JPH0812647A - Photosensitive compound, photosensitive composition and waterless planographic printing plate precursor - Google Patents

Abstract

(57) [Summary] [Structure] The present invention is a photosensitive compound that has a quinonediazide group, has good sensitivity to light, and is flexible, and thus can form a good pattern even in a curved structure or a twisted structure. is there. [Effect] Since a photosensitive compound that does not drop due to cracking even when forming a pattern on a curved surface structure or a twisted structure, it can be used not only on a flat surface but also on an uneven surface or a curved surface, which has the advantage of expanding the range of applications.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive compound, and more specifically to a photosensitive compound having a quinonediazide group as a photosensitive component. The present invention relates to a photosensitive compound that can be used for printing materials such as planographic printing plates. Particularly, it is suitable for a printing material to be used by being wound around a cylindrical plate mounting cylinder.

[0002]

2. Description of the Related Art Heretofore, various photosensitive compounds having a quinonediazide group have been proposed for use in pattern formation of resist materials and printing materials.

Among these, a photosensitive compound obtained by reacting a hydroxyl group of a phenol novolac resin with a quinonediazide compound, and a photosensitive composition using these are particularly known and widely used.

However, the photosensitive compound using the phenol novolac resin has the drawback that it is hard and brittle and cracks when a bending or twisting force is applied. Therefore, when forming a pattern on a curved surface structure or a twisted structure, there is a problem that chipping due to cracking occurs. In particular, when used as a printing material, since the printing plate is mostly used by being wound around a cylindrical plate mounting cylinder, a certain level of flexibility or more is required. In this respect, the photosensitive compound using the phenol novolac resin did not have the required flexibility.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, and to provide a photosensitive compound which is free from cracking or the like even when a pattern is formed on a curved structure or a twisted structure. It is a thing.

[0006]

The object of the invention can be achieved by the following photosensitive compounds.

(1) A photosensitive compound containing at least one structure represented by the following general formula (I).

[0008]

Embedded image (In the formula, R1 is a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, and includes an ester bond, an ether bond, a thioether bond, an amide bond, a urethane bond, a urea bond, a silicon atom and a nitrogen atom. M is a quinonediazide group.) (2) A photosensitive compound having at least one structure represented by the following general formula (II).

[0009]

[Chemical 9] (In the formula, R2 is a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, and includes an ester bond, an ether bond, a thioether bond, an amide bond, a urethane bond, a urea bond, a silicon atom and a nitrogen atom. M is a quinonediazide group. (3) A photosensitive compound having at least one structure represented by the following general formula (III).

[0010]

[Chemical 10] (In the formula, R3 is a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, and includes an ester bond, an ether bond, a thioether bond, an amide bond, a urethane bond, a urea bond, a silicon atom and a nitrogen atom. M is a quinonediazide group.) (4) A photosensitive compound having at least one structure represented by the following general formula (IV).

[0011]

[Chemical 11] (In the formula, R4 is a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, and includes an ester bond, an ether bond, a thioether bond, an amide bond, a urethane bond, a urea bond, a silicon atom and a nitrogen atom. M is a quinonediazide group.)

That is, the general formula (I) and the general formula (I
The photosensitive compounds represented by I), the general formula (III) and the general formula (IV) are more flexible than the photosensitive compounds using the phenol novolac resin, and can form various patterns such as a curved structure and a twisted structure. Are better.

In the structures represented by the general formulas (I), (II), (III) and (IV), R1, R2, R3 and R4 have 1 to 100 carbon atoms.
Is a substituted or unsubstituted hydrocarbon group and may contain an ester bond, an ether bond, a thioether bond, an amide bond, a urethane bond, a urea bond, a silicon atom, or a nitrogen atom. Specific examples thereof include a substituted or unsubstituted ester bond, an ether bond, a thioether bond, an amide bond, a urethane bond, a urea bond, a silicon atom, an alkyl group which may contain a nitrogen atom, a substituted or unsubstituted ester bond, Ether bond, thioether bond,
Amide bond, urethane bond, urea bond, silicon atom,
Examples of the alkenyl group which may contain a nitrogen atom, a substituted or unsubstituted ester bond, an ether bond, a thioether bond, an amide bond, a urethane bond, a urea bond, a silicon atom, an aryl group which may contain a nitrogen atom and the like. However, it is not limited to these. Since it is advantageous that the photosensitive compound as a whole is flexible, it is preferable that 20% or more of the R1, R2, R3 and R4 skeletons are formed by other than the aromatic ring.

The quinonediazide group may be any of those generally known, and in particular, general formula (V), general formula (VI) and general formula (VI)
Those having a structure represented by I) are preferable. Specific examples of the compound having these structures include the following, but the compounds are not limited to these and may be other compounds.

1,2-naphthoquinone-2-diazide-4
-Sulfonyl group, 1,2-naphthoquinone-2-diazide-5-sulfonyl group, 1,2-naphthoquinone-2-diazide-6-sulfonyl group, 1,2-naphthoquinone-2-
Diazido-7-sulfonyl group, 1,2-benzoquinone-
2-diazide-4-sulfonyl group, 1,2-benzoquinone-2-diazide-5-sulfonyl group and the like.

The method for synthesizing the photosensitive compound of the present invention includes the methods shown in the following procedures.
The method is not limited to these and may be synthesized by another method.

A monohydric alcohol or a polyhydric alcohol is reacted with epihalohydrin to obtain an epoxy group-containing compound,
A compound obtained by reacting this compound with hydroxybenzoic acid or aminophenol to obtain a compound containing a phenol structure, and reacting a quinonediazide compound with the portion of the phenolic hydroxyl group of this compound.

