JPH01188851A - Planographic printing plate material free from dampening water - Google Patents

Abstract

PURPOSE:To improve the sticking property of the title material, and to prevent the stain of an image by composing the photosensitive layer contd. in the material of a photocrosslinking type material contg. a specified compd. or a polymer or a prepolymer capable of reacting with the compd. CONSTITUTION:The photosensitive layer and a layer contg. a repulsive substance are mounted on a supporting body, and the photosensitive layer is composed of the photocrosslinking material contg. the compds. shown by formulas I and/or II, and the polymer or the prepolymer capable of reacting with the compds. In formulas I and II, R1 and R2 are each 2-30C alkyl, aryl or aralkyl group which may be substd., R3 is alkyl, phenyl or naphthyl group which may be substd. Thus, the planographic printing plate material having the improved sticking property and the less stain of the image is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a lithographic printing plate material that does not require dampening water, and more particularly to a lithographic printing plate material that does not require dampening water and does not cause stains on printed matter.

[Prior Art] Conventionally, a lithographic printing plate material that does not require dampening water and has a photosensitive layer and a silicone rubber layer on a support in that order is used, and by exposing and developing the material, the silicone rubber layer or silicone rubber in the image area is removed. By peeling off all of the layers and the photosensitive layer, an image is formed and a printing plate is manufactured.

As photosensitive layers used in conventional lithographic printing plate materials that do not require dampening water, there are 1) photopolymerization type, 2) diazo resin type, and 2) photodimerization type. The photopolymerization type (2) utilizes photopolymerization of a monomer containing a vinyl group, and the photopolymerization is carried out by exciting the monomer directly with active light or indirectly using an initiator. When this type is used, exposed areas are made insolubilized by polymerization, and unexposed areas are eluted and removed by a solvent. As the diazo resin type (1), for example, one using a diazo resin obtained by condensing zinc chloride double salt of 4-diazo-1,1'-diphenylamine chloride and paraformaldehyde is known. When this type is used, the diazo group is photodecomposed by exposure and hydrophilicity is lost, so the unexposed areas are removed when developed with an aqueous solvent. ■As photodimerization type compounds, among the compounds that undergo a (2+2) type addition reaction and give a four-membered cyclic dimer through a photodimerization reaction, those that have been put to practical use as photosensitive resins include cinnamic acid. and cinnamylidene acetic acid are known. When this type is used, the unexposed area is eluted and removed by a solvent.

[Problems to be Solved by the Invention] However, all of the conventional photosensitive layers of types (1) to (3) have the disadvantage of poor adhesion to silicone rubber, resulting in image staining.

[Object of the Invention] Therefore, an object of the present invention is to provide a lithographic printing plate material which has excellent adhesion and does not cause image stains and does not require dampening water.

[Means for Solving the Problems] The inventor of the present invention has conducted intensive studies to achieve the above object, and as a result, has arrived at the present invention.

Namely, 1. the dampening water-free lithographic printing plate material according to the present invention (hereinafter referred to as
A dampening water-free lithographic printing plate material (also referred to simply as a plate material) is a lithographic printing plate material that does not require dampening water and has a photosensitive layer and an ink-repellent material-containing layer on a support.

The above-mentioned photosensitive layer is characterized in that it is a photocrosslinkable type containing a compound represented by formula [I] and/or [■] below and a polymer or prepolymer that can react with the compound.

[In the formula, R+ and R2 each represent an alkyl group, an aryl group, or an aralkyl group having 2 to 30 carbon atoms which may have a substituent, and both may be the same or different.] General formula [II] In the formula, R3 represents an alkyl group, a phenyl group, or a naphthyl group, each of which may have a substituent. In the present invention, examples of the fumaric acid ester compound represented by the general formula [I] include 1, for example, fumaric acid diethyl ester. , dibutyl fumarate ester, dioctyl fumarate ester, distearyl fumarate, butyl octyl fumarate, diphenyl fumarate, dibenzyl fumarate ester, bis(3-phenylpropyl) fumarate ester, dilauryl fumarate ester , fumaric acid dibehenyl ester, etc., but are not limited to these. These may be used alone or in combination of 29 or more.

