JPH11143067A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive composition enhanced in resistance and enlarged in developing solution latitude and high in sensitivity by incorporating an alkali-soluble resin prepared by condensing specified phenol components with aldehydes or ketones and specified in a peak integrated value in the13 C-NMR spectra of this resin in the dimethylsulfoxyde solution with its hydrogen converted into deuterium. SOLUTION: This photosensitive composition contains the resin prepared by condensing the phenol components comprising phenols and m-alkylphenols and p-alkylphenols, with the aldehydes or the ketones. This resin is the alkali- soluble resin controlled to A/B >=0.6, where A is the peak integrated value in 23.0-31.0 ppm and B is that of 23.0-37.0 ppm in the13 C-NMR spectra of this resin in the dimethylsulfoxide solution with its hydrogen converted into deuterium. The composition contains, in addition, a dye having absorption in the infrared region, a compound capable of generating an acid by irradiation with acivated rays, and a compound having a bond decomposable by the acid or a group cross-linkable by the acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive composition having improved chemical resistance, improved developer latitude, and high sensitivity.

[0002]

2. Description of the Related Art Recording materials having a photosensitive layer containing an acid generator and an acid-decomposable compound are widely known.

As a technique focusing on acid-decomposable compounds, US Pat. No. 3,779,778 discloses a compound having an orthocarboxylic acid ester group or a carboxylic acid amide acetal group. A compound having an acetal or ketal bond in the main chain is disclosed, and a silyl ether compound is disclosed in JP-A-60-37549. It is a recording material having a photosensitive layer.

On the other hand, US Pat. No. 5,340,699 discloses a recording material having an acid generator, a resole resin, a novolak resin and an infrared absorber. This technique is a recording material having a negative photosensitive layer which can record both infrared rays and ultraviolet rays, is hardened at an exposed portion, becomes insoluble in a developing solution, and becomes an image portion.

On the other hand, Japanese Patent Application No. 7-138519 discloses a recording material having a photosensitive layer comprising a high molecular weight phenol resin, an O-quinonediazide compound, an organic solvent having a boiling point of 110 ° C. or lower and an organic solvent having a boiling point of 120 ° C. or higher. And also
U.S. Pat. Nos. 3,666,473 and 4,115,12
Nos. 8 and 4,173,470 disclose a novolak-type phenol resin and / or a naphthoquinonediazide-substituted compound, and furthermore, “Introduction to Microlithography” (ACS Publishing, No.
No. 219, pages 112 to 121) discloses a novolak resin composed of cresol-formaldehyde and / or trihydroxybenzophenone-1,2-naphthoquinonediazidosulfonic acid ester. This is a recording material having a positive photosensitive layer serving as an image area.

The prior art is summarized as follows for each claim of the present invention. 1) Prior art of high-ortho novolak resin according to claims 1 to 3 of the present invention Novolak resin has been conventionally improved in various ways, and among them, ortho-novolak resin is compared with novolak synthesized by polycondensation reaction using an acid catalyst. A resin called a so-called high orthonovolak resin containing many ortho bonds is known.
This resin is used in the field of photoresists, and attempts to increase the γ value (Japanese Patent Publication No. Hei 4-2181), a high sensitivity, a wide defocus latitude, and an ionizing radiation-sensitive resin composition that does not easily generate scum (Japanese Patent Application Laid-Open No. Hei 4-218). Kaihei 3-25385
No. 9) or a positive photoresist composition that hardly causes pattern defects due to fine foaming during exposure and hardly causes fine defects due to scum (Japanese Unexamined Patent Publication No. 3-25 / 1991).
No. 3860), and in recent years, chemical resistance, high sensitivity, and high contrast have been improved in combination with quinonediazide (Japanese Patent Application Laid-Open No. 8-184964). However, in each case, image formation is performed by using ultraviolet rays, and thus the method is not simple. 2) Conventional tandem type novolak resin according to claim 4 of the present invention Various improvements have been seen in the conventional novolak resin. Among them, Japanese Patent Publication No. 6-54386 (Nippon Synthetic Rubber) uses a tandem type novolak resin. We have provided a photoresist material with excellent heat resistance, sensitivity, and developability. However, each of them was a photosensitive lithographic printing plate or a photoresist in which an exposed portion was alkali-solubilized by ultraviolet rays and became a non-image portion. 3) Conventional technology of aromatic-containing condensate according to claims 5 to 7 of the present invention The above-described photosensitive material including 1) and 2) is a conventional technology. In addition, JP-A-2-300752 and JP-A-6-2
No. 42601, U.S. Pat. Nos. 5,571,886, 5,266,440, JP-A-8-234421, JP-A-9-90626, JP-A-5-289331, JP-A-2-300751, Kaihei 8-21601,
In JP-A-60-31138 and JP-A-8-272093, a photosensitive lithographic printing plate or a photoresist, in which an exposed portion is alkali-solubilized by ultraviolet rays and becomes a non-image portion, is used. 4) Conventional technology of naphthol novolak resin according to claim 8 of the present invention The above-described photosensitive material including 1) and 2) is a conventional technology. Japanese Patent Application Laid-Open No. Hei 9-127691 discloses a photoresist made of a resin having an acid-decomposable group, a photoacid generator, and a naphthol novolak resin having a molecular weight of 2,000 or less. It could not be used with the inventive laser.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive composition having improved chemical resistance, improved developer latitude, and high sensitivity.

[0008]

The object of the present invention is to provide: 1.1) a resin obtained by condensing a phenol component and aldehydes or ketones comprising the following (1) to (3);
And the deuterated dimethyl sulfoxide solution of this resin
_{In the 13} C-NMR spectrum, 23.0 to 31.
The peak integrated value up to 0 ppm is A, 23.0-37.0.
When the integrated value up to ppm is B, the value of X = A / B is X ≧ 0.6, alkali-soluble resin, 2) dye having absorption in infrared light, 3) A photosensitive composition comprising: a compound capable of generating an acid upon irradiation with actinic rays; 4) a compound having a bond capable of being decomposed by an acid or a group crosslinkable by an acid; and a phenol component (1) phenols 0 to 50 mol%. (2) m-alkylphenols 20-80 mol% (3) p-alkylphenols 20-80 mol%

[0009] 2. The photosensitive composition according to the above 1, wherein the photosensitive composition contains at least one kind of the phenol component.

[0010] 3. 3. The photosensitive composition according to 1 or 2, wherein the phenolic resin has a molecular weight of 500 to 5,000.

4. 3. The resin according to the above 1 or 2, wherein the molecular weight is 2
A photosensitive composition comprising a resin obtained by condensing phenols and aldehydes or ketones containing a compound represented by the following general formula (1) with a novolak resin having a size of from 00 to 3000:

[0012]

Embedded image

5.1) Gel obtained by condensing an alkali-soluble novolak resin with phenols and aldehydes or ketones containing the compound represented by the above general formula (1) and using monodisperse polystyrene as a standard. The molecular weight in terms of polystyrene determined by the permeation and chromatograph (GPC) method is from 6500 to 30000,
When the maximum heights of the peaks in the range of 00 to 6000 and 100 to 950 are a, b and c, respectively, a /
a resin in which b = 0 to 1.5 and c / b = 0.05 to 1.5,
2) a dye having absorption in infrared light, 3) a compound capable of generating an acid upon irradiation with actinic light, 4) a photosensitive composition comprising a bond capable of decomposing by an acid or a compound having a group crosslinkable by an acid;

6.1) As an alkali-soluble novolak resin, a novolak resin obtained by condensing phenols and aromatic aldehydes containing a compound represented by the above general formula (1), 2) absorbing an infrared ray A photosensitive composition comprising a compound capable of generating an acid upon irradiation with actinic rays, a compound having a bond which can be decomposed by an acid or a group capable of crosslinking by an acid,

[0015] 7. The photosensitive composition according to the above 6, wherein the molecular weight of the novolak resin is in the range of 300 to 20,000.

8. A photosensitive composition comprising salicylaldehyde or benzaldehyde as the condensate of the phenol according to claim 6 or 7,

9.1) Naphthol novolak resin, 2)
A photosensitive composition comprising a dye having absorption in infrared light, 3) a compound capable of generating an acid upon irradiation with actinic light, 4) a compound having a bond which can be decomposed by an acid or a group which is cross-linked by an acid;

10. 10. The photosensitive composition according to the above 9, wherein the naphthol novolak resin has a molecular weight in the range of 300 to 10,000.

In the prior art, image exposure was limited to ultraviolet light, but the present invention has made it possible to form an image by infrared exposure. That is, in the prior art, image exposure was generally performed by irradiation ultraviolet rays from a halogen lamp, a high-pressure mercury lamp, or the like via a mask film or the like. Exposure with a short wavelength laser such as an argon laser or a helium-cadmium laser is also possible, but the apparatus is expensive and large, and the sensitivity of the photosensitive material is not sufficient. In the present invention, it is possible to form an image by infrared exposure using a cheap and compact semiconductor laser or the like. In addition, this makes it possible to easily form a digital image without requiring a mask film and a process and equipment for producing the mask film.

In a conventional photosensitive lithographic printing plate on which an image is formed by using an infrared dye, an image is formed, but a phenomenon occurs in which the image portion is liable to be rubbed by the latitude of the developing solution, that is, the concentration of the developing solution (exposure portion). Phenomenon due to low developer resistance). In addition, if the exposed portion is immersed in a chemical (chemical used for printing) separately from the above, the photosensitive layer easily swells with the chemical, so that the film is liable to be rubbed. Such a reduction in the film strength of the photosensitive material has been a problem until now.

However, it has been found that the use of a specific novolak resin such as the present invention and other constitutions can improve the situation.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below. Examples of the dye having absorption in the infrared light of the present invention include a cyanine dye, an aminium dye, a diimonium dye, a metal complex dye, and a pyrylium dye, and preferably a cyanine dye. The addition amount is 0.01 to 10% by weight
And preferably 0.1 to 5% by weight.

Hereinafter, the infrared dye or the infrared absorber will be described in detail.

As the infrared dye or absorber used in 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. Particularly preferred infrared absorbers are 700-1100 n
m, and the molar extinction coefficient ε at the peak is 1
0 ⁵ or more infrared-absorbing dye.

Examples of the infrared absorbing dyes 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, anthraquinone dyes, indoaniline metal complex dyes, and intermolecular CT dyes. Examples of the infrared absorbing dye include JP-A-63-139191 and JP-A-64-33547.
No., JP-A-1-160683 and 1-280750
Nos. 1-293342, 2-2074, 3-
No. 26593, No. 3-30991, No. 3-34891
No. 3-36093, No. 3-36094, No. 3-
No. 36095, No. 3-42281, No. 3-10347
No. 6 and the like.

In the present invention, a cyanine dye represented by the following formula (R-1) or (R-2) is particularly preferred as the infrared absorber.

[0027]

Embedded image

In the 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. And R ₃ and R ₄ each represent a substituent, and one of R ₃ and R ₄ has an anionic dissociable group. R ₅ , R ₆ , R ₇ and R ₈ 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 dye represented by formula (R-1) or (R-2) is represented by formula (R-1) or (R-2)
Forms a cation and includes a counter anion. In this case, as the counter anion, Cl ⁻ , Br ⁻ ,
Examples thereof include alkyl boron such as ClO ₄ ⁻ , BF ₄ ⁻ , and t-butyltriphenylboron.

