JPH03120550A - Recording material - Google Patents

Abstract

PURPOSE:To form an inexpensive and easily available recording material high in reactivity by using a hardenable polymer having an aromatic sulfonic acid as a counter ion and an unsaturated fatty acid derivative part and an ammonium salt part on side chains. CONSTITUTION:The recording material is made of the highly functional polymer material obtained by allowing a homo- or co-polymer having an aromatic sulfonate on side chains to react with an unsaturated fatty acid derivative having an aliphatic ammonium group. The aromatic sulfonate can be easily obtained by allowing / toluenesulfonyl chloride to react with alcohol. An aliphatic tertiary amino group is combined with an unsaturated fatty acid by using diethylaminothanol or dihydroxy-ethylbutylamine or the like, thus permitting such a functional polymer to have one or more unsaturated fatty acid derivative parts and one or more quaternary ammonium parts per one poly-merization unit, and to be easily hardened by light, heat, and radiation.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a recording material, and particularly to a recording material using a curable polymer having an unsaturated fatty acid derivative moiety in its side chain.

(Prior Art) Various compounds have been developed as curable polymers, especially radiation/photo-curable polymers. In particular, there are many examples of studies that have unsaturated fatty acid derivatives in their side chains. However, these generally have high oil solubility, and there is a problem in that a methanol-based mixed solvent, which is highly safe, difficult, and easy to handle, cannot be used during development, and an improvement has been awaited.

Various types of water-soluble polymers have been studied in the past, with many examples having carboxy groups, sulfo groups, or quaternary salts in their side chains. For example, JP-A-49=984
90.49-111-991.49=9.95.89.
53-6394.59-79246 etc. for details.

However, these conventional production methods have some problems when it comes to producing polymers, especially polymers having functional groups such as unsaturated fatty acid derivatives. for example,
The reactivity is low, the introduction rate of functional groups is not increased, side reactions are likely to occur, gelation is likely to occur, and raw materials are expensive.

Recently, photocurable polymers having unsaturated fatty acid derivatives and heptadmonium salt moieties in their side chains have been developed for use in recording materials.

It involves polymerizing methylstyrene and reacting its active halogen atoms with a tertiary amine such as β-cinnamoyloxyethyldiethylamine to obtain a quaternary salt. It is said that the obtained curable polymer is alcohol-soluble, and that an alcohol-based solvent can be used as a developer after photocuring.

This system is safe because alcohol-based solvents can be used.
It has great advantages in terms of operability, etc.

However, the starting material, chloromethylstyrene, is very expensive, making it extremely difficult to use as an industrial material. The present inventors focused their attention on these fibers and developed a new material.

(Object of the Invention) The present invention provides a method for producing a functional polymer by cleverly using easily available, cheap, and highly reactive compounds, and a recording material using the same. ) The object of the present invention is to develop a functional polymer characterized by reacting a homopolymer or a copolymer having an aromatic sulfonic acid ester group in the side chain with an unsaturated fatty acid derivative having an aliphatic 7-mino group. This was achieved by developing a manufacturing method and developing recording materials using this method.

In the present invention, aromatic refers to 7-aryl which may have a substituent, and the substituents include furkyl, halogen, flukoxy, substituted furkyl and the like. From the viewpoint of availability and reactivity, benzene or toluene is preferred. Particularly preferred is toluene sulfonic acid ester.

Between the main chain and this ester, there may be a divalent group having 20 or less carbon atoms selected from 7-mide, ester, ether, aromatic ring, etc.

Aromatic sulfonic acid esters can be easily obtained by reacting toluenesulfonyl chloride with alcohol. The alcohol moiety is one obtained by saponification of vinyl acetate alone or a copolymer, and (meth)7 having a hydroxy group.
Examples include homopolymers or copolymers of acrylate or (meth)acrylic 7mide, homopolymers or copolymers of hydroxymethylstyrene, and homopolymers or copolymers of hydroxyethyl vinyl ether. From the point of view of raw materials, various (meth)7 acrylates with hydroxy groups are most advantageous.

Another manufacturing method involves monopolymerizing or copolymerizing monomers having aromatic sulfonic acid esters. For example, (meth)acrylate, styrene, which has a hydroxy group,
Aromatic sulfonate esters such as those from acryl 7mide are conveniently employed. For example, toluenesulfonyloxyethyl (meth) 7-acrylate, toluenesulfonyloxypropyl (meth)acryl 7mide, toluenesulfonyloxymethylstyrene, etc. can be conveniently used in the present invention. Regarding these,
well known.

