JPS63208036A - Plate making material - Google Patents

Abstract

PURPOSE:To permit plate making by laser beams by incorporating a photopolymn. initiator contg. a specific polymethine dye and photopolymerizable photosensitive component as essential components into the titled material. CONSTITUTION:The photopolymn. initiator contg. the polymethine dye expressed by formula I and the photopolymerizable photosensitive component are incorporated as the essential components into the above-mentioned material. In formula, R1-R5 denote a hydrogen atom, alkyl group, substd. alkyl group, cyclic alkyl group, alkenyl group, aralkyl group, substd. aralkyl group, aryl group, substd. aryl group, styryl group, substd. styryl group, heterocyclic group, substd. heterocyclic group; (m) denotes 0 or 1; (n) denotes 0 or 1, 2; X- denotes an anion group. The polymethine dye, therefore, has large absorptive power in a near IR region. Plate making by an IR lamp, semiconductor laser, etc., are thereby permitted, by which the miniaturization and simplification of a plate making device are permitted.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a plate-making material, and more particularly to a printing plate material that is sensitized with a polymethine dye and can be made by laser beams, and a plate-making material used in the printing plate. .

[Prior Art] In recent years, there has been an increasing demand for faster and more efficient printing, and there is also a desire for faster and more efficient plate making in the printing process.

In the conventional plate-making process, a light mask is created using photographic technology.
Thereafter, a photomask film is placed over the 25th plate, the entire surface is exposed, and a development process is performed to create a printing plate. However, the process of creating this optical mask requires a large amount of silver, is complex, and requires a lot of labor, so there is a method that omits this process: direct plate making, in which plate making is performed directly from the original onto the plate material. is attracting attention.

This direct plate making system includes a method of placing a toner image on a printing plate using electrophotography and making a plate, and a laser direct plate making system using laser technology.

Recording methods used in laser direct plate making systems include plate making methods such as electrophotography, heat mode plate making, and photopolymer curing. The laser light source used for these plate-making processes is Ar or H in electrophotography.
e-Me laser, YAG laser for heat mode
, Ar lasers are mainly used for photopolymers.

By using laser technology in this way.

It is possible to make plates with the information digitally processed, speeding up plate making and reducing costs, but because laser light sources are expensive and large, they are not fully utilized.

[Problems to be Solved by the Invention] The present invention has been made to solve the above problems, and provides a plate-making material that can be made using a small and low-cost semiconductor laser. The purpose is to

[Means for solving the problem] and [effect], that is,
The present invention is a plate-making material characterized by containing a photoinitiator composition containing a polymethine dye represented by the following general formula (1) and a photopolymerizable photosensitive component as main components.

General formula (I) (wherein R+, R*, '81. R4 and R11 are hydrogen atoms, alkyl groups, substituted alkyl groups, cyclic alkyl groups,
Indicates an alkenyl group, an aralkyl group, a substituted aralkyl group, an aryl group, a substituted aryl group, a styryl group, a substituted styryl group, a hetero R group, and a substituted heterocyclic group. m is O or 1. n is O or 1.2, and xo represents an anion group. ) The following is a detailed explanation of the present invention.

The object of the present invention is to provide a photoinitiator composition containing at least one type of polymethine dye represented by the above general formula (I) and a photopolymerizable composition containing a photopolymerizable photosensitive component as a main component. achieved.

In the general formula (1), " + R2r R3+
R4 and R5 are hydrogen atoms or alkyl groups (for example,
Methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, 5ec-butyl group, 1so-butyl group, t-butyl group, n-amyl group, t-amyl group,
n-hexyl group, n-octyl group, t-octyl group, etc.), and also other alkyl groups, such as substituted alkyl groups (e.g. 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 2-hydroxybutyl group, -acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 2-sulfoethyl group, 3
-Sulfopropyl group, 4-sulfobutyl group, 3-sulfatepropyl group, 4-sulfatebutyl group, N-(
methylsulfonyl)-carbamylmethyl group, 3-(acetylsulfamyl)propyl, 4-(acetylsulfamyl)butyl group, etc.), cyclic alkyl group (e.g., cyclohexyl group, etc.), alkenyl group ( Vinyl group.

Allyl group, propenyl group, butenyl group, pentenyl group,
(hexenyl group, heptenyl group, octenyl group, dodecynyl group, prenyl group, etc.), aralkyl group (e.g. benzyl group, phenethyl group, α-naphthylmethyl group, β-
naphthylmethyl group), substituted aralkyl group (e.g.
carboxybenzyl group, sulfobenzyl group, hydroxybenzyl group, etc.). Furthermore, R1, R2, R
3.