Here, specific examples of the monohydric alcohol include:
Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-hexanol, 2-hexanol, 3-hexanol, 2- Methyl-1-pentanol, 3-methyl-
1-pentanol, 2-methyl-2-pentanol, 3
-Methyl-2-pentanol, 1-octanol, 2-
Examples thereof include octanol, 1-decanol, and 2-decanol, but the present invention is not limited to these and may be other ones. Among these, ethanol, 1-propanol, 1
-Butanol, 2-methyl-2-propanol, 1-hexanol, 2-methyl-1-pentanol, 3-methyl-2-pentanol, 1-octanol, 1-decanol and 2-decanol are preferred.

Specific examples of the polyhydric alcohol include ethylene glycol, 1,2-propanediol, 1,3
-Propanediol, 1,2-butanediol, 1,3
-Butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 1,3-hexanediol, 2-methylpentane-1,5-diol, 3-methylpentane-1,5-
Diol, 2,3-dimethylbutane-1,4-diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, di Examples thereof include propylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and polyvinyl alcohol, but the invention is not limited to these and may be other. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol. , Triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and polyvinyl alcohol are particularly preferable.

By reacting at least one hydroxyl group of these monohydric alcohols or polyhydric alcohols with epihalohydrin, an epolicy group-containing compound can be obtained. Examples of epihalohydrin include epichlorohydrin, epibromohydrin, and epiiodohydrin.

Examples of hydroxybenzoic acid include substituted or unsubstituted 2-hydroxybenzoic acid, substituted or unsubstituted 3-hydroxybenzoic acid, and substituted or unsubstituted 4-hydroxybenzoic acid.
-Hydroxybenzoic acid.

As aminophenol, substituted or unsubstituted 2-aminophenol, substituted or unsubstituted 3-aminophenol or substituted or unsubstituted 4
-Aminophenols are mentioned.

The quinonediazide compound may be any one known in the art, and in particular, the general formula (V), the general formula (VI) and the general formula (VI)
Those having a structure represented by I) are preferable. Specific examples of the compound having these structures include the following, but the compounds are not limited to these and may be other compounds.

1,2-naphthoquinone-2-diazide-4
-Sulfonic acid, 1,2-naphthoquinone-2-diazide-
4-sulfonic acid chloride, 1,2-naphthoquinone-2-
Diazide-4-sulfonic acid bromide, 1,2-naphthoquinone-2-diazide-4-sulfonic acid sodium salt, 1,
Potassium 2-naphthoquinone-2-diazide-4-sulfonate, 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride, 1,2-naphthoquinone -2-diazide-5-sulfonic acid bromide, 1,2-naphthoquinone-
Sodium 2-diazide-5-sulfonate, potassium 1,2-naphthoquinone-2-diazide-5-sulfonate,
1,2-benzoquinone-2-diazide-4-sulfonic acid, 1,2-benzoquinone-2-diazide-4-sulfonic acid chloride, 1,2-benzoquinone-2-diazide-
4-sulfonic acid bromide, 1,2-benzoquinone-2-
Sodium diazide-4-sulfonate, potassium 1,2-benzoquinone-2-diazide-4-sulfonate and the like.

The desired photosensitive compound can be obtained by the synthetic method as shown in (4) or any other method. Here, among the compounds represented by, those using hydroxybenzoic acid are represented by the general formula (I) and the general formula (I
The compounds represented by formula (I), which use aminophenol, are the compounds represented by formula (III) and formula (IV).

The photosensitive compound of the present invention is mixed with a resin or the like to form a suitable photosensitive composition, whereby a photoresist,
It can be used as a resist composition such as an electron beam resist, or as a photosensitive composition for printing plate materials such as letterpress and planographic printing.

When used as a resist composition, the photosensitive compound may be mixed with a novolac resin or the like. The resist composition can be patterned by forming a coating film of the resist composition on an appropriate support and selectively exposing it to ultraviolet rays or electron beams.

When used as a photosensitive composition for a printing plate material, the photosensitive compound may be mixed with polyurethane, polyamide or the like. A printing plate material is obtained by forming a coating film (photosensitive layer) made of a photosensitive composition for a printing plate material on an appropriate support, and the printing plate material is patterned by selectively exposing it to ultraviolet rays. By doing so, a printing plate can be obtained.

The photosensitive composition for a printing plate material of the present invention is particularly suitable for use as a photosensitive layer of a waterless planographic printing plate.

The structure of the waterless planographic printing plate precursor will be described below.

The waterless planographic printing plate precursor comprises at least a photosensitive layer and a silicone rubber layer laminated in this order on a substrate, and utilizes the ink repulsion property of the silicone rubber layer without using dampening water. Can be printed on.

The substrate may be any of those used in ordinary waterless lithographic printing plates or those proposed, such as metal plates of aluminum, copper, zinc, steel, polyethylene terephthalate, polystyrene, etc. Examples thereof include, but are not limited to, a plastic film or sheet such as polypropylene, chloroprene rubber, a substrate having rubber elasticity such as NBR, or coated paper. It is optional to perform appropriate processing on the surface of these substrates to improve the adhesiveness with the upper layer. Among these, a metal plate is preferable, and an aluminum plate whose surface is plain or uneven is preferable.