Esterification is carried out according to conventional methods.

Furthermore, there are many commercially available (meth)7-acrylates of diols and polyols, which can be selected from the viewpoints of adhesiveness, light resistance, compatibility, hardness, alkali solubility, etc.

These monomers are also detailed in earlier patents. Monomers to be copolymerized include styrene, (meth)7 acrylate, and acrylic 7, which may have substituents.
There are mido etc. For example, styrene, methyl methacrylate, human O-oxyethyl (meth) 7-acrylate, hexyl (meth) acrylate, (meth)acrylic acid, vinyl acrylic 7-midoacetate, cellosolve (meth) 7-acrylate, vinyltoluene, α-cyano 4-methoxycinnamate. Examples include moyloxyethyl (meth) 7-acrylate and 7-crylonitrile.

For more information on methods such as radical polymerization, see Bottom. For example, W-R-5orenson” Preparati
ve Methods of P.

lymer Chemistry"l J. Bran
drup″Polymer Handbo.

See k″Wiley&　5ons　etc.

Homopolymers or copolymers are generally obtained by radical polymerization reactions. Preferred examples include 7zo compounds, peroxides, and redox compounds.

Unsaturated fatty acid derivatives having an aliphatic tertiary 7-mino group will be described.

The aliphatic tertiary amino group refers to a tertiary amine consisting of two selected from furkyl or 7ralkyl, and furkyl substituted with at least one unsaturated fatty acid.

Furkyl or 7ralkyl may have an unsaturated fatty acid derivative, an unsaturated bond, etc. as a substituent. Dimethyl 7mino, diethyl 7mino, dibutyl 7mino, methylbenzyl 7mino, ethylpargyl 7mino, diallyl 7mino, allylethyl 7mino, dibenzyl 7mino, N-hydroxypropynoethyl 7mino, N-7 clyloxyethyl 7mino, dihydroxyethyl 7mino, morpholino,
Piperazino and the like are preferred as the tertiary amine residue.

Examples of unsaturated fatty acids include beta-naphthyl acrylic acid, acrylic acid, methacrylic acid, cinnamic acid, thienyl acrylic acid, furyl-7-acrylic acid, ρ-ethoxycarbonyl cinnamic acid, alpha-cyanocinnamic acid, sorbic acid, phosphoric acid, Examples include dimethyl maleic anhydride, maleic anhydride, cinnamylidene acetic acid, and siftienyl pentadiene acid.

The bond between the aliphatic tertiary 7-mino group and the unsaturated fatty acid is preferably a divalent group having 12 carbon atoms and which may have ether, ester, 7-mide, ureido, urea, etc. Halogen atoms, as long as they do not interfere with the quaternary salt formation reaction.
It may have a human Ooxy group, a difurkyl7mino7lyl group, etc.

From the viewpoint of availability of raw materials, it is preferable to react a halide, preferably an O-lide, of an unsaturated fatty acid with an alcohol, thioalcohol or amine having the above-mentioned heptamine residue.

Diethyl 7-minoethanol, dimethyl 7-minoethanol, dihydroxyethylbutyl 7-mine, N-human O-oxyethylmorpholine, ethyl 7-rilmine, diethylpropanolamine, dimethyl 7-minomethylbenzyl alcohol, diethyl 7-minomethylcinnamyl alcohol, 7-mino Ethylimidazole, bis-H-oxyethyl pyrazine, 7-minoethylpy-O-lidone, human-O-oxyethyl bi-O-lidone, hydroxyethylhexamethyleneimine, etc.

Preferred examples include 7-minopropyldiethylamine, aminoethylmorpholine, 7-minoethyldibutyl-7mine, triethyldiethylamine, dimethylaminomethyl-7diphosphorus, and 7-minobutyldiethanolamine.

In this case, amine compounds such as triethylamine, jetanolamine, tributylamine, cinnamyldimeth7lylamine, ethyl7lylmine, diallyl7minoethylcinnamate, dicrotylbutylamine, diallylcinnamylamine, dicrotylcinnamylamine,
It is also possible to use diethylbutoxyethylamine etc. in combination.

These include halogen atoms, human Ooxy groups, difurkyl 7mino 7
It may have a lyl group or the like.

A salt is formed by the reaction of an aromatic sulfonic acid ester and an amine, and the counterion part is strictly an aromatic sulforane, but for convenience, it is described as an aromatic sulfonic acid in this specification.