In the present invention, as a maleimide compound represented by the general formula [■], R3 is a straight chain branched or cyclic alkyl group having 1 to 22 carbon atoms, a straight chain or branched alkyl group having 1 to 6 carbon atoms, or a phenyl group or naphthyl group substituted or unsubstituted with a halogen atom, and a maleimide substituted with Nf11, such as an aralkyl group in which an alkyl group having 1 to 6 carbon atoms is substituted with a phenyl group. , or a divalent hydrocarbon residue such as an alkylene group having 1 to 12 carbon atoms, a phenylene group, a biphenylene group, a 1,6-hexamethylenebiphenylene group, a methylenebiphenylene group, a 2,2-diphenylenepropane group, etc. Examples include maleimide compounds in which a maleimide group is bonded at the N position.

Specific examples include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, dobutylmaleimide, N-bezotylmaleimide, n-hexylmaleimide, and N-cyclohexylmaleimide.

N-n-octylmaleimide, N-2-ethylhexylmaleimide, N-n-decylmaleimide, traurylmaleimide, N-stearylmaleimide, N-behenylmaleimide, N-phenylmaleimide, tochlorphenylmaleimide, N7) Ryl Maleimide, N-xylylmaleimide, N-benzylmaleimide, N-(6-phenylhexyl)maleimide, methylene bismaleimide, ethylene bismaleimide, trimethylene bismaleimide, hexamethylene bismaleimide, decamethylene bismaleimide, dodecamethylene bismaleimide , phenylene bismaleimide F, 2.2-diphenylenepropanbismaleimide, diphenylenemethane bismaleimide, N-(
4-hydroxyphenyl)maleimide and the like, preferably toalkylmaleimide, N-phenylmaleimide, N-benzylmaleimide, and N-(4-hydroxyphenyl)maleimide in which the alkyl group has 6 to 22 carbon atoms, More preferred is N-(4-hydroxyphenyl)maleimide.

The photosensitive layer of the present invention includes the above-mentioned -ritual [work] or -ritual [r].
One or more of the compounds represented by [I] can be selected and used.

In the present invention, it is preferable to use compounds represented by general formula [I] and general formula [rl] in combination with Mi.

The amount of the compound represented by -ritual [I] or -ritual [+1] is 5 to 80% by weight, preferably 10 to 40% by weight.

In the present invention, the polymer or prepolymer that can react with the compound represented by the general formula [I] or [■1] has the general formula [I] or [II] in the main chain, terminal or side chain of the molecule. Polymers or prepolymers are used that contain carbon-carbon unsaturation capable of reacting with the represented compounds.

[Specific examples] (i) Epoxy resin having an unsaturated group at the terminal or side chain, for example (i-1) Acrylic acid ester of epoxy resin (n=1 is bisphenol A-diglycidyl ether diacrylate), (prepolymer).

(i-2) Epoxy acrylate made from epoxy resin, acrylic acid, and methyltetrahydrophthalic anhydride, (j-3) GHz-CHCOOCHtCIls + Epo +
C) I2CIIJCOCII=CIIg Epoxy resin reacted with 2-hydroxyethyl acrylate, (T4) (i-1) reacted with maleic anhydride, (i-
5) → +EpO+(:1ICIl□0COCIl=CH2
0COCR=C1lz An epoxy resin reacted with acrylic anhydride to simultaneously esterify two unsaturated groups at the terminals.

(i-6) A product obtained by reacting (i-1) with glycidyl methacrylate or a dibasic carboxylic acid containing halogen.

(i-7) A product obtained by reacting an epoxy resin with butylamine and glycidyl methacrylate. (i-8) A product obtained by reacting a diglycidyl ether of an epoxy resin with diallylamine.

(i-9) Polyesters obtained by etherifying (i-]) with ]N-methylolacrylamide (ii) Polyesters having a perturbable bond in the main chain, side chain, or terminal, e.g. (ii-1) (ii-2 ) (ii-3) (ii-4) (ii-5) ? H3 ←+CH2CHz09C0CH=CHCOO+, CH2
CHGH20COC-CH2H (I) Polyurethane having an unsaturated group at the end, e.g. (iii-]) (iii-2) (iii-3) (iv) Polyvinyl alcohol having an unsaturated group at the side chain, e.g. (i-1) CIIJIIICOCII'(:II.

(iv-2) +C11□-C11+ (iv-3) +ClLa-Cl+)-+CHt-CI++l- Epoxy resin is preferably used.