In the general formulas (R-1) and (R-2), the number of carbon atoms (n) in a conjugated bond chain represented by L
When a laser emitting infrared light is used as a light source for image exposure, it is preferable to select an effective value according to the transmission wavelength of the laser. For example, an emission wavelength of 10
When using a 60 nm YAG laser, n is 9 to
13 is preferred. The conjugate bond may have any substituent, and the conjugate bond may form a ring with a plurality of substituents. Further, the ring represented by X ₁ and the ring represented by X ₂ can have an arbitrary substituent. As the substituent, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -SO
A group selected from ₃ M and -COOM (M is a hydrogen atom or an alkali metal atom) is preferable. R ₃ and R ₄ are each an optional substituent, preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms;
_{((CH 2) n -O-)} k - (CH 2) m OR (n and m are each an integer of 1 to 3, k is 0 or 1, R represents an alkyl group having 1 to 5 carbon atoms. One of R ₃ and R ₄ 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); ₃ and one is -R-COOM other hand is -R-COO of _{R 4} ^- (R is an alkyl group having 1 to 5 carbon atoms, M represents an alkali metal atom.) it is. R ₃ and _{R 4} are, in terms of sensitivity and developability, while the above-mentioned _{R 3} and _{R 4} -R-SO ₃ ^- or -R-COO ^-, the other is said -R-SO ₃ M or -R- Preferably it is COOM.

The cyanine dye represented by formula (R-1) or (R-2) is 750 to 900 nm when a semiconductor laser is used as a light source for image exposure, and 900 to 900 when a YAG laser is used. Those exhibiting an absorption peak at 1200 nm and having a molar extinction coefficient of ε> 1 × 10 ⁵ are preferred.

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

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

These dyes can be synthesized by known methods, but commercially available products can also be used as described below.

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, SIR10
3 (phthalocyanine); KIR101, SIR114
(Anthraquinone type); PA1001, PA1005
PA1006, SIR128 (metal complex type), Dainippon Ink & Chemicals: Fastogen blue 8120, Midori Kagaku: MIR-101, 1011, 1021 and the like. In addition, it is also commercially available from companies such as Nippon Kogaku Dye, Sumitomo Chemical, and Fuji Photo Film.

In the present invention, the amount of the infrared absorber added is preferably in the range of 0.01 to 10% by weight. If the addition amount exceeds 10% by weight, the developability of the non-image area (exposed area) decreases, and if it is less than 0.01% by weight, the development resistance of the image area decreases.

The acid generator or photoacid generator of the present invention includes:
Preferred are triazine-based compounds. The addition amount is 0.0
It is 1 to 20% by weight, preferably 0.1 to 10% by weight.

The details will be described below. Examples of the compound capable of generating an acid upon irradiation with actinic rays (hereinafter referred to as "photoacid generator") used in the present invention include various known compounds and mixtures. For example, diazonium, phosphonium, sulfonium, and iodonium BF ₄ ⁻ , PF ₆ ⁻ ,
Salts such as SbF ₆ ⁻ , SiF ₆ ²⁻ , and ClO ₄ ⁻ , organic halogen compounds, orthoquinone-diazidosulfonyl chloride, and organometallic / organic halogen compounds also form or separate acids upon irradiation with actinic rays. It is a photosensitive component and can be used as a photoacid generator in the present invention. In principle, all organic halogen compounds known as free radical-forming photoinitiators are compounds which form hydrohalic acid and can be used as photoacid generators in the present invention.

Examples of the compounds forming the above-mentioned hydrohalic acid include US Pat. Nos. 3,515,552, 3,536,489 and 3,779,778, and West German Patent Publication. No. 2,243,621, and compounds capable of generating an acid by photolysis described in, for example, West German Patent Publication No. 2,610,842 can also be used. Further, o-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-50-36209 can be used.

In the present invention, a photoacid generator is preferable from the viewpoints of sensitivity of an organic halogen compound to image formation by infrared exposure and storage stability when used as an 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 include JP-A-54-74728, JP-A-55-24113, JP-A-55-77742, JP-A-60-3626 and JP-A-60-3626. 2-halomethyl-1,3,4-oxadiazole compounds described in JP-A-60-138538. 2-halomethyl-1,3,4
Preferred examples of the oxadiazole-based photoacid generator are shown below.

[0054]

Embedded image

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

[0056]

Embedded image

In the general formula (K), R is an alkyl group,
A halogen-substituted alkyl group, a phenylvinylene group or an aryl group (for example, a phenyl group, a naphthyl group or the like) which may be substituted with an alkoxy group, or a substituted product thereof;
X ₃ represents a halogen atom. S represented by the general formula (K)
-Examples of compounds of the triazine-based photoacid generator are shown below.

[0058]

Embedded image

[0059]

Embedded image

In the present invention, the content of the photoacid generator can be varied over a wide range depending on its chemical properties, photosensitive composition and the like, or its physical properties. The range is suitably about 0.01 to about 20% by weight, preferably 0.1 to 10% by weight, based on the total weight of the solid content of the photosensitive layer.

The compound having a bond decomposable by an acid or the acid-decomposable compound of the present invention is preferably a compound having at least one acetal or ketal group. The amount of addition is 1 to 80% by weight, preferably 5 to 60% by weight.

The details will be described below. The compound having a bond decomposable by an acid used in the present invention (hereinafter referred to as "acid-decomposable compound") is specifically described in JP-A-48-89.
No. 003, No. 51-120714, No. 53-1334
No. 29, 55-12995, 55-126236
And C-O-C described in JP-A-56-17345.
Compound having a bond, JP-A-60-37549, JP-A-60-37549
Compounds having a Si-OC bond described in JP-A No. 0-112446;
No. 0247, other acid-decomposable compounds, and further, compounds having an Si—N bond described in Japanese Patent Application No. 61-16687 and Japanese Patent Application No. 61-9.
No. 4603, carbonated ester disclosed in Japanese Patent Application No. Sho 60
Orthocarbonate described in Japanese Patent Application No. 251744, orthotitanate described in Japanese Patent Application No. 61-125473, orthosilicate described in Japanese Patent Application No. 61-125474, Japanese Patent Application No. 61-125474. Fifteen
Acetal and ketal described in No. 5481,
Compounds having a CS bond described in Japanese Patent Application No. 61-87769 are exemplified.

Of the above, the above-mentioned JP-A-53-133429
No., 56-17345, 60-12446,
No. 60-37549 and Japanese Patent Application No. 60-251744
And C-O- described in JP-A-61-155481.
Compounds having a C bond, compounds having a Si-OC bond, orthocarbonates, acetals, ketals, and silyl ethers are preferred. Among them, an organic polymer compound having an acetal or ketal moiety in the main chain described in JP-A-53-133429, whose solubility in a developer is increased by the action of an acid, and JP-A-63-133429. The following structural unit described in No. 10153

[0064]

Embedded image

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

Specific examples of the acid-decomposable compound used in the present invention include the compounds described in the above-mentioned known examples. The methods for synthesizing the compounds are also described in the above-mentioned known examples.

In the present invention, the acid-decomposable compound is-
(CH ₂ CH ₂ O) _n -group (n represents an integer of 2 to 5)
Are preferred from the viewpoint of the balance between sensitivity and developability. Further, among these compounds, a compound having a number n of ethyleneoxy groups of 3 or 4 is particularly preferred. The above-(CH ₂
Specific examples of the compound having a (CH ₂ O) _n -group include a condensation product of dimethoxycyclohexane, benzaldehyde and a substituted derivative thereof with any one of diethylene glycol, triethylene glycol, tetraethylene glycol and pentaethylene glycol.

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

[0069]

Embedded image

Wherein R, R ₁ and R ₂ are each a hydrogen atom,
Represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a sulfo group, a carboxyl group or a hydroxyl group, p, q and r each represent an integer of 1 to 3,
m and n each represent an integer of 1 to 5. R, R ₁ and R ₂
The alkyl group represented by may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, and a pentyl group. Examples of the alkoxy group include a methoxy group and an ethoxy group. , Propoxy group, isopropoxy group, butoxy group, tert
-Butoxy group, pentoxy group and the like, and the sulfo group and the carboxyl group include salts thereof. Among the compounds represented by the general formula (L), compounds wherein m and n are 1 or 2 are particularly preferred. The compound represented by the general formula (L) can be synthesized by a known method.

In the present invention, the content of the acid-decomposable compound is preferably from 1 to 80% by weight based on the total solid content of the photosensitive composition or the composition forming the photosensitive layer when used as an image forming material. Particularly preferably, it is 5 to 60% by weight. The acid-decomposable compounds may be used singly or as a mixture of two or more.

The compounds or crosslinkers having a group capable of being crosslinked by an acid according to the present invention are shown below, and the addition amount is 1 to 80% by weight, preferably 5 to 60% by weight.

In the present invention, the compound having a group capable of crosslinking with an acid includes a compound capable of crosslinking with an alkali-soluble resin in the presence of an acid (hereinafter referred to as a crosslinking agent), that is, a compound capable of crosslinking and reducing solubility in alkali. It is a crosslinking agent. The degree to which the solubility in alkali can be reduced may be changed to physical properties in which the resin shows alkali insolubility by crosslinking with an alkali-soluble resin.Specifically, when used as an image forming material, What was originally alkali-soluble by the action of the crosslinking agent shows insolubility in an alkali solution used as a developer,
It represents the state remaining on the support. Examples of the cross-linking agent include a methylol group or a derivative of a methylol group, a melamine resin, a furan resin, an isocyanate, a blocked-isocyanate (an isocyanate having a protective group), and the like, which has a methylol group or an acetylated methylol group. Preferred crosslinking agents are desirable. The amount added to the photosensitive composition is 1 to 80% by weight, preferably 5 to 60% by weight.

As the binder, another resin may be used in combination. For example, an acrylic binder, a novolak resin or the like can be used alone or in combination. Hereinafter, this point will be described in detail.

As the binder resin, polyester resin, polyvinyl acetal resin, polyurethane resin, polyamide resin, cellulose resin, olefin resin, vinyl chloride resin, (meth) acrylic resin,
Styrene-based resin, polycarbonate, polyvinyl alcohol, polyvinylpyrrolidone, polysulfone, polycaprolactone resin, polyacrylonitrile resin, urea resin, epoxy resin, phenoxy resin, rubber-based resin, and the like. Further, a resin having an unsaturated bond in the resin, for example, diallyl phthalate resin and its derivative, chlorinated polypropylene and the like can be polymerized with the above-mentioned compound having an ethylenically unsaturated bond, so that it is suitably used depending on the application. be able to. As the binder resin, one or more of the above resins can be used in combination.

As the binder that can be used in the present invention, any type of lipophilic polymer soluble in the organic solvent contained in the present invention may be used as long as it functions as a binder. Lipophilic polymer compounds having a value of 20 to 250 are preferred.

Examples of these polymer weights include, for example,
Examples include polyamide, polyester, polycarbonate, polystyrene, polyurethane, polyvinyl chloride, and copolymers thereof, polyvinyl butyral resin, polyvinyl formal resin, shellac, epoxy resin, phenol resin, and acrylic resin. Among these, a preferable high molecular weight polymer is a copolymer high molecular weight obtained by copolymerizing a mixture of monomers described in the following (1) to (17).

