JPH10111564A - Image forming material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a positive and negative image forming material having high sensitivity and to obtain an image forming method by forming a photosensitive layer containing a compd. which can produce acid by irradiation of active rays, drawing an image with IR rays and removing the exposed part with an alkali developer. SOLUTION: A photosensitive layer containing a compd. which produces acid by irradiation of active rays, a compd. which decomposes or crosslinks in the presence of acid, an IR absorbent and solid fine particles is formed on a supporting body. After an image is drawn with IR rays, the exposed part is removed by using an alkali developer. The compd. which can produce acid by irradiation of active rays is a compd. such as diazonium and phosphonium or a combination mixture of org. metals/org. halides. The compd. which crosslinks in the presence of acid is an amino compd. having at least two alkoxymethyl groups as functional groups. As for the IR absorbent, an IR absorbing dye or the like showing absorption over >=700nm wavelength can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive layer comprising an infrared-sensitive composition comprising a compound capable of generating an acid upon irradiation with an actinic ray, a compound capable of decomposing or crosslinking in the presence of an acid, and an infrared absorber. The present invention relates to an image forming material and an image forming method using the same.

[0002]

2. Description of the Related Art Conventionally, an image forming material having a photosensitive layer containing an acid generator and an acid-decomposable compound as a positive photosensitive layer solubilized by irradiation with actinic light is known.
That is, U.S. Pat. No. 3,779,779 discloses a photosensitive composition containing a compound having an orthocarboxylic acid or a carboxylic amide acetal group.
JP-A-33429 discloses a photosensitive composition containing a compound having an acetal or ketal group in the main chain, and JP-A-60-37549 discloses a composition containing a compound having a silyl ether group. It has been disclosed. However, all of these are sensitive to ultraviolet light, and are alkali-solubilized by exposure to ultraviolet light to become non-image portions, and cannot be used for image exposure with infrared light such as inexpensive and compact semiconductor lasers.

On the other hand, US Pat. No. 5,340,69 discloses a technique capable of exposing an image with infrared rays such as a semiconductor laser.
No. 9 has a photosensitive layer containing an acid generator, a resole resin, a novolak resin and an infrared absorber, and is used as a negative image by performing a heat treatment after image exposure and before development. In addition, there is disclosed a technique which is used as a positive type image forming material unless the above heat treatment is performed. However, there is a disadvantage that the sensitivity is low in both the negative type and the positive type.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive type image forming material and a negative type image forming material capable of forming an image by exposure to infrared rays and having high sensitivity, and an image forming method using the same. It is to provide.

[0005]

The present invention that achieves the above object is the following (1) and (2).

(1) A photosensitive layer containing, on a support, a compound capable of generating an acid upon irradiation with actinic rays, a compound capable of decomposing or crosslinking in the presence of an acid, an infrared absorber and solid fine particles. Image forming material.

(2) An image forming method comprising: drawing an image on the photosensitive layer of the image forming material according to claim 1 using infrared rays; and removing exposed portions with an alkaline developer.

Hereinafter, the present invention will be described in detail.

The compound capable of generating an acid upon irradiation with actinic rays (hereinafter referred to as "acid generator") used for the photosensitive layer of the image forming material of the present invention includes various known compounds and mixtures. For example, BF ₄ ⁻ , P of diazonium, phosphonium, sulfonium, and iodonium
Salts such as F ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ²⁻ , ClO ₄ ⁻ , organohalogen compounds, orthoquinone-diazidosulfonyl chloride, and combinations of organometallic / organohalogen compounds are also affected by irradiation with actinic rays. And is an actinic ray-sensitive component that forms or separates, and can be used as an acid generator. In principle, all organic halogen compounds known as free radical-forming photoinitiators are compounds which form hydrohalic acids and can be used as acid generators.

Examples of the above-mentioned compounds forming a hydrohalic acid are described in US Pat. Nos. 3,515,552, 3,536,489 and 3,779,778, and West German Patent Publication. The compounds described in JP-A-2,243,621 can be mentioned, and for example, compounds capable of generating an acid by photolysis described in West German Patent Publication No. 2,610,842 can also be used. .

