to flexible carriers made from an aluminum alloy in an amount of at least 95%, or transparent resin films made, for example, from cellulose esters (eg cellulose triacetate), polypropylene, polycarbonate or polyesters (eg polyethylene terephthalate). The support may be in the form of a sheet, ribbon or web and may be required to be hydrophilic to improve adhesion to the overlying heat-sensitive layer or to provide a hydrophilic surface. It may be primed. The support may be made from an opaque resin composition, for example made from opaque polyethylene terephthalate by pigments and / or microvoids and / or coated with an opaque pigment-binder layer. It can be referred to as synthetic paper or paper-like film. Information on such supports is given in EP 194106.
And 234563 and US-P 3,944,699,418.
7113, 4780402 and 5059579.

The production of an aluminum or aluminum foil having a hydrophilic surface according to the invention comprises the following steps: polishing, anodizing and optionally sealing the foil. Electrochemical polishing is preferred because it can form very fine and uniform particles and uniform surface roughness with a large average surface area.

"Handbook of Imaging Materials",
Arthur S. Diamond-Diamond Research Corporat
ion − Ventura, Calfornia, Marcel Dekker, Inc.
270 Madison Avenue, New York, New York 1
In thermal printing, as described in 0016 (1991) pp. 498-502, the image signal is converted to electrical pulses and then selectively transmitted to a thermal printhead through a drive circuit. Thermal printheads consist of tiny heating resistance elements, which convert electrical signals into heat by the Joule effect. The electrical signal thus converted to a thermal signal represents itself as heat transferred to the surface of the thermal paper where the chemical reactions occurring in color development take place. Such a thermal printhead can be used in contact with or near the recording layer. The operating temperature of a typical thermal printhead is in the range of 300-400 ° C., the heating time per pixel can be less than 1.0 ms, and the pressure contact between the recording material and the thermal printhead is For example, 200 to ensure good transmission
Is a -500g / cm ^2. A suitable thermal print head is, for example, a Fujitsu thermal head (FTP-040).
MCS001), TDK thermal head F415 HH
7-1089 and ROHM Thermal Head KE2008-
F3.

The thermographic material can be heated image-wise or pattern-wise by a modulated laser beam. For example, an image-modulated infrared laser light is absorbed by the thermographic material by an infrared light absorbing substance that converts the infrared light into the heat required for the imaging reaction. In this example, the thermographic material is a light-to-heat conversion material, such as WO 95/07822 and US
-Contains an infrared absorbing substance as described in P54097797. The use of infrared light emitting lasers and dye-donor elements containing infrared light absorbing materials is described, for example, in U.S. Pat.
2083. Infrared absorbing dyes suitable for laser-induced thermal dye transfer are described, for example, in U.S. Pat.
777, which must be read in combination therewith with US patents for lasers and dyes applied to direct thermal imaging.

The laser light applied according to the image need not be infrared light. This is because the power of the laser in the visible light range, and even in the ultraviolet range, can be so high as to generate sufficient heat by the absorption of the laser light in the thermographic material. The type of laser used is not limited, and may be a gas laser, a gas ion laser (eg, an argon ion laser), a solid state laser (eg, a Nd: YAG laser), a dye laser, or a semiconductor laser.

Such thermographic materials require light absorbing substances, so-called antihalation or acutance dyes, which absorb the light transmitted through the layer and thereby prevent its reflection. It is, for example, US-P
3515559, DE-P1927412, US-P4
033948, US-P4197131, EP-A12
020, CA-P1139149, US-P42712
63, EP-B101646, EP-B102781,
US-P4752559, EP-A3777961, US
-P5300420, EP-A627660, EP-A
652473, US-P5382504 and US-P5
395747.

The image signal for modulating the current or the laser beam in the micro-resistor of the thermal printhead can be obtained, for example, from an optoelectronic scanning device or from an intermediate storage means (for example, a magnetic disk or tape or optical disk storage medium; Connected to a digital imaging workstation that can be processed to satisfy

European Patent Application No. 9320326
3.4 describes a method of forming an image by heating according to an image by means of a thermal head having a heating element to which voltage can be applied, according to which activation of the heating element is performed according to a duty cycled pulse.