The above-mentioned monomer mixture may be mixed with another monomer which can be copolymerized with the above-mentioned monomer. Further, the high-molecular polymer may be a copolymer obtained by copolymerizing the above-mentioned monomers, for example, modified with glycidyl acrylate, glycidyl methacrylate, or the like. (1) Monomers having an aromatic hydroxyl group, for example, o-hydroxystyrene, p-hydroxystyrene, m-hydroxystyrene, o-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, m-
Hydroxyphenyl acrylate and the like. (2) Monomers having an aliphatic hydroxyl group, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5
-Hydroxypentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide,
Hydroxyethyl vinyl ether and the like. (3) a monomer having an aminosulfonyl group, for example,
m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl acrylate, p-aminophenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide and the like . (4) a monomer having a sulfonamide group, for example, N
-(P-toluenesulfonyl) acrylamide, N-
(P-toluenesulfonic) methacrylamide and the like. (5) α, β-unsaturated carboxylic acids, for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like. (6) Substituted or unsubstituted alkyl acrylates, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, acrylic Decyl acid, undecyl acrylate, dodecyl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, glycidyl acrylate, and the like. (7) substituted or unsubstituted alkyl methacrylates, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate;
Octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate and the like. (8) Acrylamide or methacrylamides, for example, acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide , N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like. (9) A monomer containing a fluorinated alkyl group, for example,
Trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N-butyl-N- (2-acryloxyethyl) hepta Decafluorooctylsulfonamide and the like. (10) Vinyl ethers, for example, ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and the like. (11) Vinyl esters, for example, vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate and the like. (12) Styrenes, for example, styrene, methylstyrene, chloromethylstyrene and the like. (13) Vinyl ketones, for example, methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone and the like. (14) Olefins, for example, ethylene, propylene, isobutylene, butadiene, isoprene and the like. (15) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like. (16) Monomers having a cyano group, for example, acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethylacrylate, o-cyanostyrene, m-cyanostyrene, p-cyanostyrene etc. (17) Monomers having an amino group, for example, N, N-
Diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene, urethane acrylate, N, N-dimethylaminopropylacrylamide, N, N-dimethylacrylamide, acryloylmorpholine, N-isopropylacrylamide , N, N
-Diethylacrylamide and the like.

The copolymer preferably has a weight average molecular weight of 10,000 to 200,000 as measured by gel permeation chromatography (GPC).
The weight average molecular weight is not limited to this range.

If necessary, any other polymer such as polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, novolak resin and natural resin may be used in combination with the above polymer. You may. The content of these high molecular polymers in the photosensitive composition is preferably in the range of 20 to 90% by weight,
More preferably, it is in the range of 70 to 70% by weight.

In the present invention, among the above high molecular compounds, an acrylic polymer is preferable.

As other materials of the present invention, conventionally known materials can be used without any particular limitation.

(Surfactant) In the present invention, it is preferable to contain 0.001 to 5% by weight of a fluorine-based surfactant from the viewpoint of preventing the generation of stains on the non-image area with the passage of time.
Examples of the fluorine-based surfactant include the following compounds.

C ₇ F ₁₅ CO ₂ NH ₄ , C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) CH ₂ COOK, C ₈ F ₁₇ SO ₂ NHC ₃ H ₆ N ⁺ (CH ₃ ) ₂ C
1 ⁻ , C ₇ F ₁₅ CONH (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₂ C ₂
H ₄ COO ⁻ , C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ (OC
_{3 H 6) 5 OH, C} 7 F 15 CONHC 3 H 6 N + (CH 3) 2 (C
H ₂ ) ₂ COO ⁻ ,

[0085]

Embedded image

C ₈ F ₁₇ SO ₂ NHC ₃ H ₆ N ⁺ (CH
_{3) 2 C 2 H 5 OS} - O 2 OC 2 H 5, C 7 F 15 CONHC 3 H 6 N + (CH 3) 3 Cl -,

[0087]

Embedded image

C ₈ F ₁₇ SO ₂ N (CH ₃ ) CH ₂ CH
₂ O ₂ OCH = CH ₂ ,

[0089]

Embedded image

As the fluorinated surfactant, commercially available products can be used. For example, Surflon “S-381” and “S
-382 "," SC-101 "," SC-102 ",
"SC-103", "SC-104" (all manufactured by Asahi Glass Co., Ltd.), Florard "FC-430", "FC-4"
31 "," FC-173 "(all from Fluorochemicals-Sumitomo 3M), F-top" EF352 "," EF
301 ”and“ EF303 ”(both from Shin-Akita Chemical Co., Ltd.)
Manufactured), Shubego Fuller “8035”, “8036”
(All manufactured by Schwegman), "BM1000", "B
M1100 "(all manufactured by BM Himmy), MegaFac" F-171 "," F-177 "," F-17 "
9 "(all manufactured by Dainippon Ink and Chemicals, Inc.).

In the present invention, the fluorine content of the fluorine-containing surfactant is 0.05 to 2%, preferably 0.1 to 1%.
%. The above-mentioned fluorine-based surfactants can be used alone or in combination of two or more, and can be used in combination with other surfactants.

Further, a lipophilic resin can be added to the photosensitive composition of the present invention in order to improve oil sensitivity. Examples of the lipophilic resin include, for example,
No. 3 to 1 carbon atoms as described in
A condensate of a phenol substituted with an alkyl group and an aldehyde, for example, a t-butylphenol formaldehyde resin or the like can be used.

(Solvent for Coating) The solvent used in the photosensitive composition of the present invention will be described.

For example, n-propanol, isopropyl alcohol, n-butanol, sec-butanol, isobutanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 2-methyl-2-butanol
Ethyl-1-butanol, 1-pentanol, 2-pentanol, 3-pentanol, n-hexanol, 2-
Hexanol, cyclohexanol, methylcyclohexanol, 1-heptanol, 2-heptanol, 3-
Heptanol, 1-octanol, 4-methyl-2-pentanol, 2-hexyl alcohol, benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol,
1,3-propanediol, 1,5-pentane glycol, dimethyltriglycol, furfuryl alcohol,
Hexylene glycol, hexyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, butylphenyl ether, ethylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, Propylene glycol monobutyl ether, propylene glycol phenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, methyl carbitol, ethyl carbitol, Ethyl carbitol acetate, butyl carbitol Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol dimethyl ether, diacetone alcohol, acetophenone, cyclohexanone, methylcyclohexanone, acetonylacetone, isophorone, methyl lactate, ethyl lactate, butyl lactate, propylene carbonate, phenyl acetate, -Sec-butyl acetate, cyclohexyl acetate, diethyl oxalate, methyl benzoate, ethyl benzoate, γ-butyl lactone, 3-methoxy-1-butanol, 4-methoxy-1-butanol,
3-ethoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-ethyl-1
-Pentanol, 4-ethoxy-1-pentanol, 5
-Methoxy-1-hexanol, 3-hydroxy-2-
Butanone, 4-hydroxy-2-butanone, 4-hydroxy-2-pentanone, 5-hydroxy-2-pentanone, 4-hydroxy-3-pentanone, 6-hydroxy-2-pentanone, 4-hydroxy-3-pentanone,
6-hydroxy-2-hexanone, 3-methyl-3-hydroxy-2-pentanone, methylcellosolve (M
C), ethyl cellosolve (EC) and the like.

Allyl alcohol, isopropyl ether, butyl ether, anisole, propylene glycol monomethyl ether acetate, diethyl carbitol, tetrahydrofuran, dioxane, dioxolan,
Acetone, methyl propyl ketone, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, 3
-Hydroxy-2-butanone, 4-hydroxy-2-butanone, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, methoxybutyl acetate, methyl propionate,
Ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, N-methyl-2-pyrrolidone, acetonitrile, dimethylformamide (DM
F), dimethylacetamide (DMAc), n-pentane, 2-methylpentane, 3-ethylpentane, methylcyclopentane, n-hexane, isohexane, cyclohexane, methylcyclohexane, n-heptane, cycloheptane, n-octane, isooctane , Nonane, decane, benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene,
Cumene, n-amylbenzene, dimethyldiglycol (DMDG), ethanol and the like.

The image formation of the image forming material of the present invention is evaluated using a light source of 700 nm or more. Examples of the light source include, but are not limited to, a semiconductor laser, a He-Ne laser, a YAG laser, and a carbon dioxide laser.
The output is suitably 50 mW or more, preferably 100 mW.
W or more.

(Developer Solution and Developing Conditions) The concentration of the metal salt contained in the alkali agent is in the range of 0.05 to 20% by weight.
More preferably, it is 0.1 to 10% by weight. JP 57
No. 7427 and Japanese Patent Publication No. 57-7427 are also possible.

The photosensitive composition of the present invention may optionally contain
Further, other than the above, dyes, pigments, sensitizers, visible paints and the like can be contained.

<2> Image Forming Material The image forming material of the present invention is characterized by comprising a support having thereon a photosensitive layer containing the above photosensitive composition.
Specifically, it is obtained by applying a coating solution of the above-mentioned photosensitive composition (containing a solvent satisfying the conditions of the present invention) to the surface of a suitable support, providing a photosensitive layer, and drying.

In the present invention, the amount of the residual solvent in the photosensitive layer is preferably 5 mg / m ² or less, more preferably 3 mg / m ² or less.

As the support, aluminum, zinc,
Metal plates such as steel, copper, etc., and metal plates, paper, plastic films and glass plates plated or deposited with chromium, zinc, copper, nickel, aluminum, iron, etc., paper coated with resin, metal foil such as aluminum Paper, hydrophilically treated plastic film, and the like.

When the present invention is applied to a photosensitive lithographic printing plate,
It is preferable to use an aluminum plate that has been subjected to surface treatment such as graining treatment, anodic oxidation treatment and, if necessary, sealing treatment as the support. 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. Etching by electrolysis is performed using a bath in which an inorganic acid such as phosphoric acid, sulfuric acid, hydrochloric acid, or nitric acid is 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
It is. The amount of the anodic oxide film is determined, for example, by immersing the aluminum plate in a chromic phosphate 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 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.

<3> Method for Producing Image Forming Material The method for producing an image forming material of the present invention comprises the steps of: providing the above photosensitive composition on an aluminum support, and then drying at a temperature of 85 ° C. or more and a drying time of 10 seconds or more. It is characterized by processing under conditions. The drying temperature is preferably 90 ° C. or more, and the drying time is 30 seconds or more. Under these conditions, it is preferable to carry out the treatment so that the amount of the residual solvent on the surface of the photosensitive layer is 5 mg / m ² or less.

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, in the case of a photosensitive lithographic printing plate, a solid content of 0.5 to 5.
0 g / m ² is preferred.

The image forming material of the present invention has a wavelength of 700 nm.
It is preferable to perform image exposure using the above light sources. The light source is a semiconductor laser, He-Ne laser, YAG
Laser, carbon dioxide laser and the like. Output is 5
0 mW or more is appropriate, and preferably 100 mW or more.

As the developing solution used for developing the image forming material of the present invention, an aqueous alkaline developing solution is preferable. Examples of the aqueous alkaline developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate. ,
Aqueous solutions of alkali metal salts such as sodium metasilicate, potassium metasilicate, dibasic sodium phosphate, and tribasic sodium phosphate are included. The temperature 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, if necessary.

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

(Visible dye of the present invention) R ₁ , R ₂ , R
The alkyl group of ₃ indicates an alkyl group in the range of C _{1 to} C ₅ , and is preferably C _{1 to} C ₃ . Also, it may be a hydrogen atom. The alkoxy group is preferably a methoxy group, an ethoxy group, or a butoxy group. The alkylhydroxy group is preferably a hydroxymethyl group or a hydroxyethyl group.
The alkyloxy group is preferably a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, or the like.

X is preferably halogen, chlorine, bromine or iodine as a halogen atom.
ＺｎZnCl ₂ or the like is not particularly limited.

The amount of addition is 0.1 to
It is preferably 10% by weight, more preferably 0.5 to 5% by weight.

The peak of the dye absorption is preferably a wavelength which is easy to see as a visible image. Further, in the present photosensitive material, since the photosensitive material is exposed with an infrared laser, there is no limitation as long as the wavelength does not provide absorption. In particular, a wavelength of 400 to 700 nm is preferable as the visible dye for use in the present photographic material.