Photopolymerization initiators useful in the photosensitive layer of the present invention include benzophenone, Michler's ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, α-methylolbenzoin, α-methylolbenzoin isomethyl ether, α-methoxybenzoin ether, benzoin phenyl ether, α-t-butylbenzoin, 2,2-dimethoxyphenylacetophenone,
2.2-jethoxyphenylacetophenone, 2.2-
Examples include jetoxyacetophenone, benzyl, bihaloin, anthraquinone, benzanthraquinone, 2-ethylanthraquinone, and 2-chloroanthraquinone. Such a photopolymerization initiator is preferably added in an effective amount for polymerization, that is, at least 0.01% by weight, and generally preferably in a range of 0.1 to 10% by weight.

The photosensitive layer of the present invention may contain a thermal polymerization inhibitor of 1% by weight of 0.001 to 2Tf. As this thermal polymerization inhibitor, 1
For example, 2,6-di-t-butyl-p-cresol, p-
Methoxyphenol, Vegetaerythritol Tetrakis (3-(:l'', 5--di-t-butyl-4'-hydroxy)phenylpropionate), Hydroquinone,
t-phthylcatechol, t-butylhydroxyanisole, 4,4'-thulydenbis(3-methyl-6-t
-butyl) phenol, etc.

The ink-repellent material-containing layer used in the present invention preferably has as a main component a linear organic polysiloxane having the following repeating unit and having a molecular weight of several thousand to several tens of blades.

Here, R is preferably an alkyl group, an alkenyl group, or a phenyl group having 1 to 10 atomic atoms, or one in which R is 60% or more or a methyl group. Such linear organic polysiloxanes are generally crosslinked by adding a reactive crosslinking agent to form silicone rubber. So-called room temperature (low temperature)
Crosslinking agents used in curable silicone rubber include silanes such as acetoxysilane, ketoxime, silane, aminoxysilane, amidosilane, alkoxysilane, and hydroxysilane, which may or may not have a monovalent organic group bonded to a silicon atom. , siloxanes which are low polymerization degree condensates of these, organo-hydrodiene polysiloxanes, etc. In addition, in order to improve the adhesion between the photosensitive layer and the silicone rubber layer and prevent the interlayer adhesion from decreasing even after a long period of time, a reactive silane compound having an allyl isocyanurate group,
A reactive silane compound having an aminoalkyl group or the like may be added to the silicone rubber composition.

The above reactive crosslinking agent and/or contained in the silicone rubber layer
Or the amount of reactive silane compound added is preferably 0.0
5-10%, more preferably 0.1-5% is selected.

Moreover, these adhesive components can also be used in combination.

Furthermore, a small amount of an organic tin compound is generally added to the silicone rubber layer as a catalyst.

The support used in the present invention preferably has the flexibility to be set in a normal lithographic printing machine and the ability to withstand the load applied during printing. Typical examples include metal plates such as aluminum, zinc, copper, and steel; and metal plates plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, etc.

Examples include paper, plastic films and glass plates, resin-coated paper, paper covered with metal foil such as aluminum, and plastic films treated with wood-protecting treatments. Among these, aluminum plates are preferred. When using an aluminum plate, it may be subjected to known surface treatments such as graining, anodizing, and sealing as needed. Further coating may be applied.

The thickness of each layer constituting the plate material used in the present invention is preferably 50 to 400 pm, more preferably 1
00-300pm, and the photosensitive layer is 0.05-10 lm
is preferable, more preferably 0.2 to 5 pLm,
The ink-repellent substance-containing layer preferably has a thickness of 0.5 to 100 IL, more preferably 1 to 10 IL+*.

In the present invention, an adhesive layer (primer layer) may be provided between the support and the photosensitive layer. The primer layer used in the present invention preferably satisfies the following conditions. and the photosensitive layer, and is stable over time. Furthermore, since the primer layer is exposed by exposure and development, it receives ink well, and has good solvent resistance to the solvent of the developer. .

Examples of materials that satisfy these conditions include epoxy resins and polyurethane resins that are heat-cured using a suitable curing agent. Further, a photocured resin made of a photodimerizable curing agent resin can also be used, but epoxy resins are particularly preferred.

Typical examples of epoxy resins used in the primer layer of the present invention are as follows.

