JPS5813899B2 - Kankousei Soseibutsu - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention applies to a wide range of photochemical processes such as lithography, letterpress printing, gravure printing and silk stalin printing, and photomechanical processes such as printed circuit manufacturing, chemical milling and chemical etching. Novel photoreactive compositions particularly suitable as photopolymers, photoinitiators and photosensitizers in photosensitive coatings used in lithographic printing plates. It is.

In lithographic printing, a photosensitive film on a backing is usually exposed to light under controlled conditions and then allowed to develop to form image areas that are insoluble in a particular solvent and non-image areas that are soluble in the solvent.

The streaked area is fat-receptive and water-repellent, while the non-stretched area is water-receptive and fat-repellent.

The fatty ink therefore adheres only to the image area and can be transferred to the surface by a suitable printing operation, such as offset printing.

Early lithographic printing plates had photosensitive surface films, which usually contained dichromate-doped colloids, such as dichromate-doped albumin, which underwent a sol-gel transition upon exposure to light.

These dichromate-doped colloids are susceptible to the action of moisture and thus deteriorate rapidly under atmospheric conditions, and their use is therefore usually in the form of so-called "Waibon plates", that is, coating a dichromate photosensitive film on a plate or backing. It is limited to systems that are exposed immediately after being applied.

Therefore, photosensitive diazo compounds have been used as photoresists in presensitized plates, ie plates provided with a diazo photoresist before actual use.

Although diazo-coated plates are widely used industrially, such plates suffer from several problems, such as short shelf life and the need to provide a barrier film between the diazo-sensitive coating and the backing. There are some drawbacks.

Furthermore, the diazo photoresist film is susceptible to the effects of heat, moisture, and tungsten light, resulting in handling problems.

In recent years, in order to overcome the drawbacks of some prior art compositions, compositions have been developed that can be applied to a suitable backing material for a longer period of time before actual use and that upon exposure to light become insoluble by photopolymerization or cross-linking. A method using a photopolymer coating agent was attempted.

Such photopolymer coatings are composed of various materials, such as those based on polyvinyl alcohol and cinnamic ester resins of hycellulose and Epoquine resins.

Other types of photopolymerizable coatings previously mentioned include acrylic coatings and polyamide coatings.

However, such known photopolymer coatings often require the addition of photosensitizers and photoinitiators.

Also, when used in lithography, such known photopolymer coatings suffer from relatively difficult manufacturing problems, and such coatings require more complex development methods than are desired.

Therefore, the main object of the present invention is to obtain a novel photosensitive composition which is characterized by excellent photoreactivity and can be used in a wide range of photochemical and photomechanical processes.

Another object of this invention is to provide new and useful photoreactive compositions that can be used in virtually all printing processes, including lithographic, letterpress, gravure and silk screen printing processes.

Another object of this invention is to provide novel and useful photoreactive compositions that can be used alone or in combination with a wide variety of saturated and unsaturated resins to provide superior photoreactive coatings. I'm trying to get it.

Another object of the present invention is to provide novel photoreactive compositions containing effective amounts of polyfunctional alkoxyaromatic glioquine substituents.

Another object of the present invention is to form a repeating structure in which a plurality of alkoxyaromatic glyoxy7 groups are arranged in a pe-ndant chain.
The object of the present invention is to obtain photoreactive polymer compositions suitable for use as photoinitiators, photosensitizers or photopolymers.

Another object of the invention is to obtain photoreactive compositions which are characterized by a long shelf life and are suitable for use as photoinitiators, photosensitizers and photopolymers, in particular suitable for use in presentized plates. It is an object of the present invention to provide photoreactive coatings that are developable in water- or alcohol-based solvents or disencentizers when used alone or in combination with a wide variety of resins. The purpose is to obtain a sexual composition.

It is an object of the present invention to provide an excellent reactive composition capable of forming an insoluble image on the backing of a lithographic printing plate which exhibits long-term continuous properties when exposed to actinic radiation under controlled conditions. It's about trying to get something.

Another object of the present invention is to provide an excellent photoreactive composition which, when used in ink and coating compositions, can make such ink and coating compositions photocurable.