(Basic Compound) The basic compound can be used without any particular limitation in addition to the compounds described above as long as it can capture protons.

These basic compounds may be used alone or in combination of two or more. The amount used is 0.0
It is preferably from 0.01 to 10% by weight, more preferably from 0.01 to 5% by weight. When the content is 0.001% by weight or less, there is no effect of improving the storage stability and suppressing a decrease in reproducibility of small spots with time after exposure.

Incidentally, the photosensitive layer of this type of planographic printing plate includes:
It is also possible to add a mat agent described in detail below,
There are also two forms, that is, the form is contained in the photosensitive layer or the form is fixed to the surface of the photosensitive layer.

Matting Agent-Containing Type The lithographic printing plate material of this type comprises a) a support on a support in the presence of a compound capable of generating an acid upon irradiation with actinic rays, a compound having a bonding portion decomposable by the acid, or an acid. Containing a compound which can be insolubilized with alkali, an infrared absorbing agent and a matting agent having a particle size greater than or equal to the dry film thickness of the photosensitive layer, or b) generating an acid on a support by irradiation with actinic rays A photosensitive layer having a compound capable of being decomposed by an acid, a compound having a bonding portion decomposable by an acid, and an infrared absorbing agent, and having a matting agent on the surface of the photosensitive layer, specifically, one which is fixed to the surface of the layer. .

(Ultraviolet absorber) As the ultraviolet absorber used in the present invention, various known ones can be used.
For example, salicylic acid-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based and the like can be mentioned, and specific examples of these are shown below.

P-tert-butylphenyl salicylate p-octylphenyl salicylate phenyl salicylate 2,4-hydroxybenzophenone 2-hydroxy-4-methoxybenzophenone 2-hydroxy-4-octoxybenzophenone 2-hydroxy-4-dodecyloxybenzophenone 2 2,2'-Dihydroxy-4-methoxybenzophenone 2,2'-dihydroxy-4,4'-dimethoxybenzophenone 2-hydroxy-4-methoxy-5-sulfobenzophenone 2- (2'-hydroxy-5'-methoxyphenyl) Benzotriazole 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole 2- (2'-hydroxy-3 ', 5'-di-tert-
Butylphenyl) benzotriazole 2- (2'-hydroxy-3'-tert-butyl-
5'-methylphenyl) -5-benzotriazole 2- (2'-hydroxy-3 ', 5'-di-tert-
(Butylphenyl) -5-chlorobenzotriazole 2- (2'-hydroxy-3 ', 5'-di-tert-
Amylphenyl) benzotriazole 2- (2'-hydroxy-3 ', 5'-bis (α, α'
-Dimethylbenzylphenyl) -5-chlorobenzotriazole Among these ultraviolet absorbers, preferred are benzophenone-based, benzotriazole-based, and cyanoacrylate-based ones. These ultraviolet absorbers may be used alone or in combination of two or more.

The amount of the ultraviolet absorber used in the present invention is selected in consideration of the laser light source (absorption wavelength and intensity) used.

(Matting agent) Preferred examples of the matting agent (fine powder or fine particles) include polyvinyl acetate, polyvinylidene chloride, polyethylene oxide, polyethylene glycol, polyacrylic acid, polyacrylamide, polyacrylic acid alkyl ester, and polystyrene. And polystyrene derivatives and copolymers using monomers forming these polymers, polyvinyl methyl ether,
Epoxy resins, phenolic resins, polyamides, polyvinyl butyral, silicon dioxide, diatomaceous earth, zinc oxide, titanium oxide, zirconium oxide, glass, alumina, dextrin, starch, calcium stearate, zinc stearate, polysaccharide fatty acid esters, synthetic polymers, etc. be able to. These matting agents are preferably soluble in a developing solution, and are desirably appropriately selected depending on the developing solution. For example, when a strong alkaline aqueous solution is used as the developer, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, polynitrile pyrrolidone, polyvinyl alcohol, polyacrylic acid, polyacrylic acid alkyl ester, polystyrene derivatives, and phenol resins are preferable. Applied. As another developer, when an organic solvent such as alcohols, glycols, and ketones is used, a cellulose derivative,
Polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, polyvinylidene chloride, polyacrylic acid,
Polyacrylamide, alkyl polyacrylate, polystyrene, alkyl acrylate, acrylamide, a copolymer having styrene as one of the monomers,
Epoxy resins, phenol resins and the like are preferably applied.

A matting agent composed of a fusible polymer for forming a melt adhered to the surface of the photosensitive layer is powdered (sprinkled, dispersed, or sprayed) on the surface of the photosensitive layer, and is subjected to heat treatment. The matting agent causes a melting phenomenon,
It solidifies as the temperature drops and forms a spherical hat-shaped melt.

Preferred as these matting agents are polyvinyl acetate, polyvinylidene chloride, polyethylene oxide, polyethylene glycol, polyacrylic acid,
Polyacrylamide, alkyl polyacrylate, polystyrene and polystyrene derivatives and copolymers using monomers of these polymers, polyvinyl methyl ether, epoxy resin, fusible phenol resin, polyamide, polyvinyl butyral, etc. Can be. It is desirable to appropriately select these depending on the developer of the photosensitive layer composition. For example, when a strong alkaline aqueous solution is used for the developer, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid , Polyacrylalkyl esters, polystyrene derivatives, and fusible phenol resins are preferably used. When organic solvents such as alcohols, glycols and ketones are used, cellulose derivatives, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, polyvinylidene chloride, polyacrylate alkyl esters, polystyrene, epoxy resins, fusible phenols A resin and a copolymer containing at least one of acrylic acid, acrylamide, alkyl acrylate, and styrene as monomers are preferably applied.

The shape of the matting agent may be spherical, irregular, or any other specific shape. The surface of the matting agent may be modified for the purpose of preventing aggregation of the matting agents. The average particle size of the matting agent is 0.1 when provided in the photosensitive layer.
1 to 30 μm is preferable, and 1 to 10 μm is more preferable. At this time, it is essential that a matting agent having a particle diameter larger than the dry film thickness of the photosensitive layer exists. On the other hand, when it is present on the surface of the photosensitive layer, the thickness is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm.

As a method for forming a matting agent, when the matting agent is contained in the photosensitive layer, the matting agent is added to the coating solution for the photosensitive layer, and the matting agent is obtained immediately after the matting agent is dispersed by ultrasonic dispersion. The photosensitive layer coating solution is applied to a support. On the other hand, when a matting agent is present on the surface of the photosensitive layer,
The amount of the photosensitive layer surface with the matting agent is 0.005 to 3 g / m ^2.
And more preferably 0.05 to 1 g / m ² .

As a specific method for causing the matting agent to be present on the surface of the photosensitive layer, for example, powdering the matting agent, directly applying a dispersion of the matting agent to the photosensitive layer, and fusing the matting agent to the surface during drying, A method of spraying (spraying) a dispersion or solution of the agent and fusing it to the surface at the time of drying can be used.

In order to apply the matting agent to the surface of the photosensitive layer by powdering, that is, the matting agent is applied by a method such as a powder coating method, a fluid immersion method, an electrostatic powder spraying method, and an electrostatic fluid immersion method. It is preferred to uniformly disperse or scatter on the photosensitive layer formed on the support in advance. After the powdering, a matting agent can be fused to the surface of the photosensitive layer by appropriately performing a heat treatment (fusion treatment). The fusion process is performed using a heat source such as hot air or an infrared heater.
The matting agent is placed in a furnace heated to 30 ° C. or melted through a heating roll. At this time, some matting agents may be integrated with each other, and the obtained melt is fixed and dispersed in a spherical cap shape on the photosensitive layer, and the effect of preventing blocking of the present invention can be effectively exerted. . The contact between the matting agents is fixed to the surface and inside of the melt, but does not affect the printing plate.

The dispersion of the matting agent is applied directly to the photosensitive layer,
In the case of fusing to the surface during drying, an organic solvent or water that does not dissolve the photosensitive layer, a matting agent is added to a mixed solvent composed of a plurality of types, and the matting agent is immediately dispersed on the photosensitive layer by ultrasonic dispersion. This is achieved by applying a matting agent dispersion and drying.

In the case where the dispersion of the matting agent is sprayed and fused on the surface during drying, it is achieved by spraying the ultrasonic dispersion of the matting agent on the surface of the photosensitive layer, drying and fusing the surface. You. As a dispersion solvent of the dispersion, water is preferable in terms of explosion proof, environmental suitability, workability and the like, and the content of the matting agent in the matting agent dispersion is desirably 10 to 30% by weight. As a spraying method, a known method such as an air spray method, an airless spray method, an electrostatic air spray method, an electrostatic atomizing electrostatic coating method, or the like can be adopted.

Incidentally, the photosensitive layer of this type of planographic printing plate includes:
It is also possible to add the above-mentioned basic compounds, and the effects obtained thereby are also as described above.

[Hyortho novolak resin according to claims 1 to 3] A novolak resin produced by co-condensing a phenol component having a specific composition with an aldehyde or a ketone and having a predetermined X value as defined above. Is required, and the effect of the present invention cannot be obtained even if any one of them is missing. When producing such a resin, the phenol component is composed of (1) phenols 0 to 50.
Mol%, (2) m-alkylphenols 20 to 80
Mol%, (3) p-alkylphenols 20 to 80
It is preferably selected from the range of mol%, and preferably contains at least one of (2) m-alkylphenols and (3) p-alkylphenols together with (1) phenol.
The alkyl group of the m-, p-alkyl group phenol is a lower alkyl group such as methyl, ethyl, propyl, octyl, nonyl, hexyl, i-propyl and the like.

More preferably, (1) phenols 0
５０50 mol%, (2) m-alkylphenols 20
~ 80 mol%, (3) p-alkylphenols 20
A resin produced using a phenol component consisting of ８０80 mol%, a phenol component of 0-40 mol%, (2) 30-80 mol% of m-alkylphenols, and (3) a p-alkylphenol 20 It is preferably composed of ８０80 mol%.

[Low-molecular-weight high-ortho novolac according to claim 4 → co-condensation again] The low-molecular-weight high-ortho novolak synthesized according to the detailed description of claims 1 to 3 above is again mixed with a phenol component (the above-mentioned phenol compound). A novolak resin comprising a resin obtained by condensation of aldehydes or ketones (secondary reaction, polymerization conditions are the same as normal conditions). The content of the photosensitive layer of the novolak resin is the same as in claims 1 to 3 above.

[High Ortho Novolak Resin According to Claim 4] The content of the photosensitive layer of the novolak resin is as defined in Claim 1 above.
Same as ~ 3.

[Resin Condensed with Aromatic Aldehydes and Aromatic Ketones According to Claims 5 to 7] As aromatic aldehydes (monoaldehyde, dialdehyde, trialdehyde, etc.) are particularly preferable. It is a hydroxyl group-containing aromatic aldehyde.

[Naphthol novolak resin according to claims 8 to 9] The content of the photosensitive layer of the novolak resin is the same as in the above claims 1 to 3.

(Sensitive Material Film Surface pH) Next, the definition of the film surface pH will be described. Measuring device: Digital pH meter HM of Toa Denpa Kogyo
-18B Preparation: Printing plate with ² g / m ² photosensitive material photosensitive layer on support Measurement: After standardizing the pH meter, measure 10 μl of pure water with a micropipette, drop it on the sample to be measured and drop it on the water drop. On the other hand, the measuring part of the pH meter was lowered vertically and the film was placed on the membrane surface, and the measured value 2 minutes later was taken as the membrane surface pH.