Further, Japanese Patent Application Laid-Open No. 54-74728,
JP-A-55-24113, JP-A-55-7774
No. 2, JP-A-60-3626, JP-A-60-60
2-halomethyl-1,3,3 described in JP-B-138539
Specifically, 2-trichloromethyl-5- [β (2-benzofuryl) vinyl] -1,3,4-oxadiazole such as a 4-oxadiazole-based compound can be used.

A specific example of the acid generator is disclosed in
No. 17345 can be mentioned.
Further, o-naphthoquinonediazido-4-sulfonic acid halogenide described in JP-A-50-36209 can be used.

In the present invention, particularly preferred acid generators are diazonium salts and oxadiazole organic halogen compounds from the viewpoint of sensitivity. Further, when used as a lithographic printing plate, diazonium salts are most preferred from the viewpoint of printing performance.

In the present invention, an organic halogen compound is preferred as an acid generator from the viewpoint of sensitivity in image formation by infrared exposure and storage stability of the image forming material. As the organic halogen compound, a triazine having a halogen-substituted alkyl group and an oxadiazole having a halogen-substituted alkyl group are preferable, and an s-triazine having a halogen-substituted alkyl group is particularly preferable.

Specific examples of oxadiazoles having a halogen-substituted alkyl group are described in JP-A-54-74728.
JP-A-55-24113, JP-A-55-7774
No. 2, JP-A-60-3626 and JP-A-60-138
No. 539, 2-halomethyl-1,3,4-
Oxadiazole-based compounds are exemplified. Of these, 2-trichloromethyl-5- {β (2-benzofuryl) vinyl} -1,3,4-oxadiazole is preferred.

S- having a halogen-substituted alkyl group
As the triazine, a compound represented by the following general formula (1) is preferable.

[0017]

Embedded image

In the general formula (1), R is an alkyl group,
X represents a halogen-substituted alkyl group or an aryl group (for example, a phenyl group or a naphthyl group) or a substituted product thereof, and X represents a halogen atom.

Specific examples of the s-triazine represented by the general formula (1) are shown below.

[0020]

Embedded image

[0021]

Embedded image

In the present invention, the content of the acid generator can be varied over a wide range depending on its chemical properties and the composition or physical properties of the photosensitive layer of the image forming material of the present invention.
The amount is suitably in the range of about 0.1 to about 20% by weight, preferably 0.2 to 10% by weight, based on the total weight of the solid content of the photosensitive layer.
Range.

The compound used in the photosensitive layer of the image forming material of the present invention and having at least one bond decomposable by an acid (hereinafter referred to as "acid-decomposable compound") is specifically described in JP-A-48-89003. No. 51-120714
No. 53-133429, No. 55-12959,
Nos. 55-126236 and 56-17345, compounds having a C—O—C bond described in the specification of the same;
Compounds having a Si-OC bond described in the specifications of JP-A-60-37549 and JP-A-60-112446, and compounds described in JP-A-60-3625 and JP-A-60-10247. Other acid-decomposable compounds described, and compounds having an Si-N bond described in the specification of Japanese Patent Application No. 61-16687, Japanese Patent Application No. 61-9 / 1986.
Carbonates described in the specification of US Pat.
Ortho carbonate described in the specification of Japanese Patent Application No. 60-251744, orthotitanate described in the specification of Japanese Patent Application No. 61-125473, specification of Japanese Patent Application No. 61-125474. Orthosilicates described in the specification, acetal and ketal described in the specification of Japanese Patent Application No. 61-155481, and C described in the specification of Japanese Patent Application No. 61-87769.
A compound having a -S bond or the like can be used.

Of the above, Japanese Patent Application Laid-Open No. Sho 53-13342
No. 9, 56-17345, 60-12446
No., Japanese Patent Application No. 60-37549 and Japanese Patent Application No. Sho 60-2.
Compounds having a C—O—C bond described in the specification of Nos. 51744 and 61-155481, Si—O—
Compounds having a C bond, orthocarbonates, acetals, ketals and silyl ethers are preferred.

Among them, JP-A-53-13342
Japanese Patent Application Laid-open No. Sho 63-93 discloses an organic polymer compound having a repeating acetal or ketal moiety in the main chain and having its solubility in a developer increased by the action of an acid.
The following structural unit described in -10153

[0026]

Embedded image

Compounds having the formula and which can be decomposed by an acid are particularly preferred.