The present invention provides novel compounds that are soluble in suitable solvents, such as aqueous solvents or organic solvents such as acetone or methyl ethyl ketone.

Such novel compounds react with light and become insoluble when exposed to actinic light.

The compounds according to the invention are particularly suitable for use in reactive processes, including photochemical processes as well as photomechanical processes, and are advantageously used alone or otherwise in photoreactive coatings for use on lithographic printing plates. Can be used in combination with other substances.

The novel composition of the present invention has the following general formula; It is characterized by containing a poly(p-glyoxyphenyl grindyl ether) compound consisting of a basic unit represented by the following formula.

Preferred alkali metals in the definition of M are sodium, potassium and lithium.

Substituted ammonium groups included in the definition of M are groups that provide water-soluble compounds, such as, for example, triethylamine, ethylamine, aniline, substituted anilines (e.g. chloroaniline, cyananiline and methoxyaniline), pyridine, substituted pyridine ( For example picoline and 2
, 6-lutidine), for example mono-, di- and tri-alkanolamines in which the alkanol residue represents an ethanol residue or an isopropanol residue, e.g. Alkylamines, such as
Morpholine and cycloaliphatic amines such as cyclohexylamine.

As mentioned above, the photoreactive compositions of the present invention can be used alone or in combination with other materials to provide photoreactive compositions suitable for a wide variety of photochemical and photomechanical processes. .

For example, such novel compositions exhibit advantageous use as photoinitiators in combination with saturated and unsaturated resins, including resins that are not themselves photosensitizers.

In particular, the use of the photoreactive compositions of the present invention as photosensitizers in conjunction with a wide variety of resins results in the formation of durable, insoluble photoreaction products.

Examples of resins used in combination with the composition of the present invention include acrylic polymers, polymethyl methacrylate, polyethyl methacrylate, and copolymers of methyl methacrylate and butyl methacrylate [for example, Elvacite (trade name, El
acrylic ester resins such as acrylic ester resins (e.g. , Estane)
"Polyurethane resin]; For example, phenol block polyurethane resin [For example, "Tranco (trade name, TRAN
block urethane resins such as "Epon (trade name, Epon) 1004 J";
Condensation product of bisphenol A and epichlorohydrin to form]; Phenoquine resin [e.g. Bakelite (trade name) PKRHJ phenoquine resin]; Vinyl acetate/
Vinyl chloride copolymer [e.g. “Bakelite (trade name)
VYHHJ medium molecular weight resin consisting of a copolymer of vinyl chloride 86 and vinyl acetate 14; 2-501%
Vinyl-modified polyethylene such as ethylene/vinyl acetate copolymer containing vinyl acetate (e.g. [Ultracene (trade name, UHrethene) J, ethylene/vinyl acetate copolymer]; partially (5-80%) hydrolyzed acetic acid Vinyl resin [for example, "Bakeley hJMA28-18.
18% hydrolyzed vinyl acetate]; Phenol resin [e.g. “Ple-nco (trade name, Ple-nco) 1000
modified acrylamide polymers such as acrylamide and diacetone acrylamide homopolymers, N-methylolacrylamide, N-alcoquinemethylacrylamide and partially hydrolyzed acrylamide; alkoxylated cellulose and hyokinepropyl cellulose [e.g. Trade name, Klucel)
”, water-soluble cellulose derivatives such as Oquinp Pill Cellulose]; and polyalkylene Oquinde [e.g. “Polyox WSRN-80”
There are water-soluble polyether resins such as polyethylene oxide.

The amount of poly(p-glyoquine phenyl grindyl ether) used in the photoreactive compositions of the present invention varies over a wide range depending on the effect of the compound in the composition.

For this reason, the concentration of the active ingredient in a given photoreactive composition is best described as an "effective amount," and this concentration ranges from 0.601% to 100% by weight of the total reactive material in the composition. .

For example, when the above poly(p-cryoquine phenyl grindyl ether) is used as a photoinitiator in a specific coating composition containing a polymerizable monomer (e.g., an acrylic or vinyl monomer), Ordinarily, the amount of the compound will be about 0.01 to 10 parts by weight of the total reactive materials in the composition.