The pH of the film surface is preferably 4 to 8 for improving the storage stability and suppressing the decrease in reproducibility of small spots with time after exposure. More preferably, when the film surface pH is 5 to 7.4 or less, there is no effect of improving the storage stability and suppressing the decrease in small point reproducibility with time after exposure, and when the film surface pH is 8 or more, the sensitivity is significantly reduced.

Next, the coating solution pH will be described. Measurement device: Digital pH meter HM-30S manufactured by Toa Denpa Kogyo KK Adjustment: A solid material having a solid content of 10% by weight dissolved in an arbitrary organic solvent or water or a plurality of mixed solvents used for coating.

Measurement: After standardizing the pH meter, the measuring part of the pH meter was lowered vertically to the coating solution to be measured, and the measured value was obtained by immersing the coating solution in the coating solution for 2 minutes.

The coating solution pH is preferably 3.5 to 8 for improving the storage stability and suppressing the decrease in reproducibility of small spots with time after exposure. More preferably, it is 4 to 6.5.
There is no effect of suppressing a decrease in reproducibility of small spots over time after exposure.

Next, the basic compound will be described. The basic compound is a compound capable of capturing a proton (H ⁺ ).

Amine compounds: The following Schiff bases: The following triphenylsulfonium acetates can be mentioned.

Basic nitrogen-containing resins described in JP-A-8-123030, organic basic compounds described in JP-A-9-54437, amine compounds and nitrogen-containing heteroaromatic compounds described in JP-A-8-22120, Thiosulfonate compounds described in JP-A-8-212598, JP-A-7-219217
In the case of using a heat-neutralized basic compound such as a sulfonyl hydrazide compound described above, the sensitivity is greatly improved by heating (post-baking) before exposure and development.

As long as the compound can capture proton (H ⁺ ), any compound other than the above compounds can be used without limitation.

These basic compounds may be used alone or in combination of two or more. The amount used is 0.1 in the photosensitive layer.
001 to 10% by weight is preferable, and 0.01 to 5% by weight is more preferable. When the content is 0.001 or less, there is no effect of improving storage stability and suppressing a decrease in reproducibility of small spots with time after exposure.
Above, the sensitivity is significantly reduced.

Specific examples of the amine compound include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, isopropylamine, and n-propylamine. Butylamine, isobutylamine, sec-butylamine, tert-butylamine, cyclohexylamine, benzylamine, α
-Phenylethylamine, β-phenylethylamine,
Ethylenediamine, tetramethylenediamine, hexamethylenediamine, tetramethylammonium hydroxide, aniline, methylaniline, dimethylaniline, diphenylamine, triphenylamine, o-toluidine, m-
Toluidine, p-toluidine, o-anisidine, m-anisidine, p-anisidine, o-chloroaniline, m-
Chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-
Nitroaniline, m-nitroaniline, p-nitroaniline, 2,4-dinitroaniline, 2,4,6-trinitroaniline, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, benzidine, p
-Aminobenzoic acid, sulfanilic acid, sulfanilamide, pyridine, 4-dimethylaminopyridine, piperidine, piperazine, urea and the like.

The Schiff base is specifically represented by the general formula

[0151]

Embedded image [However, R ₁ and R ₂ represent a hydrocarbon group (eg, an alkyl group such as a methyl group, an isopropyl group, an octyl group, a heptadecyl group, a cycloalkyl group such as a cyclobutyl group and a cyclohexyl group, an aryl group such as a phenyl group and a tolyl group) Such]
The following are mentioned as a specific example.

[0152]

Embedded image

Specific examples of these phenol components include:
Examples of the phenol (1) include phenol, monohydric, dihydric, and trihydric phenols such as catechol, resorcin, hydroquinone, and pyrogallol, with monohydric phenol being preferred. Examples of the m-alkylphenol of (2) include m-cresol, 3,5-xylenol, carvacrol, and thymol, and examples of the p-alkylphenol of (3) include p-cresol and 2,4-xylenol. However, these can be used alone or in combination. However, the phenol contains monohydric phenol at 95 mol% or more, and the m-alkylphenol contains m-cresol at 95 mol% or more,
As the p-alkylphenol, it is preferable to use one containing 95 mol% or more of p-cresol.

Examples of the aldehydes include formaldehyde, acetaldehyde, benzaldehyde, acrolein, methacrolein, crotonaldehyde, acrolein dimethyl acetal, furfural, and the like. Preferred are formaldehyde and benzaldehyde. As formaldehyde, an aqueous formaldehyde solution (formalin) and paraformaldehyde which is an oligomer of formaldehyde can be used.
In particular, 37% formalin is industrially produced in large quantities, which is advantageous.

Examples of ketones include acetone and methyl ethyl ketone.

As the method for producing the novolak resin of the present invention, a known method used for this kind of reaction, in particular, a method for producing a high-ortho novolak resin can be appropriately applied. For example, an organic acid salt of a specific divalent metal as shown in Japanese Patent Publication No.
A method of addition-condensing phenols containing m- / p-mixed cresols with aldehydes under the conditions of, or partially adding and condensing phenols and aldehydes with an organic acid salt of a divalent metal as a catalyst, There is a method of performing addition condensation using an acid as a catalyst.

In addition, J.I. appl. Chem 1957
As described on pages 676 to 688, a method of addition-condensing a phenol with an aldehyde using a hydroxide or oxide of a divalent metal as a catalyst, There is a method in which a phenol and an aldehyde are partially addition-condensed as a catalyst, and then addition-condensation is further performed using an acid as a catalyst. Further, a method of adding an aqueous solution of formalin to phenols prepared by mixing m- / p-cresol at a predetermined ratio and condensing the mixture with triethylamine (JP-A-3-253859, JP-A-3-2538)
No. 60), a method in which phenols and paraformaldehyde are dissolved in a non-polar solvent such as toluene, and heated to a high temperature under pressure. Acid catalysts such as oxalic acid are widely used in the production of novolak resins, but the resin produced by the method of producing a high-ortho novolak resin has a lower X value than the resin obtained by the usual production method of a novolak resin. Tends to be higher. In the present invention, it is preferable to apply a method using an organic acid salt or oxide of a divalent metal as a catalyst.

In the novolak resin of the present invention, in the ¹³ C-NMR spectrum of a deuterated dimethyl sulfoxide solution of this resin, the integrated value of the peak from 23.0 to 31.0 ppm is A, 23.0 to 37.0 ppm. When the integrated value of the peak up to B is B, the value of X = A / B is X ≧ 0.
57.

Here, ¹³ C-NMR measurement is performed under the following conditions. Using JOEL EX-270 type Fourier transform nuclear magnetic resonance apparatus (resonance frequency 67.00 MHz),
Inverse gated decoupling method (non-NOE decoupling measurement) is applied. The measurement temperature was 22 to 24 ° C., the pulse width was 6.8 μs (approximately 45 degrees), the holding time was 3 seconds, the observation frequency width was 20,000 Hz, the number of data points was 33 K, and the number of integrations was 4000 or more.
ppm.

All of the peaks of the ¹³ C-NMR spectrum defined here should be attributed to the methylene bond between aromatic rings, and the peak ratio and the X value are two different.
Alternatively, it is to be understood that the ring corresponds to a specific bonding mode of both, including the configuration, of the same ring.

However, in reality, in a mixed novolak resin of phenol and alkylphenol, the spectrum of this portion is wide and consists of a mixture of many peaks. It is not yet clear what the individual assignments are, and various types of bonding are included in the X value.
Roughly, it seems that phenol and alkylphenol are correlated with the ratio of those bonded at the ortho position to each other.

The novolak resin of the present invention has an X value of X
≧ 0.57, but more preferably satisfies X ≧ 0.60.

The weight average molecular weight Mw of the novolak resin of the present invention is determined by gel permeation chromatography (G
When the display in terms of polystyrene measured by PC) is performed, it is preferably in the range of 3.0 × 10 ^{2 to} 3.0 × 10 ⁴ , particularly 1.0 × 10 ^{3 to} 1.0 × 10 ^4. Is preferably within the range. In general, if it is less than 3.0 × 10 ² , the film-forming property is poor, and if it exceeds 3.0 × 10 ⁴ , the sensitivity is remarkably reduced.

The amount of the unreacted monomer in the novolak resin of the present invention is at most 5 mol%, preferably at most 2 mol%. If the amount of the unreacted monomer exceeds 5 mol%, it is not preferable because chemical resistance may be deteriorated or printing performance may be reduced. In order to reduce the amount of the unreacted monomer of the resin to 2 mol% or less, for example, after the condensation reaction, the object can be achieved by increasing the degree of reduced pressure.

The proportion of the novolak resin in the photosensitive composition for a printing plate (at the time of forming the photosensitive layer) of the present invention is usually 5%.
To 80% by weight, more preferably 10 to 70% by weight.
It is.

As an alkali-soluble novolak resin, m
-Cresol 30 to 90 mol% and the general formula (2)

[0167]

Embedded image [Wherein X is _{-CH 3, -C 2 H 5,} -C (CH 3) 3,
—CO ₂ CH ₃ or —CO ₂ C ₂ H ₅ , and 3 ≧ n
≧ 1, 3 ≧ m ≧ 1] (provided that m-
(Excluding cresol) A polystyrene-equivalent molecular weight obtained by condensing a phenol containing 70 to 10 mol% with formaldehyde and obtained by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard is 6300 to 25000. , 2500 to 6000 and 150 to 900, where a / b = 0 to 1.
It is intended to provide a positive radiation-sensitive resin composition characterized by using a resin having a ratio of 5 and c / b = 0.5 to 1.5.

In the composition of the present invention, formaldehyde is condensed with a phenol containing 30 to 90 mol% of m-cresol and 30 to 90 mol% of the compound of the formula (2) as an alkali-soluble novolak resin. The resulting resin is used.

The compound of the general formula (2) used in the present invention includes, for example, o-cresol, 3,5-dimethylphenol, 2,5-dimethylphenol, 2,3-dimethylphenol,
Dimethylphenol, 2,4-dimethylphenol,
2,6-dimethylphenol, 3,4-dimethylphenol, 2,3,5-trimethylphenol, 4-t-butylphenol, 2-t-butylphenol, 3-t-
Butylphenol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 4-
t-butercatechol, 4-methoxyphenol, 3-
Methoxyphenol, 2-methoxyphenol, 2-methoxycatechol, 2-methoxyresorcinol, 3-
Methoxyresorcinol, 2,3-dimethoxyphenol, 2,5-dimethoxyphenol, 3,5-dimethoxyphenol, methyl gallate, ethyl gallate,
Methyl methoxy-4,5-dihydroxybenzoate, 3-
Ethyl methoxy-4,5-dihydroxybenzoate, 4-
Methyl methoxy-3,5-dihydroxybenzoate, 4-
Ethyl methoxy-3,5-dihydroxybenzoate, 3,
Methyl 4-dimethoxy-5-hydroxybenzoate, 3,
Ethyl 4-dimethoxy-5-hydroxybenzoate, 3,
Methyl 5-dimethoxy-4-hydroxybenzoate, 3,
Ethyl 5-dimethoxy-4-hydroxybenzoate, 3-
Ethylphenol, 2-ethylphenol, 4-ethylphenol, 2,3,5-triethylphenol, 3,
5-diethylphenol, 2,5-diethylphenol, 2,3-diethylphenol and the like can be mentioned. These compounds are used alone or in combination of two or more.

The use ratio (mol%) of m-cresol to the compound of the general formula (2) is from 30 to 90/70 to 10
It is.