(1) Reaction product between bisphenol A and epichlorohydrin (2) Reaction product I and product between novolak resin and epichlorohydrin (3) Reaction product between bisphenol F and epichlorohydrin (4) Reaction product between tetrabromobisphenol A and epichlorohydrin Product (5) Cycloaliphatic epoxy resin (compound having a cyclohexene oxide group, tricyclohexene oxide group, or cyclopentene oxide group) (6) Glycidyl ester-based epoxy resin (reaction product of polyhydric carboxylic acid and epichlorohydrin) (7 ) Glycidylamine-based epoxy resin (reaction product of amine and epichlorohydrin) (8) Heterocyclic epoxy resin (hydantoin-type epoxy resin with glycidylated hydantoin ring and triglycidyl isocyanurate with triazine ring) As the epoxy resin, In addition, any known epoxy resin, ie, one having an average of at least one epoxy group per molecule, can be used, but particularly preferred is the bisphenol A-based epoxy resin shown in (1). -The ceremony is as follows, and there are various epoxy equivalents, but the epoxy equivalent is 180 to 400.
0 is preferred.

As curing agents for the above epoxy resin, aliphatic polyamines, aromatic polyamines, polyamide amines, polymercaptans, acid anhydrides, and tertiary amines are effective.Among them, acid anhydrides are used as curing agents, and tertiary amines are used to cure It is most effective when used as a promoter.

The amount of acid anhydride curing agent added is 2 to 1 per epoxy resin.
00% by weight (hereinafter abbreviated as %). A particularly preferable range varies depending on the type of epoxy resin and acid anhydride used, but as an example, an epoxy equivalent of 5
When using an epoxy resin of 0.00 and an acid anhydride with an acid anhydride equivalent of 150, it is 10 to 50%.

The amount of the tertiary amine compound used as a curing accelerator is 0.5 to 30%, particularly preferably 5 to 30%, based on the epoxy resin.
It is in the range of 20%.

The above-mentioned epoxy resin, acid anhydride, and tertiary amine compound are dissolved in a suitable organic solvent, coated on a support, and then cured by heating at a temperature of 80 to 150''C.

In this primer layer, if necessary, a filler such as titanium oxide, an antihalation agent, a dye or an acid generator for imparting print-out properties may be appropriately mixed and used.

The thickness of the above primer layer is 0.1 l~100 alm
1. is preferable, more preferably 1. OJLm~15#Lm
It is.

Note that a protective layer may be provided on the upper surface of the ink-repellent material-containing layer, if necessary.

The dampening water-free plate material described above is manufactured, for example, as follows.

A composition solution to form a photosensitive layer is coated onto the support using a conventional coater such as a reverse roll coater, an air knife coater, a Meyer coater, or a rotary coater such as a Whaler. After drying and, if necessary, heat curing. ,
If necessary, apply an adhesive layer on the photosensitive layer in the same manner, and after drying.

Apply the silicone rubber solution onto the adhesive layer in the same way,
The ink-repellent material-containing layer (silicone rubber layer) is formed by heat treatment, usually at a temperature of 100 to 120° C. for several minutes, to fully cure the ink-repellent material. If necessary, a protective film can be provided on the silicone rubber layer using a laminator or the like.

To obtain a printing plate using the plate material obtained as described above, a positive film, which is an original, is vacuum electrodeposited on the surface of the plate material,
Expose. As a light source for this exposure, a mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, etc., which generate abundant ultraviolet light, are used. A photo-insolubilized portion is formed in the photosensitive layer by exposure. Next, the unexposed area is eluted and removed using a solvent and developed to form one image area (concave area).

As the developer, one known as a developer for plate materials that do not require dampening water can be used. For example, aliphatic hydrocarbons (hexane,
Heptane, 'Isopar E, H.

G” (trade name of aliphatic hydrocarbons manufactured by Esso Chemical) or gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene, etc.), or halogenated hydrocarbons (triclene, etc.)
It is preferable to add the following polar solvent to the above.

Alcohols (methanol, ethanol, water, etc.) Ethers (methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl calpitol, ethyl carpitol, butyl caldotol, dioxane, etc.) Ketones (acetone, methyl ethyl ketone, etc.) Esters (ethyl acetate, Methyl cellosolve acetate, selonlube acetate, carpitol acetate, etc.) It is also possible to dye the image area at the same time as development by adding a dye such as crystal violet or astrazone red to the developer.

Development can be carried out by a known method, such as rubbing with a developing pad containing a developer as described above, or pouring a developer onto the printing plate and then rubbing with a developing brush. As a result, the silicone rubber layer and photosensitive layer in the image area are removed, and the surface of the primer layer is exposed, which becomes an ink receiving area.

The depth of the ink receiving portion may be only the thickness of the photosensitive layer and the ink-repellent material-containing layer, or may be only the thickness of the photosensitive layer or the ink-repellent material-containing layer.