It is also possible to coat these substrates with a primer layer for the purpose of preventing halation and for other purposes. As the constituent components of the primer layer, for example, epoxy resin, acrylic resin, urea resin, polyurethane resin, polyester resin, polystyrene resin, amide resin, menamine resin, benzoguanamine resin, phenol resin, diazo resin, milk casein,
Examples include, but are not limited to, gelatin, soy protein, albumin, and the like. These resins can be used alone or in combination of two or more. By adding a cross-linking agent such as a polyfunctional isocyanate or a silane coupling agent to these resins, it is possible to improve the adhesiveness to the substrate or the photosensitive layer. Further, it is optional to add additives such as a dye, a pigment, a photosensitizer and a photocoloring agent as needed for the purpose of improving the plate inspection property and other purposes.
Further, it is also optional to add a known catalyst.

The mixing ratio of each component in the primer layer is not particularly limited, but preferably 100 parts by weight of one or more of the above resins, and optionally 0 to 100 parts by weight of a crosslinking agent, a dye or 0 to 100 parts by weight of additives such as pigments, 0 to 10 parts by weight of known catalysts,
Film thickness 0.1 to 100 μm, more preferably 0.5 to 50
What is obtained by providing it with μm is preferable.

Examples of the photosensitive layer include photosensitive layers containing the photosensitive compound of the present invention. In such a photosensitive layer, when crosslinking or modification is not carried out, the exposed photosensitive layer and the silicone rubber layer thereon are removed by development. When crosslinking or modification is performed, the exposed photosensitive layer is not removed by development, and only the silicone rubber layer on the exposed photosensitive layer is removed.

When a crosslinking agent is used in the photosensitive layer, the crosslinking agent may be a polyfunctional isocyanate such as paraphenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, Hexamethylene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl isocyanate or adducts thereof, or polyfunctional epoxy compounds such as polyethylene glycol diglycidyl ethers, polypropylene glycol diglycidyl ethers, bisphenol A diglycidyl ether, trimethylolpropane Examples thereof include, but are not limited to, triglycidyl ether.
It is preferable that the heat curing is carried out at a temperature that does not lose the photosensitivity of the photosensitive compound, usually at 130 ° C. or lower, and therefore a catalyst or the like is usually used together.

Further, as a method for modifying the photosensitive layer by reacting it with a monofunctional compound to make it insoluble or insoluble in a developing solution, similarly, the active group of the photosensitive compound is similarly esterified, amidated, or the like. Examples thereof include conversion to urethane. The compound that reacts with the active group of the photosensitive compound may be a low molecular weight compound or a relatively high molecular weight compound,
A monomer may be graft-polymerized on the photosensitive compound.

When the photosensitive compound of the present invention is used in such a waterless lithographic printing plate, it is possible to add another photosensitive compound in order to improve the sensitivity efficiency to light.

Other photosensitive compounds include phenol formaldehyde resins (phenol, p-tert-butylphenol, p-octylphenol, p-nonylphenol, cardanol, cresol, xylenol,
Resins obtained by condensing phenols and formaldehydes such as catechol and pyrogallol under acidic catalyst) with quinonediazide group added, resole resins (for example, the above phenols and formaldehydes are condensed under alkaline catalyst) The resin obtained by adding a quinonediazide group, a resin obtained by adding a quinonediazide group to a resorcinbenzaldehyde condensation resin, a product obtained by adding a quinonediazide group to a pyrogallolacetone resin, and the like. Here, the quinonediazide group is 1,2-
A benzoquinone-2-diazide-4-sulfonyl group,
Examples thereof include, but are not limited to, a 1,2-naphthoquinone-2-diazido-4-sulfonyl group and a 1,2-naphthoquinone-2-diazide-5-sulfonyl group.

If necessary, an organic polymer compound which can be mixed with these compounds can be added to the photosensitive layer. Examples of such organic polymer compounds include, but are not limited to, the following polymers and copolymers.

Polymers of acrylic acid ester, methacrylic acid ester, acrylonitrile, such as polyethyl acrylate, polybutyl acrylate, polymethyl methacrylate, and copolymers thereof.

Unblended rubbers such as polybutadiene, polyisobutylene, polychloroprene, styrene-butadiene rubber and the like.

Vinyl polymers such as polyvinyl acetate,
Polyvinyl alcohol, polybutyl butyral and the like, and copolymers thereof.

Polyethers such as polyethylene oxide.

Reaction products of polyesters such as phthalic acid, isophthalic acid, maleic acid and adipic acid with ethylene glycol, 1,4-butanediol, 1,6-hexanediol and neopentyl glycol.

Reaction formation of polyurethane, for example, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, etc. with polyester polyol obtained by polyether polyol of 1,4-butanediol, 1,6-hexanediol, etc. Stuff.

Epoxy Resin Polyamide These organic polymer compounds can be used alone or in combination of two or more to improve the shape retention of the photosensitive layer film. Of these organic polymer compounds, and are particularly preferable.

Further, a known photoinitiator or photosensitizer may be added for the purpose of improving the photoreactivity of the quinonediazide compound and other purposes. As the photoinitiator or photosensitizer to be added, benzoin methyl ether, benzoin isopropyl ether, α, α-dimethoxy-α-
Benzoin derivatives such as phenylacetophenone, benzophenone, fluorenone, xanthone, thioxanthone, N-methylacridone, N-butylacridone,
4,4'-bis (dimethylamino) benzophenone,
4,4'-bis (diethylamino) benzophenone, 2
-Chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone and the like, but are not limited thereto. Among these, benzophenones are particularly effective.

In addition to the above components, if necessary, a dye,
Addition of additives such as pigments and photo-color formers and known catalysts is optional.