Specific examples of the acid-decomposable compound of the present invention include the compounds described in the above specifications. The method for synthesizing the compound is described in each of the above specifications.

In the present invention, the acid-decomposable compound is-
A compound having a (CH ₂ CH ₂ O) _n -group (n represents an integer of 2 to 5) is preferable from the viewpoint of balance between sensitivity and developability. Among these compounds, compounds in which the number n of ethyleneoxy groups is 3 or 4 are particularly preferred.

Specific examples of the above compounds include condensation products of dimethoxycyclohexane, benzaldehyde and substituted derivatives thereof with any of diethylene glycol, triethylene glycol, tetraethylene glycol and pentaethylene glycol.

In the present invention, a compound represented by the following general formula (2) is preferable as the acid-decomposable compound from the viewpoint of sensitivity and developability.

[0032]

Embedded image

Of the compounds represented by the general formula (2), m
And compounds wherein n is 1 or 2 are particularly preferred.

In the present invention, the content of the acid-decomposable compound is from 5 to 7 with respect to the total solid content of the composition for forming the photosensitive layer.
0% by weight is preferred, and particularly preferably 10 to 50% by weight.
It is. The acid-decomposable compounds of the present invention may be used alone or in a combination of two or more.

A compound capable of crosslinking in the presence of an acid contained in the photosensitive layer of the image forming material of the present invention (hereinafter referred to as "acid crosslinking compound")
) As an alkoxymethyl group as a functional group,
Amino compounds having at least two methylol groups, acetoxymethyl groups and the like, for example, melamine derivatives [hexamethoxymethylated melamine (Mitsui Cyanamid Co., Ltd.)
Cymel 300 series (1), etc.)], benzoguanamine derivatives [Methyl / ethyl mixed alkylated benzoguanamine resin (Cymel 11 manufactured by Mitsui Cyanamid Co., Ltd.)
00 series (2)), etc.), glycoluril derivatives [tetramethylol glycoluril (Cymel 1100 series (3) manufactured by Mitsui Cyanamid Co., Ltd.), etc.],
Further, at least a disubstituted aromatic compound having an alkoxymethyl group, a methylol group, an acetoxymethyl group or the like as a functional group, for example, 1,3,5-triacetoxymethylbenzene, 1,2,4,5-tetraacetoxymethyl Benzene and the like can be mentioned, and these are described in Polym. Mas
ter. Sci. Eng. , 64 , 241 (1991).
Can be synthesized.

[0036] In addition to the above, resole resins and furan resins can also be used as the acid crosslinking compound. Further, an acrylic resin synthesized from monomers including the following monomers can be used.

N-methylolacrylamide, N-methylolmethacrylamide, N, N-dimethylolacrylamide, N, N-dimethylolmethacrylamide, N
-(2-hydroxyethyl) acrylamide, N- (2
-Hydroxyethyl) methacrylamide, N, N-di (2-hydroxyethyl) acrylamide, N, N-di (2-hydroxyethyl) methacrylamide, N-hydroxymethyl-N- (2-hydroxyethyl) acrylamide, N -Hydroxymethyl-N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether, vinylbenzyl alcohol, α-methylvinylbenzyl alcohol, vinylbenzyl acetate, α-
An embodiment in which any one of methylvinylbenzyl acetate, vinylphenethyl alcohol, α-methylvinylphenethyl alcohol, vinylphenethyl acetate, and α-methylvinylphenethyl acetate is copolymerized in an amount of 1 to 50 mol%, preferably 5 to 30 mol%. .

Further, a material in which the surface of the solid fine particles contained in the photosensitive layer of the present invention is modified with a crosslinking group contained in the acid crosslinking compound as described above can be used.

The content of the acid crosslinking compound of the present invention is preferably from 5 to 60% by weight, particularly preferably from 20 to 45% by weight, based on the total solid content of the composition for forming the photosensitive layer. One kind of the acid crosslinking compound may be used alone, or two or more kinds may be used as a mixture.