Note that, if necessary, it is also preferable to embed an ink receptive substance in the recess in order to reduce the depth of the ink receiving part (printing part).

[Effects of the Invention] According to the present invention, it is possible to provide a lithographic printing plate material that does not require dampening water and has excellent adhesive properties and is free from image stains.

[Example] The present invention will be explained in further detail by giving examples below.

Example 1 The following composition for a primer layer was applied to a smooth aluminum plate degreased in a conventional manner to a dry film thickness of 2 μm, and cured by heating at 120'O for 5 minutes.

Epicoat 1001 (manufactured by Shell Chemical Co., Ltd. 100 parts by weight bisphenol A epoxy resin, epoxy equivalent 450-500) Methyltetrahydrophthalic anhydride 36 parts by weight 2.4
．． 8-) Squirrel (dimethyl amitume 12 parts by weight chill)
Phenol methyl cellosolve acetate 120 mm parts Toluene 120 parts Methyl ethyl ketone 120 parts by weight The cured primer layer can be immersed in a developer or a mixed solvent for photosensitive layer coating (methyl ethyl ketone/toluene = 1/1 parts by weight mixture). It never dissolved.

On the aluminum plate coated with the primer layer, the following photosensitive composition was applied to a dry film thickness of 0.25 gtm and dried.

Co., Ltd., Lipoxy VR-60) N-lauryl maleimide 15 parts by weight C2-ethylhexyl fumarate 15 parts by weight 2.2-
Dimethoxyphenylaceto 5 parts by weight Phenonemethyl cellosolve 1000 parts by weight Next, the following silicone rubber composition was applied to the photosensitive layer to a dry film thickness of 2 ml, and dried to obtain a cured silicone rubber layer. .

Dimethyl having hydroxyl groups at both ends 100 parts by weight Polysiloxane (molecular weight approximately 100,000) Trimethylsilyl at both ends, Propyl-3,5-3,: 1 part by weight sialyl isocyanurate dibutyltin dioctanoate 3.3 parts by weight Isopar G
(Manufactured by Esso Chemical Co., Ltd.) 1500 parts by weight A single-sided matted polypropylene film with a thickness of +2 pa+ was laminated on the surface of the silicone rubber layer obtained as above,
A plate material that does not require dampening water was manufactured.

Developer composition Isopar H (manufactured by Esso Chemical Co., Ltd.) 252! ! Parts: Turfitz (Kuraray Sobrene, 25 parts by weight, manufactured by Chemical Co., Ltd.) Methanol: 25 parts by weight Toluene: 25 parts by weight A positive film was vacuum-adhered to the top surface of the above plate material and exposed using a metal halide lamp.Then, the above developer was used. The unexposed areas of the photosensitive layer and silicone rubber layer were removed to produce a lithographic printing plate that did not require dampening water.

This was attached to a Heidelberg GTO printing machine and printed using TKU Acwares G red ink manufactured by Toyo Ink Co., Ltd., and 10,000 clean prints were obtained.

Example 2 A lithographic printing plate requiring no dampening water was obtained in the same manner as in Example 1 except that N-laurylmaleimide was changed to N-(4-hydroxyphenyl)maleimide, and printing was performed in the same manner. 000 pieces were obtained.

Comparative Example N-laurylmaleimide and di-2-ethylhexyl fumarate in Example 1 were changed to diethylene glycol diacrylate.

After 3,000 sheets, scratches and stains appeared in the non-image area.

Example 3 In Example 1, N-laurylmaleimide or di-2-
Using only one of ethylhexyl fumarate,
A lithographic printing plate without dampening water was obtained in the same manner except that the amount added was 30 parts by weight, and printing was carried out in the same manner. Although the results were inferior to Example 1 in each case, the effects of the present invention were confirmed.

Patent applicant Nobuaki Sakaguchi, agent of Konica Co., Ltd., patent attorney

Claims (1)

[Scope of Claims] A lithographic printing plate material that does not require dampening water and has a photosensitive layer and an ink-repellent material-containing layer on a support, wherein the photosensitive layer is represented by the following general formula [I] and/or [II]. A lithographic printing plate material that does not require dampening water and is a photocrosslinkable type material containing a compound and a polymer or prepolymer that can react with the compound. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. may be the same or different. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, R_3 represents an alkyl group, a phenyl group, or a naphthyl group, each of which may have a substituent. ]