The image-wise thermal development of thermographic materials can be carried out, for example, using an electrical resistance ribbon incorporated in a multilayered material in which the carbon-containing polycarbonate is coated with a thin aluminum film ( See also: Progress inBasic Principles of Im
aging Systems− Proceedings of the International
al Congress of Photographic Science Koeln (Co
logne), 1986 edition, Friedrich Granzer and E.
rik Moisar-Friedr. Vieweg & Sohn-Braunschw
eig / Wiesbaden, Figure 6.622). Current is electrically injected into the printhead electrodes in contact with the carbon-containing support and injected into the resistive ribbon by intense intensive heating of the ribbon below the energized electrode. The aluminum film may be in direct contact with the heat-sensitive recording layer or its protective outermost layer.

When using a resistive ribbon thermographic material, heat is generated directly in the resistive ribbon and only the running ribbon becomes hot (not the printhead), with the inherent advantage in printing speed. In thermal printhead technology, various elements of the thermal printhead become hot and must be cooled so that the head can print unhindered at the next location.

Thermal development according to the image or pattern of the thermographic material may be performed by ultrasonic waves modulated on a pixel basis using an ultrasonic pixel printer as described, for example, in US Pat. No. 4,908,631.

An image signal for modulating an ultrasonic pixel printer, a laser beam or an electrode can be obtained, for example, from an optoelectronic scanning device or from an intermediate storage means (eg a magnetic disk or tape or optical disk storage medium, if desired, the image information meets specific requirements). Connected to a digital imaging workstation that can be processed as such.

The photographic material according to the present invention can be used with ultraviolet, visible or infrared wavelength lasers (eg 780, 830 or 850 nm).
By a pixel-based exposure using a finely focused light source such as a He / Ne laser or IR laser diode or a light emitting diode emitting at 659 nm, for example, or with appropriate illumination (eg UV, visible or red) Exposure may be with radiation at a wavelength between the X-ray wavelength and the 5 micron wavelength so that an image is obtained by directly exposing the light reflected from the object itself or an image therefrom using external light.

The coating of any layer of the thermal recording material of the present invention can be prepared, for example, by using Modern Coating and Drying Technology,
Ed. D. Cohen and Edgar B. Gutoff, eds.
92) VCH Publishers Inc. 220 East 23rd St
reet, Suite 909 New York, NY 10010, USA.

The following components were used in the photothermographic recording material used in the method of preparing a lithographic printing plate according to the invention, which illustrates the invention: Photo-addressable thermal development material: Butvar B76: polyvinyl butyral from MONSANTO; LOWINOX 22IB46 : 2-propyl-bis (2-hydroxy-3,5-dimethylphenyl) methane from CHEM, WERKE LOWI; TMDS: tribromomethylbenzenesulfinate; SENSI:

Embedded image Protective Layer: CAB: Cellulose acetate butyrate from EASTMAN, CAB-171-15S; PMMA: Polymethyl methacrylate from ROHM & HAAS, Acryloid K120N; LOWINOX 22IB46: 2-Propyl-bis (2- Hydroxy-3,5-dimethylphenyl) methane

The present invention is illustrated by the following examples, in which the percentages and ratios used in the examples are by weight unless otherwise specified.

[0074]

【Example】

Invention Example 1-Thermal Sensitive Layer A transparent, primed polyethylene terephthalate support having a thickness of 175 μm contains the following components and 2-butanone as a solvent so that a layer containing: Doctor blade coated from the following coating composition: silver behenate 4.7 g / m ² polyvinyl butyral [Butvar B79 from Monsanto] 18.9 g / m ² benzo [1,3] oxazine-2,4-dione (toning agent) 0.33 g / m ² n-butyl 3,4-dihydroxybenzoate (reducing agent) 1.22 g / m ² silicone oil [Baysilone OE1 from Bayer AG] 0.04 g / m ² tetrachlorophthalic anhydride (stabilizer) 0.15 g / m ² Pimelic acid (inhibitor) 0.5 g / m ²

Outermost hydrophilic layer The outermost hydrophilic layer is a doctor blade on the thermosensitive layer from an aqueous coating suspension containing the following components in such amounts so as to form after drying a coating containing: coated: polyvinyl alcohol 2.2 g / m ² tetramethyl orthosilicate 2.9 g / m ² polytetrafluoroethene powder [Hostaflon TF5032 from Hoechst AG] 0.45g / m ² polyamide wax [Hoechst [Wacker Chemie Polyviol WX48 from AG] Ceridust 3910] 0.13g / m ² talc from AG (talcum) [Nippon from talc Co. Ltd. Microace talc P3] 0.13g / m 2 of sodium salt of an aryl sulfonate [Ciba-Geigy Ultravon W from AG] 0.22 g / m ² 15% aqueous dispersion of colloidal silica [Levasil VP AC 4055 from Bayer AG] 0.9 g / m ²

The outermost hydrophilic layer was then treated at 57 ° C. and 34% R
H cured for 3 days.