The mixing ratio of each component in the photosensitive layer is not particularly limited, but preferably 1 to 100 parts by weight of the photosensitive compound of the present invention, 0 to 100 parts by weight of another photosensitive compound, a crosslinking agent or a photosensitive material. 0 to 10000 parts by weight of a compound that reacts with an active group of a polymerizable compound, 0 to 10000 parts by weight of an organic polymer compound, 0 of a photoinitiator or a photosensitizer.
To 100 parts by weight, and if necessary, additives and known catalysts are added in an amount of 0 to 100 parts by weight to give a film thickness of 0.1 to 100 μ
m, preferably 0.5 to 10 μm. If it is too thin, cissing tends to occur in the photosensitive layer, and if it is too thick, it is economically disadvantageous, so the above range is preferred.

Examples of the silicone rubber layer include, but are not limited to, the following silicone rubbers.

A product obtained by crosslinking an organic polysiloxane represented by the following general formula (VIII) and having a molecular weight of 100 to 1,000,000, preferably 1,000 to 500,000.

[0053]

[Chemical 12] (In the formula, m is an integer of 2 or more, R5 and R6 are carbon numbers 1 to 5
0-substituted or unsubstituted alkyl group, 2 to 50 carbon atoms
A substituted or unsubstituted alkenyl group having 5 to 50 carbon atoms
Of at least one substituted or unsubstituted aryl group, which may be the same or different, and particularly preferably a methyl group of 60% or more. ) Such an organic polysiloxane can be made into a further crosslinked silicone rubber by adding an organic peroxide and subjecting it to heat treatment.

As a general method for crosslinking the organic polysiloxane, there may be mentioned a method for crosslinking the organic polysiloxane with a silicon compound containing a hydrolyzable functional group directly bonded to a silicon atom. In particular, an organic compound having a silanol structure at the terminal is used. Cured by the reaction of a polysiloxane and a silicon compound having two or more functional groups such as an alkoxy group directly bonded to a silicon atom, an acyloxy group, a ketoxime group amide group, an aminooxy group, an amino group, an alkenyloxy group, and hydrogen, Making rubber is a commonly used method.
It is also possible to cure the organic polysiloxane into a rubber with a radical initiator. In these curing, addition of a known catalyst is optional.

A product obtained by cross-linking by an addition reaction between an organic polysiloxane having a group represented by the following general formula (IX) and a polysiloxane compound having a group represented by the following general formula (X).

[0056]

[Chemical 13]

Embedded image (In the formula, R7 and R8 are each a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, and a substituted or unsubstituted aryl group having 5 to 50 carbon atoms. At least one selected from the group may be the same or different.) Such a silicone rubber has a polyvalent hydrogen organopolysiloxane and two or more ethylenically unsaturated bonds in one molecule. Obtained by reaction with a polysiloxane compound. Here, the group of general formula (IX) may be at either the terminal or the middle of the molecular chain. In addition, the general formula (X)
The group may be at either the terminal or the middle of the molecular chain. Examples of the organic group other than the group of the general formula (IX) and the group of the general formula (X) include a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, Examples thereof include a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, and a methyl group having 60% or more is particularly preferable. The molecular weights of the organic polysiloxane having a group represented by the general formula (IX) and the polysiloxane compound having a group represented by the general formula (X) are preferably 100 to 1,000,000, and preferably 1,000 to 500,000. The thing is more preferable. In this addition reaction, adding a known catalyst is optional.

The mixing ratio of each component in the silicone rubber layer is not particularly limited, but in the case of the silicone rubber layer, 100 parts by weight of the organic polysiloxane represented by the general formula (VIII) is added to the silicone rubber layer directly bonded to the silicon atom. 0.1 to 100 parts by weight of a decomposable functional group-containing silicon compound, and a composition containing 0 to 50 parts by weight of a known catalyst as necessary,
Film thickness 0.1 to 100 μm, preferably 0.5 to 30 μm
It is good to obtain by providing. In the case of the silicone rubber layer, 100 parts by weight of an organic polysiloxane having a group represented by the general formula (IX), a polysiloxane compound having a group represented by the general formula (X) of 0.
1 to 1000 parts by weight, if necessary, a known catalyst in an amount of 0 to 5
It may be obtained by providing 0 parts by weight of the composition with a film thickness of 0.1 to 100 μm, preferably 0.5 to 30 μm.

In the waterless planographic printing plate as described above,
Adhesion between the substrate and the photosensitive layer, the photosensitive layer and the silicone rubber layer,
Since it is very important for basic plate performance such as image reproducibility and printing durability, it is possible to provide an adhesive layer between each layer and add an adhesiveness improving component to each layer if necessary. Is. In particular, for adhesion between the photosensitive layer and the silicone rubber layer, it is effective to provide a known silicone primer or a silane coupling agent between the layers or add a silicone primer or a silane coupling agent to the silicone rubber layer or the photosensitive layer. When such an adhesive layer is provided, the thickness of the adhesive layer is not particularly limited,
It is good to obtain it by providing it with 0.05 to 100 μm, preferably 0.5 to 30 μm.

For the purpose of protecting the silicone rubber layer forming the surface of the waterless planographic printing plate constructed as described above, a protective film laminated or plastic is provided on the surface of the silicone rubber layer with a plain or uneven surface treatment. It is also possible to apply or transfer a sheet material to form a protective layer. The film thickness of such a protective film or protective layer is not particularly limited, but may be 0.05 to
It may be obtained by providing it with a thickness of 1000 μm, preferably 0.5-100 μm.