7 In mididation and esterification, it is preferable to use a base as a catalyst. Caustic soda, caustic acid, pyridine, triethylamine and the like are preferred. It is also preferable to use polar solvents such as 7cetonitrile, dimethyl 7cetomide, sulfolane, and OO benzene.

Since the functional polymer of the present invention has one unsaturated fatty acid derivative and a quaternary salt moiety per polymerization unit, recording materials using it are easily cured by radiation, light, heat, etc. be.

In particular, it has excellent mordant effect, dye dispersibility, and curing speed, and is hydrophilic, so it has the advantage that it can be conveniently used for image formation using alkaline water treatment, alcohol, water-containing solvent treatment, etc. Examples of use in such applications are already detailed.
Kosar"Light 5ensistive S
systems “Kakuda” Photosensitive resin” Japanese Patent Application Publication No. 1999-1059
44th grade.

As the sensitizer, compounds that promote crosslinking and polymerization of unsaturated fatty acid derivatives are conveniently used.

These are well known, for example, JP-A-57-1
79836, 62-143044, USP463289
9.4634657.4647952.4670374
．． 4701402.4716095.4753865.

Representative examples include aromatic ketones, nitro, quinones, amines, cyanine borates, or combinations thereof.
1 to 10% is used.

When used as a recording material, various additives such as surfactants, plasticizers, dyes, pigments, stabilizers, antioxidants, sensitizers, and development aids are appropriately used in accordance with conventional methods.

For example, for dyes and pigments, Japanese Patent Publication No. 61-3687
2, USP 4806451.4427758, etc., and JP-A-64-4805 regarding initiators, stabilizers, etc.
9. JP-A-1-31147, LISP4822719.
4816379 etc. are detailed. Further, these and the patents and publications cited above provide detailed information on various forms, additives, usage, supports, coating methods, etc.

In particular, the polymer of the present invention has good dispersibility of dyes and pigments.

Depending on the purpose, the support may be glass, epoxy, aluminum,
PET, polyimide, etc. are used, and the material and shape are not limited.

The present invention will be described in detail with reference to Examples below.

Synthesis example 1.2 MEK18Qml, tosylate of human O-oxyethyl 7-acrylate 0.1 mol, butyl methacrylate 0.1
Mol (synthesis example 1) and a catalytic amount of 7zobisisobutyronitrile were stirred at 65 to 78 degrees for 6.5 hours while passing nitrogen gas according to a conventional method to obtain a copolymer. Conversion was approximately 80%. A similar operation was carried out with 0.08 mol of tosylate of hydroxyethyl methacrylate and 0.0 mol of methyl methacrylate.
The experiment was carried out using 2 mol (Synthesis Example 2).

The thus obtained copolymers having tosyl esters are referred to as polymers 1 and 2, respectively.

49 Polymer 1 was weighed and dissolved in 0 ml of DMFL, 0.01 mole of dimethyl 7minoethyl cinnamate was added, and the mixture was maintained at 60 degrees for 50 minutes.

The resulting quaternary salt polymer was precipitated from ethyl acetate/hexane and isolated. Example C) The same operation as above was carried out using diethyl 7 minopovircinnam 7 mido. (Example 2) Using Polymer 2, the same operation as above was carried out to obtain a quaternary salt polymer. (Example 3, 4
) Examples 1 to 4 Each of the polymers obtained in Examples 1 to 4 having a cinnamic acid derivative moiety and a quaternary salt moiety in the side chain was treated with 8% of a sensitizer (N-methylbenzoyl methylene naphthothiapurin). ) was added and dissolved in DMF. Place this on an electrolytically treated aluminum plate so that the thickness after drying is 2 microns.
dip-c.

It was at. Irradiation was performed for 2 minutes from a distance of 30 cm using a 400W high-pressure mercury lamp. The exposed area did not come off even after rinsing with a solvent (methanol/ethyl acetate mixture).

Example 5 % Os 3r' of N-methylbenzoylmethylenenaphthothiazoline was added to the reaction mixture as reacted in Example 3 above in DMF. Dip this onto an electrolytically treated aluminum plate so that the thickness after drying is 2 microns.
-coatL, above and how to use mercury lamp 30
Irradiation was carried out for 2 minutes from a distance of 1 cm. The exposed areas were not removed even after rinsing with a 6:4 mixed solvent of ethyl acetate and methanol, and it was found that they were strongly cured. Furthermore, this image gave a clearer image when stained with bromothymol blue.

Claims (1)

[Claims] A recording material characterized by using a curable polymer having aromatic sulfonic acid as a counterion in the side chain, an unsaturated fatty acid derivative portion, and an ammonium salt partial skeleton.