Thermal Imaging and Processing A 10 cm × 10 cm sheet of the resulting thermographic material is printed at a resolution of 300 dpi and a line time of 19 ms (line time is the time required to print one line). , 70% duty cycle, 5 W / mm ² average print output (which is the total amount of electrical input energy per line time divided by the line time and by the surface area of the heat generating resistor) and about 230 g / linear cm. AGFA-GEVAERT NV operated with pressure between thermal head and thermographic material applied along the thermal head
DRYSTAR from thin film thermal head printer
The image was thermally developed with a printer according to the image.

After image-wise thermal development, the sheet of thermographic material was cooled to room temperature. The outermost hydrophilic layer on the same side of the thermographic material was then in intimate contact with an adhesive tape (TESA 4122 from Beiersdorf AG) as a thermosensitive layer. The tape is then stripped from those areas of the outermost hydrophilic layer corresponding to the areas thermally developed according to the image of the thermographic material adhered thereto, thereby removing those portions of the outermost hydrophilic layer from the thermosensitive layer. separated.

-Printing Experiments: Pre-wetted with a 3% aqueous solution of the humidification solution G671 ™ from AGFA-GEVAERT NV and then with the material produced using an offset printer type 360 Varn from AB Dick Inc. An ink experiment was performed. In that experiment, the image area of the lithographic printing plate was used with the oily lithographic printing ink (printing ink Rubberbase VS from Van Son Inc.).
2329) and found that the non-image areas do not accept this ink. Excellent discrimination in ink receptive behavior between image and non-image areas was obtained from MACBETH Inc.
D904 using a densitometer were measured through a visible filter with a minimum optical density and maximum optical density of 1.25 0.07, no sharp background obtained by printing on 80 g / m ² offset paper Confirmed by print.

Invention Example 2-Aluminum foil support Using a 0.15 mm thick aluminum foil lithographic printing plate,
It is electrochemically roughened and anodized, using conventional manufacturing techniques for lithographic printing plates, with a 0.5 μm D
A hydrophilic surface having a surface topology of average center line roughness Ra according to IN4768 and ISO4287 / 1 was formed.

-Silver halide emulsions For example, TH James, "Theory of the Photog
raphic Process ", 4th edition, Macmillan Publishing
Co. Inc., New York (1977), Chapter 3, 88-
ROUSSELO as a dispersant in deionized water using conventional silver halide manufacturing techniques as described on page 104
Type 16875 from T, 0.47% by weight of phthaloyl gelatin, 3.11% by weight of silver halide grains consisting of 97 mol% of silver bromide and 3 mol% of silver iodide having a weight average particle size of 50 nm An emulsion was prepared.

Silver Behenate / Silver Halide Emulsion A solution of 67 l of 2-propanol at 6.8 kg of behenic acid at 65 ° C. was added to a 400 l vessel heated to maintain the temperature of the contents at 65 ° C. 0 in deionized water.
76.8 l of 25 M sodium hydroxide are added with stirring, and then 10.5 kg of the above silver halide emulsion at 40 ° C.
A silver behenate / silver halide emulsion is prepared by converting 96% of the behenic acid to sodium behenate by adding with stirring and finally adding 48 l of a 0.4 M solution of silver nitrate in deionized water with stirring. did.
After the addition of silver nitrate is complete, cool the contents of the container,
The precipitate was filtered, washed, slurried with water, filtered again and finally dried at 40 ° C. for 72 hours.

Next, 7 kg of dry powder containing 9 mol% of silver halide and 4 mol% of behenic acid, based on silver behenate, are combined with 15.6 kg of 25.6 kg of conventional powder using a conventional dispersion technique to produce a 33% by weight dispersion. 700 in butanone
g of Butvar B76. Then 7.4 kg
Of 2-butanone was added with stirring, and the resulting dispersion was homogenized in a microfluidizer. Finally, a 2.8kg Butv
ar B76 was added with stirring to produce a dispersion having 31% by weight solids.