R4 and R5 are substituted or unsubstituted aryl groups (e.g., phenyl group, naphthyl group, tolyl group, xylyl group, methoxyphenyl group, dimethoxyphenyl group, trimethoxyphenyl group, ethoxyphenyl group, dimethylaminophenyl group, diethylaminophenyl group) group, dipropylaminophenyl group, dibenzylaminophenyl group, diphenylaminophenyl group, etc.), substituted or unsubstituted heterocyclic groups (e.g., pyridyl group, quinolyl group, lepidyl group, methylpyridyl group, furyl group, chenyl group) , indolyl group, pyrrole group, carbazolyl group, N-ethylcarbazolyl group) or substituted or unsubstituted styryl group (e.g. styryl group, methoxystyryl group, dimethoxystyryl group, trimethoxystyryl group, ethoxystyryl group, Dimethylaminostyryl group, diethylaminostyryl group, dipropylaminostyryl group, dibenzylaminostyryl group, diphenylaminostyryl group, 2.2
-diphenylvinyl group, 2-phenyl-2-methylvinyl group, 2-(dimethylaminophenyl)-2-phenylvinyl group, 2-(diethylaminophenyl)-2-phenylvinyl group, 2-(dibenzylaminophenyl) -2
-phenylvinyl group, 2,2-di(diethylaminophenyl)vinyl group, 2,2-di(methoxyphenyl)vinyl group, 2,2-di(ethoxyphenyl)vinyl group, 2-
(dimethylaminophenyl)-2-methylvinyl group, 2
-(diethylaminophenyl)=2-ethylvinyl group, etc.) is 0 or 1, and n is 0.1 or 2.
It is.

xo represents an anion group, for example, chloride ion, bromide ion, iodide ion, perchlorate ion, benzenesulfone m salt ion, p-toluenesulfone m salt ion, methyl sulfate ion.

Ethyl sulfate ion, propyl sulfate ion, tetrafluoroborous salt ion, tetraphenylborate ion, hexafluorophosphate ion, benzenesulfinate ion, acetate ion, triple oloacetate ion, propionic acetate ion, benzoate ion, oxalate ion, succinate ion, malonate ion, oleate ion, stearate ion, citrate ion, -hydrogen diphosphate ion, dihydrogen-・phosphorus Acid salt ion, pentachlorostannate ion, chlorosulfonate ion, fluorosulfonate ion, trifluoromethanesulfonate ion, hexafluoroantimonate ion, molybdate ion, tungstate ion, titanate ion ion, anion such as zirconate ion.

The polymethine dye has a large absorption peak with an extinction coefficient of 105 or more in the near-infrared region around 800 nm,
It is preferable to use a material that can absorb 780 nm or 830 nm light from an infrared lamp or a semiconductor laser and efficiently convert it into heat.

Next, representative examples of the polymethine dye represented by the general formula (I) will be listed.

BF4゜Such polymethine dyes have good solubility in organic solvents. Commonly usable solvents include acetone, ketones such as methyl ethyl ketone, ethers such as tetrahydrofuran, dioxane, di-isopropyl ether, di-n-propyl ether, di-n-butyl ether, methyl acetate, ethyl acetate, butyl acetate, Dairy ethyl.

esters such as, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethylene, trichloroethylene, aromatics such as benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, anisole, isopropyl alcohol, n-butanol, etc. Examples include alcohols.

Using the above-mentioned solvent, a film containing a photoinitiator composition containing a polymethine dye and a photocombinable photosensitive component as a product can be formed on a substrate in a dispersed or dissolved state. In addition, a binder may be used as appropriate to improve film properties, adhesive properties, and durability, and any polymer capable of forming a coating film can be used as the binder. As a binder, for example, polyvinylpyrrolidone.

Examples include polymethyl methacrylate, polystyrene, polyvinyl acetate, and copolymers thereof.

The photoinitiator composition of the present invention preferably contains an organic peroxide as a photoinitiator, and the organic peroxide is an organic compound having at least one nitrogen-oxygen bond in the molecule. Includes almost everything. For example, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis(tert-butylperoxy)-3,3,5- Trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, n-butyl-4,
4-bis(tert-butylperoxy)valerate, 2,2-bis(tert-butylperoxy)butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, para-menthane hydroperoxide , 2,5-dimethylhexane-2, sivitrotro-oxide, 1,1,3. : l-Tetramethylbutylhydroberoxide, ditertiarybutyl peroxide, tertiarybutyltamyl peroxide, dicumyl peroxide, α,α'-bis(tertiarybutylperoxyisopropyl)benzene, 2.5
-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, acetyl peroxide, isobutyryl peroxide, octanoyl Peroxide, decanoyl peroxide, lauroyl peroxide, :l, 5.5-trimethylhexanoyl peroxide, succinic peroxide, benzoyl peroxide, 2.4-dichlorobenzoyl peroxide,
Meta-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di( 3-Methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxy pivalate, tert-butyl peroxyneodecanoate, tert-butyl peroxyisobutyrate Butyl peroxyoctanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate.