The waterless planographic printing plate described above is manufactured, for example, as follows, but the invention is not limited thereto.
First, on the substrate, a reverse roll coater, an air knife coater, a normal coater such as a Mayer bar coater, or a spin coater such as a hoela, or another coater,
If necessary, the composition solution to form the primer layer is applied, dried and, if necessary, heat-cured, then the composition solution to form the photosensitive layer is applied, dried, and optionally heat-cured, Thereafter, if necessary, a composition solution for forming an adhesive layer is applied onto the photosensitive layer, dried, and optionally heat-cured, and a composition solution for forming a silicone rubber layer is applied thereon, dried, If necessary, heat cure, and finally, if necessary, apply a protective film using a laminator or the like.

The waterless lithographic printing plate precursor thus produced is, for example, in the case of a light-transmitting protective film, as it is or after peeling it, and in the case of a film having poor light-transmitting property, it is vacuum-bonded negatively. Exposed to actinic radiation through the film. The light source used in this exposure step is one that generates abundant ultraviolet rays, and a mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a tungsten lamp, a fluorescent lamp or the like can be used.
It is not limited to these.

Then, if there is a protective film, peel it off and rub the plate surface with a developing pad containing a developing solution to remove the silicone rubber layer in the exposed area and, in some cases, the photosensitive layer below it. It becomes a receiving part.

Any developer may be used as long as it is proposed as a developer for a waterless lithographic printing plate, and examples thereof include water, aliphatic hydrocarbons, aromatic hydrocarbons and alcohols. , Ethers, esters, and mixtures of two or more thereof, but are not limited thereto.

The developing method may be manual development or development by a known developing device, but it is preferable to use a developing device in which a pretreatment section, a development section, and a posttreatment section are provided in this order.

[0065]

EXAMPLES Hereinafter, specific synthesis examples and examples will be shown, but the present invention is not limited to these, and other synthesis methods may be used, and the present invention may be applied to practice in other fields.

Synthesis Example 1

[Chemical 15] Ethylene glycol 30.0g, epichlorohydrin 9
5 g, 40.0 g of sodium hydroxide and 200.0 g of water were mixed and reacted by heating under reflux for 10 hours while stirring. After the reaction, water was removed by drying under reduced pressure, and a product and a by-product sodium chloride were separated by filtration.

85.0 g of this product, 140.0 g of 4-hydroxybenzoic acid, 2.5 g of triethylbenzylammonium chloride and 200 g of dioxane were mixed and reacted at 70 ° C. for 8 hours while stirring. After the reaction, water and diethyl ether were added, the mixture was separated using a separating funnel, and the organic layer was dried over sodium sulfate. Sodium sulfate was removed by filtration, and the solvent was removed by drying under reduced pressure to obtain a product.

20.0 g of this product and 20.0 of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride
and g were dissolved in 200.0 g of dioxane. Next, 6.0 g of sodium carbonate was dissolved in 54.0 g of water, and the 10 wt% sodium carbonate aqueous solution was added dropwise to the above dioxane solution over 10 minutes. (At this time, the dioxane solution was stirred and the liquid temperature was kept at 40 ° C.) After the dropping was completed, the reaction was carried out while stirring for 4 hours while keeping the liquid temperature at 40 ° C. After the reaction, the reaction solution was poured into 1000.0 g of water to precipitate a product, and the product was allowed to stand for 10 hours to precipitate the product. The supernatant liquid is removed by decantation and dried under reduced pressure to obtain the desired photosensitive compound A.
I got

[0069] (IR _{^{data) 3600~3000cm -1 νOH 2115~2170cm -1 νN 2}} 1599,1567cm -1 νC = O (NMR data) 3.4~4.1ppm m 14H 7.9 ppm d 2H 7.0 ppm d 4H 8.0 ppm d 4H 7.4 ppm d 2H 8.2 ppm d 2H 7.7 ppm t 2H 8.6 ppm d 2H (decomposition point) 155 ° C. Synthesis example 2 In Synthesis example 1, 1, 2 -Naphthoquinone-2-diazide-5-sulfonic acid chloride 20.0 g was added to 1,2-naphthoquinone-2-diazide-4-sulfonic acid chloride 2
All were synthesized by the same method as in Synthesis Example 1 except that the amount was changed to 0.0 g to obtain the intended photosensitive compound B.

[0070] (IR _{^{data) 3600~3000cm -1 νOH 2115~2170cm -1 νN 2}} 1599,1567cm -1 νC = O (NMR data) 3.4~4.1ppm m 14H 7.9 ppm d 2H 7.0 ppm d 4H 8.0 ppm d 4H 7.3 ppm t 2H 8.4 ppm d 2H 7.7 ppm t 2H 8.5 ppm d 2H (decomposition point) 157 ° C. Synthesis example 3 In Synthesis example 1, 1, 2 -Naphthoquinone-2-diazide-5-sulfonic acid chloride 20.0 g was added to 1,2-benzoquinone-2-diazide-4-sulfonic acid chloride 1
Synthesis was carried out by the same method as in Synthesis Example 1 except that the amount was changed to 5.0 g to obtain the intended photosensitive compound C.

[0071] (IR _{^{data) 3600~3000cm -1 νOH 2115~2170cm -1 νN 2}} 1599,1567cm -1 νC = O (NMR data) 3.4~4.1ppm m 14H 7.7 ppm d 2H 7.0 ppm t 4H 7.9 ppm d 2H 7.3 ppm d 2H 8.0 ppm t 4H (decomposition point) 157 ° C. Synthesis Example 4 In Synthesis Example 1, 4-hydroxybenzoic acid 140.0.
Synthesis was carried out by the same method as in Synthesis Example 1 except that g was changed to 140.0 g of 2-hydroxybenzoic acid to obtain the desired photosensitive compound D.