Coating and drying of silver behenate / silver halide emulsion layer 40.86 in the following order while stirring the following solution or liquid:
A coating composition was prepared for the emulsion layer of the photothermographic material by adding to 6. g of the above silver behenate / silver halide emulsion: 6.87 g of 2-butanone,
Add 0.95 g of a 9% solution of tetramethylammonium bromide perbromide in methanol and add 2
Stir for 0.2 h, add 0.2 g of a 11% solution of calcium bromide in methanol and 1.39 g of 2-butanone, stir for 30 min, and add 0.21 g of LOWINOX 22I
A solution consisting of B46, 0.5 g of TMPS and 9.24 g of 2-butanone was added and stirred for 15 minutes, and 1.8 g of
A 0.11% solution of SENSI in methanol was added and stirred for 30 minutes, and finally 4.35 g Butvar B76 was added and stirred for 45 minutes.

The anodized (hydrophilic) side of the aluminum foil was then coated with a coating composition of the emulsion layer of the photothermographic material to a wet layer thickness of 75 μm by 100 μm.
The doctor blade was coated with a blade setting of 5% and dried on an aluminum plate in a dryer at 80 ° C. for 5 minutes before producing a layer having the following composition: Butvar B76 8.70 g / m ² from ROUSSELOT Phthaloyl gelatin type 16875 0.045 g / m ² AgBr _0.97 I _0.03 0.301 g / m ² Silver behenate 7.929 g / m ² Tetramethylammonium bromide Perbromide 0.0855 g / m ² (15.2 mmol / mol silver behenate ) calcium bromide ^{0.022g / m 2 LOWINOX 22IB46 0.210g /} m 2 SENSI 0.002g / m 2 TMPS 0.500g / m 2

Outermost hydrophobic layer The outermost hydrophobic layer coating composition for the photothermographic material was prepared by adding 56.06 g of 2-butanone and 5.2 g.
Prepared by dissolving 4.08 g of CAB and 0.16 g of PMMA in 0.5 g of methanol and adding the following solution or liquid with stirring in the following order: 0.5 g of phthalazine, 0.2 g of 4-methylphthalic acid 0.1 g tetrachlorophthalic acid, 0.2 g tetrachlorophthalic anhydride and 2.55 g LOWINOX 22IB46 and 5.9
Solution consisting of 5 g of 2-butanone.

The photothermographic emulsion layer was then coated with an outermost hydrophobic layer composition of 100 μm to a wet layer thickness of 80 μm.
Doctor blade coating with a blade setting of μm, which was dried on an aluminum plate in a drier at 80 ° C. for 8 minutes before producing a layer having the following composition: PMMA 0.16 g / m ² CAB 4.08 g / m ² phthalazine 0.50 g / m ² 4-methylphthalic 0.20 g / m ² tetrachlorophthalic anhydride 0.20 g / m ² tetrachlorophthalic acid ^{0.10g / m 2 LOWINOX 22IB46 2.55g /} m 2

Imagewise exposure and heat treatment The thermographic material was then exposed for 30 seconds to an EG & G lamp through a wedge filter and an L775 filter with an optical density varying between 0 and 3.0 in steps of 0.15. .

The heat treatment was performed by bringing the aluminum drum heated to a temperature of 115 ° C. for 15 seconds into close contact with the coated side of the photothermographic material.

The change in the optical density of the generated wedge image was evaluated by reflection with a MACBETH RD918-SB densitometer using a visible filter. It was measured at a _{Dmax of} 1.78 and a _Dmin value of 0.63.

Delamination for the production of lithographic printing plates The photothermographic material so exposed and thermally treated is coated with a piece of adhesive tape TESAPACK 4122 supplied by BEIERSDORF. Applied by hand on the applied side under pressure and then delaminated by peeling off the tape at a speed of 6 cms ^-1 and an angle of 180 °, then peeling the exposed area of the photothermographic coating from the aluminum plate,
A lithographic printing plate was produced, leaving unexposed areas of the photothermographic coating that were not stripped.