As the infrared absorber used in the photosensitive layer of the image forming material of the present invention, an infrared absorbing dye having absorption at a wavelength of 700 nm or more, carbon black, magnetic powder and the like can be used. A particularly preferred infrared absorber is 700
It is an infrared absorbing dye having an absorption peak at 〜850 nm and a molar extinction coefficient ε at the peak of 10 ⁵ or more.

Examples of the infrared absorbing dye include cyanine dyes, squarium dyes, croconium dyes, azurenium dyes, phthalocyanine dyes, naphthalocyanine dyes, polymethine dyes, naphthoquinone dyes, thiopyrylium dyes, and dithiol metal dyes. Examples include complex dyes, anthraquino dyes, indoaniline metal complex dyes, and intermolecular CT dyes.

Further, as the above-mentioned infrared absorbing dye, JP-A-6
3-139191 and 64-33547, JP-A-1
-160683, 1-280750, 1-29
No. 3342, No. 2-2074, No. 3-26593,
3-30991, 3-34891, 3-36
Nos. 093, 3-36094, 3-36095,
The compounds described in JP-A-3-42281 and JP-A-3-103476 are exemplified.

In the present invention, a cyanine dye represented by the following general formula (3) or (4) is particularly preferred as the infrared absorber.

[0044]

Embedded image

In the above formula, Z ₁ and Z ₂ each represent a sulfur atom, a selenium atom or an oxygen atom, and X ₁ and X ₂ each form an optionally substituted benzo-fused ring or naphtho-fused ring. R ₁ and R ₂ each represent a substituent, and _one of R ₁ and R ₂ has an anionic dissociable group. R ₃ , R ₄ , R ₅ and R ₆ each represent an alkyl group having 1 to 3 carbon atoms, a hydrogen atom or a halogen atom. L represents a chain of conjugated bonds having 5 to 13 carbon atoms.

The cyanine dyes represented by the general formula (3) or (4) include those in which the general formula (3) or (4) forms a cation and has a counter anion. In this case, as the counter anion, Cl ⁻ , Br ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ ,
Alkyl boron such as t-butyltriphenylboron and the like can be mentioned.

In the general formula (3) or (4), the number of carbon atoms (n) of the conjugated bond chain represented by L is determined by using a laser emitting infrared light as a light source for image exposure. It is preferable to select an effective value according to the transmission wavelength of the light. For example, Y at an emission wavelength of 1060 nm
When an AG laser is used, n is preferably 9 to 13. The conjugate bond may have an arbitrary substituent, and the conjugate bond may form a ring with a plurality of substituents.

In the general formula (3) or (4), the ring represented by X ₁ and the ring represented by X ₂ can have any substituent. Halogen atom as the substituent, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, (the M hydrogen atom or an alkali metal atom) -SO ₃ M and -COOM is a group selected from the preferred .

[0049] Although R ₁ and R ₂ are optional substituents, preferably, an alkyl or alkoxy group ;-( CH ₂ 1 to 5 carbon _{atoms) n -O-) k - (CH} 2) m OR (n
And m are each an integer of 1 to 3, k is 0 or 1, and R represents an alkyl group having 1 to 5 carbon atoms. _One of R ₁ and R ₂ is —R—SO ₃ M and the other is —R—SO ₃ ⁻ (R represents an alkyl group having 1 to 5 carbon atoms, M represents an alkali metal atom); ₁ and one the other is -R-COOM of R ₂ is -COO ^- (R is an alkyl group having 1 to 5 carbon atoms, M
Represents an alkali metal atom. ). R ₁ and R ₂ are
In terms of sensitivity and developability, _one of R ₁ and R ₂ is -RS
O ₃ ^- or -R-COO ^-, the other is -R-SO ₃ M or -R
-COOM is preferred.

The cyanine dye represented by formula (3) or (4) has an absorption peak at 750 to 900 nm when a semiconductor laser is used as a light source for image exposure, and at 900 to 1200 nm when a YAG laser is used. And those having a molar extinction coefficient of ε> 1 × 10 ⁵ are preferred.

Representative specific examples of the infrared absorbent preferably used in the present invention are shown below, but are not limited thereto.

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

These dyes can be synthesized by a known method, but the following commercially available products can also be used.