[0072] (IR _{^{data) 3600~3000cm -1 νOH 2115~2170cm -1 νN 2}} 1599,1567cm -1 νC = O (NMR data) 3.4~4.1ppm m 14H 7.7 ppm t 2H 7.2 ppm d 2H 7.9 ppm d 2H 7.4 ppm d 2H 8.0 ppm d 2H 7.5 ppm t 2H 8.2 ppm d 2H 7.6 ppm t 2H 8.6 ppm d 2H (decomposition point) 152 C. Synthetic example 5 In Synthetic example 1, 4-hydroxybenzoic acid 140.0
All were synthesized by the same method as in Synthesis Example 1 except that g was changed to 125.0 g of 4-aminophenol to obtain the intended photosensitive compound E.

(IR data) 3600 to 3000 cm ⁻¹ νOH, νNH 2115 to 2170 cm ⁻¹ νN ₂ 1599,1567 cm ⁻¹ νC═O (NMR data) 3.4 to 4.0 ppm m 14H 7.8 ppm d 4H 4 0.0-4.1 ppm s 2H 7.9 ppm d 2H 6.9 ppm d 4H 8.2 ppm d 2H 7.4 ppm d 2H 8.6 ppm d 2H 7.7 ppm t 2H (decomposition point) 155 ° C. Synthesis Example 6 In Synthesis Example 1, 4-hydroxybenzoic acid 140.0
All were synthesized by the same method as in Synthesis Example 1 except that g was changed to 125.0 g of 2-aminophenol to obtain the desired photosensitive compound F.

(IR data) 3600 to 3000 cm ⁻¹ νOH, νNH 2115 to 2170 cm ⁻¹ νN ₂ 1599,1567 cm ⁻¹ νC = O (NMR data) 3.4 to 4.0 ppm m 14H 7.7 ppm t 2H 4 0.0-4.1 ppm s 2H 7.9 ppm d 2H 7.2 ppm d 2H 8.0 ppm d 2H 7.4 ppm d 2H 8.2 ppm d 2H 7.5 ppm t 2H 8.6 ppm d 2H 7.6 ppm t 2H (decomposition point) 152 ° C. Synthesis Example 7 Synthesis was performed using the same method as in Synthesis Example 1 except that 30.0 g of ethylene glycol was changed to 30.0 g of glycerin in Synthesis Example 1. To obtain a photosensitive compound G.

[0075] (IR _{^{data) 3600~3000cm -1 νOH 2115~2170cm -1 νN 2}} 1599,1567cm -1 νC = O (NMR data) 3.5~3.9ppm m 20H 7.9 ppm d 3H 7.0 ppm d 6H 8.0 ppm d 6H 7.4 ppm d 3H 8.2 ppm d 3H 7.7 ppm t 3H 8.6 ppm d 3H (decomposition point) 155 ° C. Synthesis example 8 In synthesis example 1, ethylene glycol 30 All were synthesized by the same method as in Synthesis Example 1 except that 0.0 g was changed to 25.0 g of trimethylol propane to obtain the target photosensitive compound H.

[0076] (IR _{^{data) 3600~3000cm -1 νOH 2115~2170cm -1 νN 2}} 1599,1567cm -1 νC = O (NMR data) 0.9 ppm t 3H 7.7 ppm t 3H 1.2 ppm q 2H 7.9 ppm d 3H 3.5 to 3.9 ppm m 21H 8.0 ppm d 6H 7.0 ppm d 6H 8.2 ppm d 3H 7.4 ppm d 3H 8.6 ppm d 3H (decomposition point) 153 C. Synthesis Example 9 Synthesis was carried out in the same manner as in Synthesis Example 5 except that 30.0 g of ethylene glycol was changed to 30.0 g of glycerin in Synthesis Example 5, to obtain a target photosensitive compound I.

(IR data) 3600 to 3000 cm ⁻¹ νOH, νNH 2115 to 2170 cm ⁻¹ νN ₂ 1599,1567 cm ⁻¹ νC═O (NMR data) 3.5 to 3.9 ppm m 20H 7.8 ppm d 6H 4 0.0 to 4.1 ppm s 3H 7.9 ppm d 3H 6.9 ppm d 6H 8.2 ppm d 3H 7.4 ppm d 3H 8.6 ppm d 3H 7.7 ppm t 3H (decomposition point) 155 ° C. Synthesis Example 10 Synthesis was carried out in the same manner as in Synthesis Example 5 except that 30.0 g of ethylene glycol was changed to 25.0 g of trimethylolpropane in Synthesis Example 5, to obtain a target photosensitive compound J.

(IR data) 3600 to 3000 cm ⁻¹ νOH, νNH 2115 to 2170 cm ⁻¹ νN ₂ 1599,1567 cm ⁻¹ νC═O (NMR data) 0.9 ppm t 3H 7.7 ppm t 3H 1.2 ppm q 2H 7.8 ppm d 6H 3.5-3.9 ppm m 21H 7.9 ppm d 3H 4.0-4.1 ppm s 3H 8.2 ppm d 3H 6.9 ppm d 6H 8.6 ppm d 3H 7.4 ppm d 3H (decomposition point) 155 ° C. Example 1 1.0 g of the photosensitive compound A synthesized in Synthesis Example 1,
1.0 g of novolak resin synthesized from 30% by weight of 3-cresol, 40% by weight of 1,4-cresol, 30% by weight of 2,5-xylenol and formalin was dissolved in 4.0 g of ethyl cellosolve acetate to obtain 0.2 μm of Millipore. A positive resist coating solution was prepared by filtering with a filter. The coating solution was spin-coated on a 0.20 mm aluminum plate whose surface had been subjected to oxidation treatment and heat treatment at 300 ° C. for 2 minutes to give a thermal strain, and a 1.0 μm coating film was obtained by pre-paging at 90 ° C. for 30 minutes. Got Sensitivity (indicated by the reciprocal of the minimum exposure time at which the residual film rate becomes 0) was determined using a mask aligner MA-10 manufactured by Kodak Corporation. The development was carried out using NMD-3 manufactured by Tokyo Ohka Co., Ltd. at 20 ° C. for 1 minute. The resolution test was performed by using the above-mentioned mask aligner using a resolution test pattern of Toppan Printing Co., Ltd.