When the proportion of m-cresol and the compound of the formula (2) is less than 30 mol% or more than 90 mol%, the resolution and the developability are reduced. In addition, this use ratio is the use ratio of the raw material at the time of synthesizing the novolak resin.

The alkali-soluble novolak resin used in the present invention is a GPC column (G200 manufactured by Toyo Soda).
0H ₆ 2 pieces, G3000H ₆ 1 piece, G4000H ₆
The molecular weight was 6300 in terms of polystyrene determined by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions of a flow rate of 1.5 ml / min, an elution solvent of tetrahydrofuran, and a column temperature of 40 ° C. When the maximum height values of the peaks in the range of ２５25000, 2500-6000 and 150-900 are a, b and c, respectively, a / b = 0-1.5
And c / b = 0.5 to 1.5.
By using this alkali-soluble novolak resin, a resin excellent in resolution, sensitivity, developability, and heat resistance can be obtained as compared with a conventional alkali-soluble novolak resin.

When the value of a / b exceeds 1.5, developability and sensitivity deteriorate. When the value of c / b exceeds 1.5, the heat resistance deteriorates, and when the value of c / b is less than 0.5, the sensitivity and the resolution decrease.

The alkali-soluble novolak resin used in the present invention is synthesized by condensing the phenol with formaldehyde in the presence of an acid catalyst, but can also be synthesized without a catalyst. As the acid catalyst used at this time,
Examples thereof include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as formic acid, oxalic acid, and acetic acid. The amount of formaldehyde used is preferably 0.7 to 3 moles per mole of phenols, and the amount of acid catalyst used is preferably 0 to 0.1 moles per mole of phenols.

In the condensation reaction, water is usually used as a reaction catalyst. However, when the phenol used does not dissolve in an aqueous formaldehyde solution and becomes heterogeneous from the beginning of the reaction, a hydrophilic solvent is used as a reaction medium. Can also be used. Examples of the hydrophilic catalyst used in this case include alcohols such as methanol, ethanol, propanol and butanol, and cyclic ethers such as tetrahydrofuran and dioxane.

The use amount of these reaction media is preferably 20 to 1000 parts by weight per 100 parts by weight of the total amount of phenols and formaldehyde.

The reaction temperature of the condensation reaction can be appropriately adjusted according to the reactivity between phenols and formaldehyde, but is usually 10 to 200 ° C., preferably 70 to 13 ° C.
0 ° C. Examples of the reaction method for obtaining the alkali-soluble novolak resin include, for example, a method in which less reactive phenols, formaldehyde and an acid catalyst are charged together and reacted, and a reaction in which phenols are added to formaldehyde and an acid catalyst as the reaction proceeds. And the like. In the method in which the phenols are added and reacted with the progress of the reaction, the alkali-soluble novolak resin is more reproducibly and stably produced,
It is preferable to first take a method in which a part of phenols, formaldehyde and an acid catalyst are charged and polymerized, and then the remaining phenols are added and reacted as the reaction proceeds. After the completion of the condensation reaction, the internal temperature is generally raised to 1 to remove unreacted substances, acid catalyst and reaction medium present in the system.
The temperature is increased to 30 to 230 ° C., and volatile components are distilled off under reduced pressure.
Next, the molten alkali-soluble novolak resin is dripped onto a steel belt or the like to recover the alkali-soluble novolak resin. Alternatively, a method in which the alkali-soluble novolak resin is recovered by dissolving it in a solvent may be used.

Examples of the aromatic aldehyde include those represented by the following general formula (3).

[0179]

Embedded image [Wherein R _{4 to} R ₈ may be the same or different, and represent a hydrogen atom, a hydroxyl group, a formyl group, a halogen atom, an alkyl group,
It represents a cycloalkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group or a nitro group. However,
At least one of R ₄ and R ₈ is a hydroxyl group, and at least one of the remaining is an alkoxy group. In R _{4 to} R ₈ of the general formula (3), the halogen atom is preferably a chlorine atom, a bromine atom or an iodine atom,
A chlorine atom is more preferred. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a t-butyl group is preferable. Is more preferable. As the cycloalkyl group, a cyclopropyl group, a cyclopentyl group, a cycloheptyl group, and a cyclooctyl group are preferred, and a cyclohexyl group is more preferred. Examples of the alkoxy group include a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group or a t-butoxy group. Is preferably an alkoxy group,
Methoxy and ethoxy groups are more preferred. As the alkenyl group, an alkenyl group having 2 to 4 carbon atoms such as a vinyl group, a propenyl group, an allyl group or a butenyl group is preferable, and a vinyl group and an allyl group are more preferable. As the aryl group, a phenyl group, a xylyl group, a triyl group or a cumenyl group is preferable, and a phenyl group is more preferable.
The aralkyl group is preferably a benzyl group, a phenethyl group or a cumyl group, and more preferably a benzyl group.

However, at least one of R _{4 to} R ₈ must be a hydroxyl group. Incidentally, the substitution position of the hydroxyl group,
There is no particular limitation. Further, at least one of the remaining is an alkoxy group, the number of the alkoxy groups is preferably 1 and 2, and the substitution position is not particularly limited.

Specific examples of the aromatic aldehyde represented by the general formula (3) are shown below, but the compounds usable in the present invention are not limited to these.

[0182]

Embedded image

[0183]

Embedded image

[0184]

Embedded image

[0185]

Embedded image

[0186]

Embedded image

A phenol represented by the general formula (2):
The mixing ratio of formaldehyde and the aromatic aldehyde represented by the general formula (3) is not particularly limited as long as the amount of the aromatic aldehyde necessary for sufficiently exerting the effects of the present invention is used. 2) Phenols 100
In the case where it contains mol% or other phenols, the aromatic aldehyde is preferably 0.01 to 50 mol% or less to 100 mol% of all the phenols, and 0.1 to 50 mol%.
More preferably, it is less than 1 to 40 mol%. This range is preferable in terms of sensitivity.

As a preferred condensate, the following general formula (4)
a) and the compounds represented by (4b).

[0189]

Embedded image

[Wherein, R _{1 to} R ₃ each independently represent a hydrogen atom, an alkyl or alkenyl group or an aryl group having 1 to 6 carbon atoms, and m represents 0, 1, 2 or 3. Or the general formula (4b)

[0191]

Embedded image

[Wherein, R _{1 to} R ₃ each independently represent a hydrogen atom, an alkyl or alkenyl group having 1 to 6 carbon atoms or an aryl group. k ′ represents 0, 1 or 2;
Or 3 is represented. A novolak resin obtained by reacting an aldehyde containing an aromatic aldehyde with a phenol compound in the presence of an acid catalyst in the presence of an acid catalyst without isolating a low molecular weight component, and further condensing with a phenol and formaldehyde; And a photosensitive resin composition comprising an o-naphthoquinonediazide compound.

The aromatic aldehydes represented by the general formulas (4a) and (4b) are preferably, for example, methylbenzaldehydes such as benzaldehyde and 4-methylbenzaldehyde, polyaldehydes such as terephthalaldehyde, o-, m- and p-. -Hydroxybenzaldehydes such as hydroxybenzaldehyde, or o-, m-
Or methoxybenzaldehydes such as p-methoxybenzaldehyde. These aromatic aldehydes are used alone or in combination of two or more.
Examples of the aldehydes include aromatic aldehydes represented by the general formulas (4a) and (4b) and one or more aliphatic aldehydes other than formaldehyde (eg, acetaldehyde or glyoxal).
May be used.

Further, without isolating low molecular weight components obtained by reacting an aldehyde containing an aromatic aldehyde with a phenol compound in the presence of an acid catalyst, a novolak resin obtained by further condensing with a phenol and formaldehyde is used. You can combine them.

The naphthol novolak compound contained in the photosensitive composition of the present invention is a novolak type compound obtained by condensing naphthol or a derivative thereof with a carbonyl compound, and is, for example, a compound represented by the following general formula (5): Can be represented.

[0196]

Embedded image

[In the formula, R ¹ and R ² may be the same or different and each is a hydrogen atom, a substituted or unsubstituted alkyl group, or a cyclic substituent, and m is an integer indicating the degree of polymerization. is there. Here, m is 15 or less, and when R ¹ and R ² are an alkyl group, the number of carbon atoms is preferably 1 to 10. The substituent that can be introduced into the alkyl group includes a halogen atom, And the like.
Furthermore, alkyl groups, hydroxyl groups, carboxyl groups,
A substituent such as a halogen atom may be introduced into the naphthalene skeleton. ]

The naphthol derivative, which is one of the starting materials for this compound, is specifically a compound having a naphthalene skeleton into which at least one hydroxyl group has been introduced, and a part of the hydrogen atoms of which is a methyl group or the like. It indicates a compound substituted with an alkyl group or a halogen atom. When there is one hydroxyl group, the position to be introduced may be any of the α-position and β-position of the naphthalene skeleton.

Examples of the carbonyl compound include formaldehyde, acetaldehyde, propanol, butyral, glyoxylic acid, acetone, butanone, propanone, pentanone, hexanone, heptanone, octanone, nonanone, decanone, and cyclic compounds thereof. Furthermore, a picicyclo compound can be used.

The above-mentioned two kinds of raw materials, naphthol or a derivative thereof and a carbonyl compound, can be appropriately selected to obtain a desired naphthol novolak compound. In particular, the carbonyl compound can be obtained by converting formaldehyde, acetaldehyde, propanol, butyral and It is preferred to select from glyoxylic acid and use this carbonyl compound and naphthol. In this case, a naphthol novolak compound which is easy to synthesize and has excellent alkali solubility and dissolution inhibiting ability can be obtained.

Such a naphthol novolak compound is
Specifically, it can be synthesized by adding a carbonyl compound to naphthol or a derivative thereof, and condensing it by the action of an acid catalyst such as oxalic acid, sulfuric acid, phosphoric acid, or diphosphorus oxychloride. At this time, the naphthol novolak compound used in the present invention is usually obtained as a mixture of a monomer to a decamer. In the present invention, the reason why the molecular weight of the naphthol novolak compound is limited to 2000 or less is that if it is outside this range, the dissolution rate during development may be reduced. On the other hand, if the molecular weight of the naphthol novolak compound is too low,
Because the dissolution inhibiting ability and the applicability of the photosensitive composition tend to decrease, the molecular weight of the naphthol novolak compound is
Preferably it is 200-2000.

Such naphthol novolak compounds may be used alone or as a mixture of two or more.

The compounding amount of the naphthol novolak compound is 3 wt% or more and 90 w / w in the total solid content of the photosensitive composition.
It is preferably less than t%.

[0204]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited to these examples.

First, the synthesis of novolak resins used in Examples and Comparative Examples will be described. [Synthesis of high-ortho novolak (corresponding to Examples 1, 2 and 3)] Production Example 1 Phenol 3.5 was placed in a 300 ml separable flask.
g, meta-cresol 45.84 g, para-cresol 3
0.56 g {phenol / meta-cresol / para-cresol = 5/57/38 (molar ratio)}, formalin (37
% Aqueous solution) 35.88 g, zinc acetate dihydrate 0.80 g
The mixture was heated and stirred in an oil bath at 110 ° C. for 1 hour to react.
The product was dried to obtain a novolak resin. G of this resin
The weight average molecular weight by PC chromatography is 450
It was 0.

Production Example 2 Metacresol 4 was placed in a 300 ml separable flask.
8 g, para-cresol 32 g {meta-cresol / para-cresol = 6/4 (molar ratio)}, formalin 33.78
A novolak resin was synthesized in the same manner as in Production Example 1 except that g was used. The weight average molecular weight of this resin determined by GPC chromatography was 3,700.