Nippon Kayaku: IR750 (anthraquinone type); IR002, IR003 (aluminum type);
R820 (polymethine type); IRG022, IRG03
3 (diimmonium-based); CY-2, CY-4, CY-
9, CY-20 Mitsui Toatsu: KIR103, SIR103 (phthalocyanine-based); KIR101, SIR114 (anthraquinone-based); PA1001, PA1005, PA1006, S
IR128 (metal complex type) Dainippon Ink and Chemicals: Fastogen blue 812
0 Midori Kagaku: MIR-101, 1011, 1021 Others are also commercially available from companies such as Nippon Kogaku Dyestuffs, Sumitomo Chemical, and Fuji Photo Film.

In the present invention, the amount of the infrared absorbent added is preferably in the range of 0.5 to 5% by weight. When the amount added is 5
%, the developability of the non-image area is reduced, and
If the amount is less than t%, the development resistance of the image portion is reduced.

The solid fine particles contained in the photosensitive layer of the image forming material of the present invention include crosslinked or uncrosslinked polymethyl methacrylate, polystyrene, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, Fine particles formed of polyethylene terephthalate, crosslinked vinyl polymer, etc., fine particles of silicon dioxide (eg, colloidal silica), diatomaceous earth, zinc oxide, titanium oxide, zirconium oxide, glass, alumina, dextrin, starch (eg, rice starch) , Calcium stearate, zinc stearate,
Polysaccharide fatty acid ester, polyvinyl acetate, polyvinylidene chloride, polyethylene oxide, polyethylene glycol, polyacrylic acid, polyacrylamide, polyacrylic acid alkyl ester, polystyrene and polystyrene derivatives, and copolymers using monomers of these polymers , Polyvinyl methyl ether, epoxy resin, fusible phenol resin, polyamide, polyvinyl butyral, and the like. In the present invention,
As the solid fine particles, silica particles or crosslinked acrylic resin particles are preferable.

In the present invention, the average particle size of the solid fine particles is preferably in the range of 0.01 to 0.5 μm. The average particle diameter of the solid fine particles can be measured by, for example, a diffusion type particle size distribution meter, and the peak is a value read from the data of “particle diameter-% by weight”.

In the present invention, the photosensitive layer may contain a binder. As the binder, for example, a high molecular weight binder can be used. As the high molecular weight binder, for example, a novolak resin, a polymer having a hydroxystyrene unit, or a polymer having a structural unit represented by the following general formula (5) And other known acrylic resins.

Examples of the novolak resin include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde copolycondensate resin described in JP-A-55-57841, and And a copolycondensate resin of p-substituted phenol and phenol or cresol and formaldehyde as described in JP-A-127553.

Examples of the polymer having a hydroxystyrene unit include polyhydroxystyrene and a hydroxystyrene copolymer described in JP-B-52-41050.

The polymer having the structural unit represented by the general formula (5) may be a homopolymer having a repeating structure composed of only the structural unit or an unsaturated dimer of the structural unit and another vinyl monomer. It is a copolymer in which one or more structural units having a structure in which a heavy bond is cleaved are combined.

[0073]

Embedded image

In the general formula (5), each of R ₁ and R ₂ represents a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, or a carboxylic acid group, and is preferably a hydrogen atom. R
₃ represents a hydrogen atom, a halogen atom such as a chlorine atom or a bromine atom or an alkyl group such as a methyl group or an ethyl group, and is preferably a hydrogen atom or a methyl group. R ₄ represents a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, a phenyl group or a naphthyl group.

Y represents a phenylene group or a naphthylene group including a substituent; examples of the substituent include an alkyl group such as a methyl group and an ethyl group; a halogen atom such as a chlorine atom and a bromine atom; a carboxylic acid group; And an alkoxy group such as ethoxy group, a hydroxyl group, a sulfonic acid group, a cyano group, a nitro group, an acyl group, etc., and preferably have no substituent or are substituted with a methyl group.

X is a divalent organic group linking a nitrogen atom and an aromatic carbon atom, and n represents an integer of 0 to 5, and is preferably 0.