Further, the percentage of the film thickness after development with respect to the film thickness before development of the unexposed area is defined as the residual film rate, which is used as a scale representing the degree of film slippage after development of the unexposed area.

Furthermore, the cross-sectional shape of the pattern was observed with an electron microscope.

The results are as shown in Table 1, showing a good resolution and a good pattern shape.

Examples 2 to 10 The same evaluations as in Example 1 were carried out except that the photosensitive compound A was changed to B to I in Example 1. The results are shown in Table 1.
As shown in Fig. 3, good resolution was exhibited and the pattern shape was also good.

Comparative Example 1 Evaluations were made in the same manner as in Example 1 except that the photosensitive compound A was changed to the following compound.

1,2-naphthoquinone-2-diazide-4
Sulfonic acid and phenol-formaldehyde novolac resin ("Sumilite resin" PR5062 manufactured by Sumitomo Durez)
Partial ester of 2) (esterification degree 5 by elemental analysis method
0%) The results are shown in Table 1, and the resolution was poor and the pattern shape was not good.

[0085]

[Table 1] Example 11 The following primer composition was applied to a degreased aluminum plate having a thickness of 0.3 mm and heat-treated at 100 ° C. for 5 minutes to form a primer layer having a thickness of 15 μm after drying.

(A) “Vylon” UR-8300 (manufactured by Toyobo Co., Ltd.); polyester polyurethane, methyl ethyl ketone / toluene 1/1 mixed solvent 30% by weight solution) 333 parts by weight (b) dipentaerythritol hexaacrylate 60 Parts by weight (c) 2,4-diethylthioxanthone 6 parts by weight (d) 4-dimethylaminobenzoic acid ethyl ester 6 parts by weight (e) "Taipek" TTO-55 (A) (manufactured by Ishihara Sangyo Co., Ltd .; ultrafine particles) Titanium oxide) 15 parts by weight (f) Propylene glycol monomethyl ether 700 parts by weight Then, using a 3 kW ultra-high pressure mercury lamp, 0.6 J / cm.
A full surface exposure of ² was performed for 20 seconds under nitrogen to cure.

The following sensitizing solution was applied onto this, and 110
Heat treatment was performed at 30 ° C. for 30 seconds to form a photosensitive layer having a film thickness of 1.5 μm after drying.

(A) Photosensitive Compound A synthesized in Synthesis Example 1 74 parts by weight (b) 1,6-hexanediisocyanate 17 parts by weight (c) 2-hydroxyethyl methacrylate / N- (4-hydroxyphenyl) methacrylamide 31 parts by weight (d) N-methylacridone 3.2 parts by weight (e) 2,4-diethylthioxanthone 3.2 parts by weight (f) Lactic acid 1 part by weight (g) Dimethyltin dilaurate 0.6 parts by weight (h) Dioxane 770 parts by weight The following silicone rubber composition was applied onto this photosensitive layer, and heat-treated at 95 ° C. for 10 minutes, and the film thickness after drying was 2 μm.
The silicone rubber layer was formed.

(A) Polydimethylsiloxane having vinyl structure at both ends (polymerization degree of about 700) 15.5 parts by weight (b) Polydimethylsiloxane having silanol structure at both ends (polymerization degree of about 8000) 2 parts by weight (c) Methyl group at both ends Structure Polydimethylsiloxane (polymerization degree: about 50) 2 parts by weight (d) 1-trimethoxysilylpropane 0.1 part by weight (e) Olefin-platinic acid 0.2 part by weight (f) Tetracyclo (methylvinyl) siloxane 0. 2 parts by weight (g) "Isopar" G (manufactured by Esso Kagaku Co., Ltd.) 90 parts by weight The surface of the silicone rubber layer thus prepared has a thickness of 6
A single-sided matted biaxially oriented polypropylene film having a thickness of μm was laminated so that the non-matted surface was in contact with the silicone rubber layer to obtain a waterless lithographic printing plate precursor.

A metal halide lamp (“Idol Fin” 200 manufactured by Iwasaki Electric Co., Ltd.) was used for this waterless planographic printing plate.
0) was used to perform exposure at 25 mJ / cm ^{2 with} a UV meter (“Light Measure Type UV-402A” manufactured by Oak Manufacturing Co., Ltd.). A negative film having a halftone dot image of 150 lines / inch is vacuum-bonded to the printing plate precursor obtained as described above, and the metal halide lamp is used for 240 m.
An exposure of J / cm2 was performed.

After exposure, the protective film was peeled off, and the temperature was kept at room temperature 28.
Development was carried out using TWL-860K (Toray Co., Ltd. waterless lithographic printing plate precursor developing apparatus) under the conditions of ° C and humidity of 60%. Here, as the pretreatment liquid, a liquid having the following composition was used.