Production Example 3 Phenol 10 was placed in a 300 ml separable flask.
g, 4-octylphenol novolak 87.65 g
｛Phenol / 4-octylphenol novolak = 2
Novolak resin was synthesized in the same manner as in Production Example 1 except that / 8 (molar ratio) and 33.78 g of formalin were used. The weight average molecular weight of this resin determined by GPC chromatography was 3,100.

[Synthesis of high-ortho novolak (low-molecular high-ortho novolak + co-condensation again) (corresponding to Example 4)] Production Example 4 Metacresol 4 was placed in a 300 ml separable flask.
8 g, paracresol 32 g {metacresol / paracresol = 6/4 (molar ratio)}, formalin 19.28
A novolak resin was synthesized in the same manner as in Production Example 1 except that g was used. (At this time, the weight average molecular weight of the resin by GPC chromatography was 900)
After the reaction was completed, 5 g of phenol was again charged using 19.28 g of formalin, and the mixture was heated and stirred in an oil bath at 110 ° C. for 1 hour to react. The product was dried to obtain a novolak resin.
The weight average molecular weight of this resin determined by GPC chromatography was 7,000.

[Synthesis of Tandem Novolak (Claim 5)
Production Example 5 Metacresol 4 was placed in a 500 ml separable flask.
8 g, paracresol 32 g {metacresol / paracresol = 6/4 (molar ratio)}, formalin 52.28
g and 0.01 g of oxalic acid were heated and stirred in an oil bath at 110 ° C. for 1 hour to cause a reaction.
g and 32 g of para-cresol {meta-cresol / para-cresol = 6/4 (molar ratio)} were continuously charged into the separable flask as the reaction proceeded, and reacted for 2 hours. Then, the oil bath temperature was raised to 180 ° C., and water, formaldehyde, unreacted meta-cresol, para-cresol and oxalic acid were removed under reduced pressure. Next, the melted novolak was returned to room temperature and collected. The weight average molecular weight of this resin measured by GPC chromatography is shown in the evaluation table.

Production Example 6 Metacresol 2 was placed in a 500 ml separable flask.
1.6 g, 4-t-butylphenol 30.0 g {metacresol / butylphenol = 6/4 (molar ratio)},
Charge 77.0 g of formalin and 0.01 g of oxalic acid 11
The mixture was heated and stirred in a 0 ° C. oil bath (inner temperature: 100 ° C.) for 1 hour to react. Thereafter, 21.6 g of meta-cresol and 30.0 g of 4-t-butylphenol (meta-cresol / butylphenol = 6/4 (molar ratio)) were used. Was continuously charged into a separable flask with the progress of the reaction, and reacted for 2 hours.
Then, the oil bath temperature was raised to 180 ° C., and water, formaldehyde, unreacted meta-cresol, para-cresol and oxalic acid were removed under reduced pressure. Next, the melted novolak was returned to room temperature and collected. The weight average molecular weight of this resin measured by GPC chromatography is shown in the evaluation table.

Production Example 7 Metacresol 3 was placed in a 500 ml separable flask.
2.4 g, 3,4-dimethylphenol 24.4 g {metacresol / 3,5-dimethylphenol = 6/4
(Molar ratio)｝, 77.0 g of formalin and 0.08 of oxalic acid
g in a 110 ° C. oil bath (inner temperature: 100 ° C.) for 1 hour while stirring and reacting.
g, 4-t-butylphenol 30.0 g {metacresol / butylphenol = 6/4 (molar ratio)} was continuously charged into the separable flask as the reaction progressed, and reacted for 2 hours. Then, the oil bath temperature was raised to 180 ° C., and water, formaldehyde, unreacted meta-cresol, para-cresol and oxalic acid were removed under reduced pressure. Next, the melted novolak was returned to room temperature and collected. G of this resin
The weight average molecular weight by PC chromatography is shown in the evaluation table.

[Synthesis of Aromatic Aldehyde Condensed Novolak (Corresponding to Claims 6, 7, and 8)] Production Example 8 Phenol 3.5 was added to a 300 ml separable flask.
g, meta-cresol 45.84 g, para-cresol 3
0.56 g {phenol / meta-cresol / para-cresol = 5/57/38 (molar ratio)} and 12.96 g of salicylaldehyde were charged and heated and stirred in a 110 ° C. oil bath for 3 hours to react. The product was dried. A novolak resin was obtained. The weight average molecular weight of this resin determined by GPC chromatography was 3,000.

Production Example 9 Phenol 3.5 was placed in a 300 ml separable flask.
g, meta-cresol 45.84 g, para-cresol 3
0.56 g {phenol / meta-cresol / para-cresol = 5/57/38 (molar ratio)} and benzaldehyde (11.26 g) were charged, and the mixture was heated and stirred in a 110 ° C. oil bath for 3 hours to react. A resin was obtained.
The weight average molecular weight of this resin determined by GPC chromatography was 3,000.

Production Example 10 Phenol 3.5 was placed in a 300 ml separable flask.
g, meta-cresol 45.84 g, para-cresol 3
0.56 g {phenol / meta-cresol / para-cresol = 5/57/38 (molar ratio)}, 2-hydroxy-
Charge 30.43 g of 4-methoxybenzaldehyde 1
The mixture was heated and stirred in a 10 ° C. oil bath for 3 hours to react, and the product was dried to obtain a novolak resin. The weight average molecular weight of this resin determined by GPC chromatography was 5,300.

Production Example 11 Phenol 3.5 was placed in a 300 ml separable flask.
g, meta-cresol 45.84 g, para-cresol 3
0.56 g {phenol / meta-cresol / para-cresol = 5/57/38 (molar ratio)}, formaldehyde (37% aqueous solution) 32.12 g and benzaldehyde 3
0.43 g was charged and stirred and heated in a 110 ° C. oil bath for 3 hours to react, and the product was dried to obtain a novolak resin. The weight average molecular weight of this resin determined by GPC chromatography was 4,700.

Production Example 12 Phenol 3.5 was placed in a 300 ml separable flask.
g, meta-cresol 45.84 g, para-cresol 3
0.56 g {phenol / meta-cresol / para-cresol = 5/57/38 (molar ratio)} and 13.4 g of terephthalaldehyde were charged and reacted by heating and stirring in an oil bath at 110 ° C. for 3 hours, and the product was dried. A novolak resin was obtained. The weight average molecular weight of this resin determined by GPC chromatography was 4,900.

[Synthesis of naphthol novolak (claim 9)
Production Example 13 α-naphthol 7 was placed in a 300 ml separable flask.
2.1 g, formaldehyde (37% aqueous solution) 20.3
The resulting mixture was heated and stirred in an oil bath at 110 ° C. for 3 hours to cause a reaction, followed by generating under reduced pressure and removing residual monomers to obtain a naphthol novolak resin. The weight average molecular weight of this resin determined by GPC chromatography was 660.

Production Example 14 α-naphthol 7 was placed in a 300 ml separable flask.
2.1 g, 37.56 g of 2-adamantanone and 50 ml of ethyl cellosolve were charged, and 3 g of phosphorous oxychloride was added thereto.
The mixture was heated and stirred in a 10 ° C. oil bath for 3 hours to cause a reaction. The reaction was generated under reduced pressure, and the residual monomer was removed to obtain a naphthol novolak resin. The weight average molecular weight of this resin determined by GPC chromatography was 350.

Production Example 15 β-naphthol 7 was placed in a 300 ml separable flask.
2.1 g, 37.56 g of 2-adamantanone and 50 ml of cyclohexanone were added, and 3 g of diphosphorus oxychloride was added thereto.
The mixture was heated and stirred in a 10 ° C. oil bath for 3 hours to cause a reaction. The reaction was generated under reduced pressure, and the residual monomer was removed to obtain a naphthol novolak resin. The weight average molecular weight of this resin determined by GPC chromatography was 530.

[Synthesis Method of Novolak Resin for Comparative Example] Production Example 16 Phenol 3.5 was placed in a 300 ml separable flask.
g, meta-cresol 45.84 g, para-cresol 3
0.56 g {phenol / meta-cresol / para-cresol = 5/57/38 (molar ratio)} and 32.1 g of formaldehyde were charged and heated and stirred in an oil bath at 110 ° C. for 3 hours to react. A resin was obtained. The weight average molecular weight of this resin determined by GPC chromatography was 3,700.

Production Example 17 Phenol 3.5 was placed in a 300 ml separable flask.
g, meta-cresol 45.84 g, para-cresol 3
0.56 g {phenol / meta-cresol / para-cresol = 5/57/38 (molar ratio)} and formaldehyde 9.2 g were charged and heated and stirred in an oil bath at 110 ° C. for 3 hours, and the product was dried and novolak was obtained. A resin was obtained. The weight average molecular weight of this resin determined by GPC chromatography was 200.

[Preparation of Support] A 0.3 mm thick aluminum plate (material 1050, tempered H16) was degreased with a 5% aqueous sodium hydroxide solution maintained at 65 ° C. for 1 minute, and then washed with water. It was immersed in a 10% sulfuric acid aqueous solution maintained at 25 ° C. for 1 minute to neutralize, and further washed with water. This aluminum plate was placed in a 1.0 wt% aqueous nitric acid solution at a temperature of 25%.
The electrolytic surface roughening was performed by using an alternating current at a temperature of 10 ° C., a current density of 10 A / dm ² , and a processing time of 60 sec. Then 5%
A desmut treatment was performed in a sodium hydroxide aqueous solution at a temperature of 60 ° C. for 10 seconds, and then an anodizing treatment was performed in a 20% sulfuric acid solution at a temperature of 20 ° C., a current density of 3 A / dm ² and a treatment time of 1 minute. . Then, the temperature was kept at 80 ° C.
% Ammonium acetate aqueous solution for 30 seconds, washed with water and dried at 80 ° C. for 3 minutes. Further, the substrate was immersed in an aqueous solution (concentration: 0.1 wt%) of carboxymethyl cellulose (abbreviated as CMC) kept at 85 ° C. for 30 seconds, and then dried at 80 ° C. for 5 minutes to prepare a support.

[Synthesis of acid-decomposable compound A] 1,1-dimethoxycyclohexanone (0.5 mol), phenyl cellosolve (1.0 mol) and p-toluenesulfonic acid 80 m
g were mixed and reacted at 120 ° C. for 8 hours while stirring. Methanol produced by the reaction and the reaction solvent were removed after the completion of the reaction. After cooling, wash with water, wash with sodium hydroxide solution, then wash with saturated saline until neutral, dehydrate the obtained compound with anhydrous potassium carbonate, and concentrate to dryness. White crystals of the acid decomposition product A were obtained.

[0224]

Embedded image

Example 1 [Preparation of photosensitive composition 1] A photosensitive composition was prepared by mixing the following proportions. Production Example 1 (high ortho novolak resin) 61.75 parts by weight Binder B molecular weight: 38000 14 parts by weight

[0226]

Embedded image

Acid decomposition product A 20 parts by weight Acid generator (A as described above) 3 parts by weight Cyanine dye (IR25 compound as described above) 1 part by weight Surfactant (Asahi Glass S-381) 0.25 parts by weight Solvent ( (PGM / MEK = 7/3) 1000 parts by weight

The photosensitive layer coating solution having the above composition was dried on the support and then coated with a wire bar so that the film thickness became 2.0 g / m ^2, and dried at 95 ° C. for 90 seconds to form an image forming material. I got

The resulting photosensitive lithographic printing plate was subjected to image exposure using a semiconductor laser (wavelength 830 nm, output 500 mw). The laser beam diameter is 1 / e ₂ of the intensity at the peak.
Was 13 μm. The resolution was 2000 dpi in both the scanning direction and the sub-scanning direction. After image exposure, Konica
The s-plate developer was diluted with SDR-1 (manufactured by Konica) / water = 1/5. Thereafter, the film was immersed in a developer maintained at 30 ° C. for 30 seconds to perform development, and then washed and dried. At this time, a non-image area (exposed area) is removed to form a positive image.