Tert-butyl peroxybenzoate, di-tert-butyl peroxy isophthalate, 2,5-dimethyl-2,5-di(benziisoperoxy)hexane, tert-butyl peroxymaleic acid, tert-butyl peroxyisopropyl carpo Examples include Nate et al.

Further, other known photopolymerization initiators may be mixed.

The photopolymerizable photosensitive component used in the present invention includes all unsaturated compounds, and these unsaturated compounds include monomers having a polymerizable ethylenically unsaturated bond,
There are oligomers and polymers, such as acrylic acid,
Unsaturated acids such as methacrylic acid, itaconic acid, maleic acid and its anhydrides, phthalic acid and its anhydrides, fumaric acid,
Methyl acrylate, ethyl (meth)acrylate,
Butyl (meth)acrylate, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate, dimethyl maleate, diethyl maleate, dimethyl fumarate,
Unsaturated acid esters such as pentaerythritol tri(meth)acrylate, trimethylolbuPpantri(meth)acrylate, ethylene glycol di(meth)acrylate, brobylene glycol di(meth)acrylate,
and styrene, acrylamide, acrylonitrile, N
Examples include -vinylpyrrolidone, vinyl acetate, and various unsaturated polyesters, unsaturated polyethers, unsaturated polyurethanes, and epoxy (meth)acrylate compounds.

The amount of the photoinitiator composition added is 0.1 to 100 parts by weight, preferably 0.5 to 100 parts by weight, per 100 parts by weight of the photopolymerizable photosensitive component.
It is 50 parts by weight.

When the photoinitiator composition contains the polymethine compound and organic peroxide as active ingredients, the weight ratio of the two is polymethine dye:organic peroxide=0.1.
: 99.9~lO mouth: 0, preferably 3~
95:97-5.

The polymethine dye represented by the general formula (I) and the organic peroxide are added to one or a mixture of two or more of the photopolymerizable photosensitive components as described above, and if necessary, ordinary dyes, A pigment, an inhibitor, a binder, etc. and a suitable solvent can be added to disperse or dissolve them, and a film can be formed on a substrate.

As the substrate, in addition to commonly used copper plates, aluminum plates, etc., films such as polyimide film, polyethylene terephthalate film, aramid film, etc. can be used.

[Example] Next, the present invention will be explained by giving examples. In addition, in the following examples, parts indicate parts by weight.

Examples 1 to 5 100 parts of trimethylolpropane triacrylate was used as a photopolymerizable photosensitive component, 35@ polymethyl methacrylate was used as a binder, and 5 parts of polymethine dye shown in Table 1 below as a photoinitiator composition and an organic Peroxide was dissolved in a solvent and applied to a polyimide film to a thickness of about 4 ml using an applicator. moreover,
On top of this was applied a film of polyvinyl alcohol about 8 μl thick.

This plate material was exposed to light using a 25 mW semiconductor laser (830 nm) and a beam diameter of 0.4 am, and the amount of energy required until the coating film was cured was measured. The results are shown in Table 1.

Table 1 Examples 6 to 1O Plate materials were prepared in the same manner as in Example 1 except that a compound having the structure of the following formula (II) was used as the photopolymerizable photosensitive component,
The energy required to cure the paint film was measured. The results are shown in Table 2.

Table 2 [Effects of the Invention] As explained above, the plate-making material of the present invention contains a photoinitiator composition containing a polymethine dye and a photopolymerizable photosensitive component as main components, and the polymethine dye has near-infrared rays. Since it has a large absorption capacity in a certain area, plate making can be performed using an infrared lamp, a semiconductor laser, etc., and it becomes possible to downsize and simplify the plate making apparatus.

Claims (2)

[Claims] (1) A plate-making material characterized by containing a photoinitiator composition containing a polymethine dye represented by the following general formula (I) and a photopolymerizable photosensitive component as main components. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, R_3, R_4, R_5 are hydrogen atoms, alkyl groups, substituted alkyl groups, cyclic alkyl groups,
Indicates an alkenyl group, an aralkyl group, a substituted aralkyl group, an aryl group, a substituted aryl group, a styryl group, a substituted styryl group, a heterocyclic group, and a substituted heterocyclic group. m is 0 or 1, n is 0, 1, or 2, and X^■ represents an anion group. ) (2) The plate-making material according to claim 1, wherein the photoinitiator composition contains an organic peroxide.