The polymer having the structural unit represented by the general formula (5) is more specifically exemplified by the following (a) to (h)
Can be represented by

[0078]

Embedded image

In (a) to (h), R _{1 to} R ₅ each represent a hydrogen atom, an alkyl group or a halogen atom;
Represents an alkyl group or a halogen atom. Also, m, n,
1, k and s represent mol% of each structural unit.

A novolak resin, a polymer having a hydroxystyrene unit, a polymer having a structural unit represented by the general formula (4), and an acrylic resin can also be used in combination.

Further, a lipophilic resin can be added to the photosensitive composition of the present invention in order to improve the oil sensitivity of the photosensitive composition.

The lipophilic resin includes, for example, those described in JP-A-50-125806.
Condensates of phenols and aldehydes substituted with an alkyl group having 3 to 15 carbon atoms, such as t-butylphenol formaldehyde resin, can be used.

If necessary, the photosensitive layer of the image forming material of the present invention may further contain other dyes, pigments, sensitizers and the like.

The photosensitive layer of the present invention is dissolved in the following solvent which dissolves each of the above-mentioned components, and these are applied to the surface of a suitable support and dried to form a photosensitive layer, and the image-forming material of the present invention is obtained. can do.

Examples of the solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate, dimethylformamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, trichloroethylene, methyl ethyl ketone and the like. No. These solvents are used alone or in combination of two or more.

The coating method can be a conventionally known method, for example, spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating and the like. The amount of application varies depending on the application, for example,
Speaking of photosensitive lithographic printing plates, 0.5 to 0.5
5.0 g / m ² is preferred.

The support on which the photosensitive layer of the present invention is provided may be a metal plate such as aluminum, zinc, steel, or copper, a metal plate plated with chromium, zinc, copper, nickel, aluminum, iron, or the like, paper, or the like. Examples thereof include a plastic film and a glass plate, a resin-coated paper, a paper covered with a metal foil such as aluminum, a plastic film subjected to a hydrophilic treatment, and the like. Of these, an aluminum plate is preferred. When the present invention is applied to a photosensitive lithographic printing plate, it is preferable to use, as a support, an aluminum plate which has been subjected to surface treatment such as graining treatment, anodic oxidation treatment and, if necessary, sealing treatment. A known method can be applied to these processes.

Examples of the graining method include a mechanical method and an electrolytic etching method.
Examples of the mechanical method include a ball polishing method, a brush polishing method, a polishing method using liquid honing, and a buff polishing method. The various methods described above can be used alone or in combination depending on the composition of the aluminum material and the like.

For etching by electrolysis, phosphoric acid,
It is carried out using a bath in which inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid are used alone or in combination of two or more. After the graining treatment, if necessary, a desmut treatment is performed with an aqueous solution of an alkali or an acid to neutralize and wash with water.

The anodic oxidation treatment is carried out by using a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid or the like as an electrolytic solution, and using an aluminum plate as an anode for electrolysis. The amount of anodic oxide film formed is 1 to 50 m
g / dm ² is suitable, and preferably 10 to 40 mg / g.
dm ² , particularly preferably 25 to 40 mg / dm ² . The amount of the anodic oxide film is determined, for example, by immersing the aluminum plate in a chromic phosphate bath solution (prepared by dissolving 35 g of phosphoric acid 85% solution and 20 g of chromium (IV) oxide in 1 liter of water) to dissolve the oxide film. It is determined from the weight change measurement before and after dissolution of the coating on the plate.

Examples of the pore-sealing treatment include boiling water treatment, steam treatment, sodium silicate treatment, and dichromate aqueous solution treatment. In addition, the aluminum plate support may be subjected to an undercoating treatment with an aqueous solution of a water-soluble polymer compound or a metal salt such as fluorinated zirconic acid.

The image forming material of the present invention has a wavelength of 700 nm.
Image exposure is performed using the above light sources. Examples of the light source include a semiconductor laser, a He-Ne laser, a YAG laser, a carbon dioxide laser, and the like. The output is suitably 50 mW or more, preferably 100 mW or more.

As the developer used for developing the image forming material of the present invention, an aqueous alkali developer is suitable. Examples of the aqueous alkaline developer include sodium hydroxide,
Aqueous solutions of alkali metal salts such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, dibasic sodium phosphate and tribasic sodium phosphate are exemplified. The concentration of the alkali metal salt is 0.1.
It is suitable to use in the range of 05 to 20% by weight, more preferably 0.1 to 10% by weight.