-Printing experiments Inks experiments were carried out on the material produced using an offset printer type Sakurai Oliver 52 from Sakurai, pre-wetted with deionized water. In this experiment, BASF Coa
Using K + E171 ink from ting & Inks as printing ink, ROTAMATIC Feuchtmi from ROTAPRINT
ttel R35 was used as the humidifier. The non-image areas of the lithographic printing plate have been found to accept the oily lithographic inks preferably used on the image areas. The identity in the ink receiving behavior between images and non-image areas was confirmed by negative print visually discernible obtained on paper 80 g / m ² offset.

Having described preferred examples of the invention in detail,
It will be apparent to those skilled in the art that numerous modifications may be included herein without departing from the scope of the invention as defined in the claims.

Continuation of the front page (56) References JP-A-6-186746 (JP, A) US Patent 3,679,414 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41N 1/14 G03F 7 / 06-7/07 G03F 7/00

Claims (8)

(57) [Claims] 1. A method for producing a lithographic printing plate comprising the following steps: (i) a lithographic printing plate comprising a support, a hydrophobic thermosensitive layer and a hydrophilic surface adjacent to the hydrophobic thermosensitive layer. Heat-developing a substantially light-insensitive thermographic material which can be used to produce a thermosensitive material according to a positive or negative image, provided that said hydrophobic thermosensitive layer comprises component A, Directly reacts with at least one other component B in thermal relationship with component A to create a portion that alters the adhesion between the hydrophobic thermosensitive layer and the adjacent hydrophilic surface, provided that component A.
Or if one of B is an organometallic salt and the other of components A or B is a reducing agent for said organometallic salt, said reducing agent is selected from the group consisting of: Aromatic compounds having at least two hydroxy groups in the above ortho- or para-position; aminophenol; p-phenylenediamine; alkoxynaphthol;
Pyrazolidin-3-one; pyrazolin-5-one; indane-1,3-dione derivative; hydroxytetronic acid;
(Hydroxytetronimide; hydroxylamine derivative; hydrazine derivative; and reductone); and (ii) separating the hydrophobic thermosensitive layer from the adjacent hydrophilic surface according to a positive or negative image. 2. A method for producing a lithographic printing plate, comprising the steps of: (i) a lithographic printing plate comprising a support, a hydrophobic thermosensitive layer and a hydrophilic surface adjacent to the hydrophobic thermosensitive layer. Exposing the thermographic material which can be used to produce a thermographic material to actinic radiation according to a positive or negative image, provided that said hydrophobic thermosensitive layer comprises a component A, which, when heated, Reacts directly with at least one other component B in the relationship to create a portion that alters the adhesion between the hydrophobic thermosensitive layer and the adjacent hydrophilic surface, and further comprises a photosensitizer in the hydrophobic thermosensitive layer. And the photosensitizer catalyzes the reaction between the component A and the component B after exposure to directly change the adhesive force between the hydrophobic thermosensitive layer and the adjacent hydrophilic surface. Can be made, provided that one of the components A or B Is an organometallic salt, and the other of components A or B is a reducing agent for said organometallic salt, said reducing agent is selected from the group consisting of: Or an aromatic compound having at least two hydroxy groups at the para-position; aminophenol; p-phenylenediamine; alkoxynaphthol; pyrazolidin-3-one; pyrazolin-5-one;
-Dione derivatives; hydroxytetronic acid; hydroxytetronimide; hydroxylamine derivatives; hydrazine derivatives; and reductone); (ii) thermally developing the imagewise exposed thermographic material; and (iii) the adjacent hydrophilic surface. From the hydrophobic thermosensitive layer according to a positive or negative image. 3. The method of claim 1, wherein said component A is a substantially non-photosensitive organic silver salt, and said component B in thermal relationship with said component A is between the hydrophobic thermosensitive layer and the adjacent hydrophilic surface. 3. The method for producing a lithographic printing plate according to claim 1, wherein the reducing agent is capable of reducing the substantially non-photosensitive organic silver salt when heated to form a hydrophobic portion that reduces the adhesive force. 4. The method for producing a lithographic printing plate according to claim 1, wherein the hydrophobic thermosensitive layer is coated on a hydrophilic surface. 5. The method according to claim 4, wherein the hydrophilic surface is a surface of a hydrophilic layer. 6. The method according to claim 4, wherein the hydrophilic surface is a surface of the support. 7. The method according to claim 1, wherein the hydrophobic thermosensitive layer is an outermost layer. 8. The method according to claim 5, wherein the hydrophilic layer is an outermost layer that provides a hydrophilic surface adjacent to the hydrophobic thermosensitive layer.