(A) Phenylpropylene glycol 0.03 parts by weight (b) Propylene glycol 1.2 parts by weight (c) 4- (1,1-Dimethylethyl) benzoic acid 0.3 parts by weight (d) Potassium hydroxide (50%) 1.5 parts by weight (e) Polyethylene oxide nonyl ether 0.01 parts by weight (f) Sodium butylnaphthalene sulfonate 0.3 parts by weight (g) Potassium silicate (silicon dioxide: 26%, potassium oxide: 13.5%) 1.3 parts by weight (h) potassium sulfite 2.7 parts by weight (i) 50% gluconic acid 0.6 parts by weight (j) triethanolamine 0.6 parts by weight (k) monoethanolamine 0 0.6 parts by weight (l) Water 53 parts by weight Water was used as the developing solution. A liquid having the following composition was used as the dyeing liquid.

(A) 20 parts by weight of “Solfit” (manufactured by Kuraray Isoprene Chemical Co., Ltd.) (b) 0.5 parts by weight of “Leodol TW-0120” (manufactured by Kao Corporation; surfactant) ) Benzyl alcohol 5 parts by weight (d) Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd .; dye) 1.0 parts by weight (e) Water 100 parts by weight This printing plate is commercial off-wheel printer ("LITHOPIA").
Mitsubishi Heavy Industries Co., Ltd.), using "Dry Ocolor" black ink, indigo, red, yellow ink manufactured by Dainippon Ink and Chemicals, Inc., 650r. p. m. ． Printing was performed on high-quality paper at the speed of and a printing durability test was performed. The results are shown in Table 2, and the printing plate was inspected after the completion of printing, but the printing plate was slightly damaged, and it was possible to continue printing.

Examples 12 to 20 Waterless lithographic plates were prepared in the same manner as in Example 11 except that the photosensitive compound A used in the photosensitive layer was changed to B to I. The same printing durability test was performed. The results are shown in Table 2, and the printing plate was inspected after the completion of printing, but the printing plate was slightly damaged, and it was possible to continue printing.

Comparative Example 2 A waterless lithographic plate was prepared in the same manner as in Example 11 except that the photosensitive compound A used in the photosensitive layer was changed to the following compound. A printing durability test was conducted.

1,2-naphthoquinone-2-diazide-5
Sulfonic acid and phenol-formaldehyde novolac resin ("Sumilite resin" PR5062 manufactured by Sumitomo Durez)
Partial ester of 2) (degree of esterification by elemental analysis 3
The results are as shown in Table 2. When the printing plate was inspected after the printing was completed, the printing plate was severely damaged and it was impossible to continue printing.

[0097]

[Table 2]

[0098]

EFFECT OF THE INVENTION Since the photosensitive compound of the present invention has the above-mentioned characteristics, it is a photosensitive compound which is not cracked even when a pattern is formed on a curved structure or a twisted structure. Therefore, for example, when a photosensitive composition is used, it can be used not only on a flat surface but also on an uneven surface or a curved surface,
This has the advantage of expanding the range of applications. For example, when it is used as a photosensitive layer of a waterless planographic printing plate precursor, it is not cracked or chipped even when it is wound around a cylindrical plate mounting cylinder.

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Claims (15)

[Claims] 1. A photosensitive compound containing at least one structure represented by the following general formula (I). Embedded image (In the formula, R1 is a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, and includes an ester bond, an ether bond, a thioether bond, an amide bond, a urethane bond, a urea bond, a silicon atom and a nitrogen atom. M is a quinonediazide group.) 2. A photosensitive compound having at least one structure represented by the following general formula (II). Embedded image (In the formula, R2 is a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, and includes an ester bond, an ether bond, a thioether bond, an amide bond, a urethane bond, a urea bond, a silicon atom and a nitrogen atom. M is a quinonediazide group.) 3. A photosensitive compound having at least one structure represented by the following general formula (III). Embedded image (In the formula, R3 is a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, and includes an ester bond, an ether bond, a thioether bond, an amide bond, a urethane bond, a urea bond, a silicon atom and a nitrogen atom. M is a quinonediazide group.) 4. A photosensitive compound having at least one structure represented by the following general formula (IV). [Chemical 4] (In the formula, R4 is a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, and includes an ester bond, an ether bond, a thioether bond, an amide bond, a urethane bond, a urea bond, a silicon atom and a nitrogen atom. M is a quinonediazide group.) 5. The photosensitive compound according to claim 1, wherein 20% or more of the number of carbon atoms in the R1 skeleton is formed by other than an aromatic ring. 6. The photosensitive compound according to claim 2, wherein 20% or more of the number of carbon atoms in the R2 skeleton is formed by other than an aromatic ring. 7. The photosensitive compound according to claim 3, wherein 20% or more of the number of carbon atoms in the R3 skeleton is formed by other than an aromatic ring. 8. The photosensitive compound according to claim 4, wherein 20% or more of the number of carbon atoms in the R4 skeleton is formed by other than an aromatic ring. 9. The photosensitive compound according to claim 1, wherein the quinonediazide group has a structure represented by the following general formula (V). Embedded image 10. A quinonediazide group represented by the following general formula (VI):
It has a structure shown by.
The photosensitive compound according to any one of 1. [Chemical 6] 11. A quinonediazide group represented by the following general formula (VI
I) having a structure represented by I).
9. The photosensitive compound according to any one of to 8. [Chemical 7] 12. A photosensitive composition containing the photosensitive compound according to any one of claims 1 to 11. 13. The photosensitive composition according to claim 12, which is a photosensitive composition for a printing plate material. 14. The photosensitive composition according to claim 12, which is a resist composition. 15. A waterless planographic printing plate precursor in which at least a photosensitive layer and a silicone rubber layer are laminated in this order on a substrate, wherein the photosensitive layer comprises the photosensitive composition according to claim 13. Waterless planographic printing plate original.