In the image forming method of the present invention, an anionic surfactant, an amphoteric surfactant or an organic solvent such as alcohol can be added to the developer as required.

As the organic solvent, propylene glycol, ethylene glycol monophenyl ether, benzene alcohol, n-propyl alcohol and the like are useful.

[0096]

Next, the present invention will be described more specifically with reference to examples.

Example 1 Preparation of Support A 0.24 mm thick aluminum plate (material: 1050, tempered H16) was degreased in a 5% aqueous sodium hydroxide solution at 60 ° C. for 1 minute, and then 0.5 mol / l. Temperature, 25 ° C., current density; 60 A / dm ² , treatment time;
The electrolytic etching was performed under the condition of 30 seconds. Then
After a desmut treatment at 60 ° C. for 10 seconds in a 5% aqueous sodium hydroxide solution, the temperature is increased to 20 ° C. in a 20% sulfuric acid solution.
Anodizing was performed under the conditions of a current density of 3 A / dm ² and a processing time of 1 minute. Further, a hot water sealing treatment was performed with hot water of 30 ° C. for 20 seconds to prepare an aluminum plate as a support for a lithographic printing plate material.

Synthesis of acid-decomposable compound A Dimethoxycyclohexane (0.5 mol), phenyl cellosolve (1.0 mol) and p-toluenesulfonic acid 8
0 mg was reacted at 100 ° C. for 1 hour while stirring, then the temperature was gradually raised to 150 ° C., and the reaction was further performed at 150 ° C. for 4 hours. Methanol generated by the reaction was distilled off during this period. After cooling, 500 ml of tetrahydrofuran and 2.5 g of anhydrous potassium carbonate were added, followed by stirring and filtration.
The solvent was distilled off from the filtrate under reduced pressure, and the low-boiling components were further distilled off at 150 ° C. and under a high vacuum.
I got

[0099]

Embedded image

A photosensitive layer coating solution having the following composition was coated on the support so that the film thickness after drying was 2 g / m ² ,
For 2 minutes to obtain an image forming material.

Composition of Photosensitive Layer Coating Solution Binder A 60 parts by weight

[0102]

Embedded image

Acid decomposable compound A 20 parts by weight Acid generator A (2-trichloromethyl-5- [β- (2-benzofuryl) vinyl] -1,3,4-oxadiazole) 10 parts by weight Infrared absorber Ex. Compound IR18 10 parts by weight Silica particles (average particle size 0.5 μm) 20 parts by weight Propylene glycol monomethyl ether 1000 parts by weight A semiconductor laser (wavelength 830 n)
m, output 500 mW). The laser beam diameter was 13 μm at 1 / e ² of the intensity at the peak. The resolution is 2000 in both the scanning direction and the sub-scanning direction.
DPI. After the exposure, the photosensitive layer was heat-treated at 120 ° C. for 30 seconds using an infrared heater. Further, the positive PS plate developing solution SDR-1 (manufactured by Konica Corporation) was immersed in a developing solution at 27 ° C. diluted 6 times with water at 27 ° C. for 25 seconds to remove non-image portions (exposed portions). And washed with water to produce a lithographic printing plate. The sensitivity was evaluated based on the exposure energy required to develop the exposed part.

Example 2 A photosensitive layer coating solution was prepared by changing 20 parts by weight of silica particles in the composition of the photosensitive layer coating solution of Example 1 to 20 parts by weight of particles composed of a polymethyl methacrylate crosslinked resin having an average particle size of 0.1 μm. The same experiment as in Example 1 was carried out except for the use.

Comparative Example 1 The same experiment as in Example 1 was conducted except that the photosensitive layer coating solution of Example 1 was prepared by removing the silica particles from the composition of the photosensitive layer coating solution.

Example 3 The same experiment as in Example 1 was conducted except that the composition of the photosensitive layer coating solution was changed as follows.