Evaluation of Sensitivity Under the above conditions, evaluation was made with exposure energy (mj / cm ² ) necessary for developing the exposed portion.

Developing Latitude A sample on which an image was formed at the above sensitivity was prepared by diluting the developing solution with SDR-1 / water = 1/3, 1/5 (normal conditions), 1
The image was developed under the same developing conditions as described above, and the sensitivity and background contamination of the non-image area were evaluated. Judgment standard 非: Non-image area is not stained. no problem. Δ: Non-image area is slightly stained. X: The non-image area is stained.

Chemical resistance The image obtained from the sensitivity evaluation image was added to the stock solution of Ultraplate Cleaner (manufactured by Dainichi Seika) for 15 minutes,
It was immersed for 0 minutes and 60 minutes, washed with water, and visually compared with the image part before immersion. Criteria 基準: There is no erosion of the image part. Δ: slight erosion of the image area, and the grain of the support under the photosensitive layer was slightly exposed. X: The image area was significantly eroded, and the grain of the support under the photosensitive layer was completely exposed.

Example 2 “Preparation of Photosensitive Composition 2” Production Example 1 (high-ortho novolak resin) 74.75 parts by weight Acid-crosslinkable resin: 20 parts by weight of hexamethoxymethylmelamine Acid generator (A in the above example) 3 Parts by weight Cyanine dye (IR25 compound exemplified above) 2 parts by weight Surfactant (Asahi Glass S-381) 0.25 parts by weight Solvent (PGM / MEK = 7/3) 1000 parts by weight

The photosensitive layer coating solution having the above composition was dried on the support, and then coated with a wire bar so that the film thickness became 2.0 g / m ^2, and dried at 95 ° C. for 90 seconds to form an image forming material. I got

The resulting photosensitive lithographic printing plate was subjected to image exposure using a semiconductor laser (wavelength: 830 nm, output: 500 mw). The laser beam diameter is 1 / e ₂ of the intensity at the peak.
Was 13 μm. The resolution was 2000 dpi in both the scanning direction and the sub-scanning direction. After image exposure, Konica
The s-plate developer was diluted with SDR-1 (manufactured by Konica) / water = 1/5. Thereafter, the film was immersed in a developer maintained at 30 ° C. for 30 seconds to perform development, and then washed and dried. At this time, a non-image area (unexposed area) is removed to form a negative image.

Sensitivity Evaluation Under the above conditions, evaluation was made with the exposure energy (mj / cm ² ) necessary for developing the exposed part.

Developing Latitude A sample on which an image was formed at the above sensitivity was prepared by diluting the developing solution with SDR-1 / water = 1/3, 1/5 (normal conditions), 1
The image was developed under the same developing conditions as described above, and the sensitivity and background contamination of the non-image area were evaluated. Judgment standard 非: Non-image area is not stained. no problem. Δ: Non-image area is slightly stained. X: The non-image area is stained.

Chemical resistance The image obtained from the sensitivity evaluation image was added to the stock solution of Ultra Plate Cleaner (manufactured by Dainichi Seika) for 15 minutes,
It was immersed for 0 minutes and 60 minutes, washed with water, and visually compared with the image part before immersion. Criteria 基準: There is no erosion of the image part. Δ: slight erosion of the image area, and the grain of the support under the photosensitive layer was slightly exposed. X: The image area was significantly eroded, and the grain of the support under the photosensitive layer was completely exposed. Other examples and comparative examples were performed as shown in the table (see the evaluation table and the attached compound table).

Example 3 [Preparation of photosensitive composition 1] Production example 1 (high-orno novolak resin) mixed at the following ratio to obtain a photosensitive composition 75.75 parts by weight Acid decomposition product A 20 parts by weight Acid generator (A in the above example) 3 parts by weight Cyanine dye (IR25 compound in the above example) 1 part by weight Surfactant (Asahi Glass S-381) 0.25 part by weight Solvent (PGM / MEK = 7/3) 1000 parts by weight Department

The photosensitive layer coating solution having the above composition was dried on the support and then coated with a wire bar so that the film thickness became 2.0 g / m ^2, and dried at 95 ° C. for 90 seconds to form an image forming material. I got

The obtained photosensitive lithographic printing plate was subjected to image exposure using a semiconductor laser (wavelength: 830 nm, output: 500 mw). The laser beam diameter is 1 / e ₂ of the intensity at the peak.
Was 13 μm. The resolution was 2000 dpi in both the scanning direction and the sub-scanning direction. After image exposure, Konica
The s-plate developer was diluted with SDR-1 (manufactured by Konica) / water = 1/5. Thereafter, the film was immersed in a developer maintained at 30 ° C. for 30 seconds to perform development, and then washed and dried. At this time, a non-image area (exposed area) is removed to form a positive image.

Sensitivity Evaluation Under the above conditions, evaluation was made with exposure energy (mj / cm ² ) necessary for developing the exposed part.

Developing Latitude A sample on which an image was formed at the above sensitivity was prepared by diluting the developing solution with SDR-1 / water = 1/3, 1/5 (normal conditions), 1
The image was developed under the same developing conditions as described above, and the sensitivity and background contamination of the non-image area were evaluated. Judgment standard 非: Non-image area is not stained. no problem. Δ: Non-image area is slightly stained. X: The non-image area is stained.

Chemical Resistance The image obtained from the sensitivity evaluation image was added to the stock solution of Ultra Plate Cleaner (manufactured by Dainichi Seika) for 15 minutes,
It was immersed for 0 minutes and 60 minutes, washed with water, and visually compared with the image part before immersion. Criteria 基準: There is no erosion of the image part. Δ: slight erosion of the image area, and the grain of the support under the photosensitive layer was slightly exposed. X: The image area was significantly eroded, and the grain of the support under the photosensitive layer was completely exposed.

Example 4 [Preparation of Photosensitive Composition 2] Production Example 1 (Hiortho novolak resin) 54.75 parts by weight Acid-crosslinkable resin: (CKP-918 methylol group-containing resole resin: Showa Polymer) 40 parts by weight Acid generator (A in the above example) 3 parts by weight Cyanine dye (IR25 compound in the above example) 2 parts by weight Surfactant (Asahi Glass S-381) 0.25 parts by weight Solvent (PGM / MEK = 7/3) 1000 parts by weight Department

The photosensitive layer coating solution having the above composition was dried on the support and then coated with a wire bar so that the film thickness became 2.0 g / m ^2, and dried at 95 ° C. for 90 seconds to form an image forming material. I got

The obtained photosensitive lithographic printing plate was subjected to image exposure with a semiconductor laser (wavelength: 830 nm, output: 500 mw). The laser beam diameter is 1 / e ₂ of the intensity at the peak.
Was 13 μm. The resolution was 2000 dpi in both the scanning direction and the sub-scanning direction. After image exposure, Konica
The s-plate developer was diluted with SDR-1 (manufactured by Konica) / water = 1/5. Thereafter, the film was immersed in a developer maintained at 30 ° C. for 30 seconds to perform development, and then washed and dried. At this time, a non-image area (unexposed area) is removed to form a negative image.

Sensitivity Evaluation Under the above conditions, evaluation was made with exposure energy (mj / cm ² ) necessary for developing the exposed portion.

Developing latitude The sample on which an image was formed at the above sensitivity was prepared by diluting the developing solution with SDR-1 / water = 1/3, 1/5 (normal conditions), 1
The image was developed under the same developing conditions as described above, and the sensitivity and background contamination of the non-image area were evaluated. Judgment standard 非: Non-image area is not stained. no problem. Δ: Non-image area is slightly stained. X: The non-image area is stained.

Chemical Resistance The image obtained from the sensitivity evaluation image was added to the stock solution of Ultraplate Cleaner (manufactured by Dainichi Seika) for 15 minutes,
It was immersed for 0 minutes and 60 minutes, washed with water, and visually compared with the image part before immersion. Criteria 基準: There is no erosion of the image part. Δ: slight erosion of the image area, and the grain of the support under the photosensitive layer was slightly exposed. X: The image area was significantly eroded, and the grain of the support under the photosensitive layer was completely exposed. Other examples and comparative examples are as shown in Tables 1 to 5.

[0251]

[Table 1]

[0252]

[Table 2]

[0253]

[Table 3]

[0254]

[Table 4]

[0255]

[Table 5]

[0256]

According to the present invention, it is possible to provide a photosensitive composition having improved chemical resistance, improved developer latitude, and high sensitivity.

Claims (10)

[Claims] 1. A ₁₃ C-NMR spectrum of a resin obtained by condensing a phenol component and aldehydes or ketones comprising the following (1) to (3), and a deuterated dimethyl sulfoxide solution of the resin: At 23.0
A, 23.0 to 31.0 ppm
When the integrated value up to 37.0 ppm is B, X =
An alkali-soluble resin having an A / B value of X ≧ 0.6, 2) a dye having absorption in infrared light, 3) a compound capable of generating an acid upon irradiation with actinic light, 4) an acid A compound having a bond which can be decomposed by a compound or a group which can be crosslinked by an acid. Phenol component (1) Phenols 0 to 50 mol% (2) m-alkylphenols 20 to 80 mol% (3) p-alkylphenols 20 to 80 mol% 2. The photosensitive composition according to claim 1, comprising at least one phenol component. 3. A photosensitive composition according to claim 1, wherein the phenolic resin has a molecular weight of 500 to 5,000. 4. The resin according to claim 1, which has a molecular weight of 20.
A photosensitive composition comprising a resin obtained by condensing a phenol and an aldehyde or a ketone containing a compound represented by the following general formula (1) with a novolak resin of 0 to 3000. Embedded image 5. A gel obtained by condensing an alkali-soluble novolak resin with a phenol and an aldehyde or a ketone containing the compound represented by the general formula (1) and using monodisperse polystyrene as a standard. The polystyrene-equivalent molecular weight determined by the permeation and chromatograph (GPC) method is 6500-30000, 1000-1000.
When the maximum heights of the peaks in the range of 6000 and 100 to 950 are a, b and c, respectively, a / b = 0
-1.5 and c / b = 0.05-1.5; 2) a dye having absorption in infrared light; 3) a compound capable of generating an acid upon irradiation with actinic light; 4) a compound decomposed by an acid. A photosensitive composition comprising a compound having a bond or a group capable of crosslinking by an acid. 6. A novolak resin obtained by condensing a phenol and an aromatic aldehyde containing a compound represented by the above general formula (1) as an alkali-soluble novolak resin, and 2) absorbing an infrared ray. A photosensitive compound comprising a compound having a bond capable of generating an acid upon irradiation with an actinic ray, and a compound having a bond capable of being decomposed by an acid or a group capable of being crosslinked by an acid. 7. The photosensitive composition according to claim 6, wherein the molecular weight of the novolak resin is in the range of 300 to 20,000. 8. A photosensitive composition comprising salicylaldehyde or benzaldehyde as a condensate of the phenol according to claim 6 or 7. 9. A 1) naphthol novolak resin, 2) a dye having absorption in infrared light, 3) a compound capable of generating an acid upon irradiation with actinic light, 4) a cross-linkable portion which can be decomposed by an acid or an acid. A photosensitive composition comprising a compound having a group. 10. The naphthol novolak resin having a molecular weight of:
The photosensitive composition according to claim 9, wherein the composition is in the range of 300 to 10,000.