Composition of Coating Solution for Photosensitive Layer Infrared Absorber Illustrative Compound IR18 2 parts by weight Acid generator A (2-trichloromethyl-5- [β- (2-benzofurin) vinyl] -1,3,4-oxadiazole 3 parts by weight 45 parts by weight of resole resin (SHOROL CKP918, manufactured by Showa Kobunshi) 45 parts by weight of novolak resin 20 parts by weight of polymethyl methacrylate crosslinked resin having an average particle diameter of 0.1 μm 20 parts by weight propylene glycol monomethyl ether 1000 parts by weight Example 2 The same experiment as in Example 3 was carried out except that the photosensitive layer coating solution in which the particles composed of the polymethyl methacrylate crosslinked resin were excluded from the composition of the photosensitive layer coating solution of Example 3 was used.

Example 4 The same experiment as in Example 1 was conducted except that the composition of the photosensitive layer coating solution was changed as follows.

Composition of photosensitive layer coating liquid Infrared absorber Exemplified compound IR18 2 parts by weight Acid generator A (2-trichloromethyl-5- [β- (2-benzofurin) vinyl] -1,3,4-oxadiazole 3 parts by weight Hexamethylol melamine 25 parts by weight Novolak resin 45 parts by weight Polymethyl methacrylate crosslinked resin particles having an average particle diameter of 0.1 μm 20 parts by weight Propylene glycol monomethyl ether 1000 parts by weight Comparative Example 3 Photosensitive layer coating solution of Example 4 The same experiment as in Example 4 was carried out except that the photosensitive layer coating solution was used except that the particles of the polymethyl methacrylate crosslinked resin were removed from the composition of Example 4.

Example 5 An experiment was conducted in the same manner as in Example 3 except that the composition of the photosensitive layer coating solution of Example 3 was changed to the polymer binder B shown below.

Synthesis of Polymeric Binder B A mixed solvent of 125 ml of acetone and 125 ml of methanol was placed in a 500 ml four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, a heater, and a nitrogen gas inlet tube.
9.0 g of ethyl acrylate (0.09
mol), ethyl methacrylate 34.2 g (0.30
mol), 15.9 g of acrylonitrile (0.30 mol
l), 0.86 g (0.01 mol) of methacrylic acid, 35.2 g (0.2 mol) of vinylbenzyl acetate,
And 4-hydroxyphenyl methacrylamide 51.6
g (0.30 mol) was dissolved. Further, 3.28 g (0.02 m) of azobisisobutyronitrile is used as a polymerization initiator.
ol) and heated under vigorous stirring under a nitrogen stream,
Reflux at about 60 ° C. for 6 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and then poured into water to precipitate a polymer compound. This was collected by filtration and vacuum dried at 50 ° C. for 24 hours to obtain 100 g of an alkali-soluble acrylic copolymer. The yield based on the total amount of monomers was 90%.

The weight-average molecular weight of the obtained alkali-soluble acrylic copolymer (polymer binder B) was measured by gel permeation chromatography (GPC) using pullulan standard and N, N-dimethylformamide (DMF) solvent. As a result, it was 50,000.

Comparative Example 4 The same experiment as in Example 5 was performed except that the photosensitive layer coating solution was prepared by removing the particles of the polymethyl methacrylate crosslinked resin from the composition of the photosensitive layer coating solution of Example 5.

The above results are shown in Table 1 below.

[0115]

[Table 1]

[0116]

According to the present invention, there is provided a positive or negative image forming material capable of forming an image by exposure to infrared rays, the image forming material having improved sensitivity to infrared rays, and image forming using the same. A method is provided.

Further, according to the present invention, there is provided an image-forming material having a photosensitive layer containing an acid generator and an acid-decomposable compound, or containing an acid generator and a compound capable of being cross-linked by an acid. An image forming material with improved sensitivity and an image forming method using the same are provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/038 601 G03F 7/038 601 7/039 601 7/039 601 7/20 505 7/20 505

Claims (2)

[Claims] A photosensitive layer containing a compound capable of generating an acid upon irradiation with an actinic ray, a compound capable of decomposing or crosslinking in the presence of an acid, an infrared absorber and solid fine particles, on a support. Image forming material. 2. An image forming method comprising: drawing an image on a photosensitive layer of the image forming material according to claim 1 using infrared rays; and removing an exposed portion with an alkaline developer.