However, when used as a photopolymer together with other saturated or unsaturated resins, the amount of the poly(p-glyoquine phenyl grindyl ether) according to the present invention may be as small as 5% by weight, but the actinic light can act. It is possible to provide a satisfactory photoreactive coating which becomes insoluble when allowed to do so.

The use of the novel compounds according to the invention alone, i.e. without combination with other thermoplastics, therefore offers advantages in virtually all photochemical and photomechanical processes, including in particular the production of presented plates. A photoreactive coating composition can be obtained that can be used for.

In such instances of the invention where the alcoquine aromatic glioquine group is present as a side chain or part of the polymer chain,
The degree of substitution by such glioquine substituents is sufficient to provide a polymer that becomes insoluble upon the action of light.

Since the acid form of such compounds is suitable for use when applied as a solution to a backing or support member, in such instances the preferred minimum degree of substitution is the total composition soluble in the solvent used in the solution. It's just a matter of providing something.

In this regard, the preferred minimum degree of substitution of the acid form of the alkokyne aromatic glioquine substituent in the polymer backbone is such that it provides all the compounds soluble in alkaline aqueous solution.

Other known photoinitiators can be used in photoreactive coatings containing such poly(p-glyoquine phenyl grindyl ether) if desired.

Such other photoinitiators that can be used include, for example, benzoin, benzoin methyl ether, alpha-methylbenzoin, alpha-allylbenzoin, biacetyl, penzophenone, benzaldehyde and acetophenone.

As mentioned above, the novel compounds according to the invention can also act as sensitizers, i.e. they absorb light and transfer energy to a photosensitive material in combination with this compound to achieve a given photosensitivity. exhibits the property of increasing photosensitivity in a reactive composition or a photoreactive composition.

Such photosensitizers can be used alone or in combination with other known sensitizers.

Other sensitizers that can be used in combination with such novel compounds include, for example, Mikler's ketone, picric acid, 2,4,6-trinitrosulfuric acid, 1,2-penzanthraquinone, 2,
5-Diphenyl-p-quinone 4,4-tetraethyldiaminodiphenyl ketone, 4,4'-1tetraethyldiaminodiphenylcarbinol, 4,4-tetramethyldiaminobenzophenonimide, 1-methyl-2-penzoylmethylene-β Monothiazoline, 4,4-diazodistilbene-2,2'-disulfonic acid and auramine base.

Other sensitizers having similar properties and properties that can be used in conjunction with the photosensitizers of the present invention will be apparent in the art.

In this regard, it should be noted that the photoreactive preservative composition of the present invention does not require the addition of other sensitizers such as those mentioned above in order to exhibit satisfactory photosensitivity.

When using the photoreactive substances according to the invention in photosensitive coatings containing monomers such as vinyl or acrylic monomers, e.g. 2,6-di-tert-butyl-p-cresol Alternatively, it has been found that antioxidants such as p,p'-biphenol can be used advantageously.

Also, although the compositions of the present invention are quite stable when stored away from light, in some cases it is sufficient to maintain the stability of the composition, but it is difficult to activate the composition after storage. It may be desirable to include a small amount of a polymerization inhibitor, such as hydroquinone, which is insufficient to prevent or significantly affect polymerization when exposed to light.

When producing an article such as a lithographic printing plate using the organic compound according to the present invention, such a novel poly(
spraying a solution of the (p-glyoxyphenyl grindyl ether) molecule alone or a solution of the above molecule to which other thermoplastic resins, photoinhibitors, photosensitizers and other optional components are added;
It is applied to the backing support member by any method such as spin coating, followed by air drying or heating to evaporate the solvent and form a thin film on the support member.

For example, the support member can be constructed from a strong base plate,
The surface is made hydrophilic and a thin film of a photoreactive composition is applied to the surface.

The constituent materials of the supporting member include glass, paper, resin-impregnated or reinforced paper provided with a coating that imparts the required properties and characteristics;
Solid resin plates or metal plates such as aluminum, zinc, magnenium or copper plates can be used.

Furthermore, the support member can be in the form of a plate, sheet or foil and can still be smooth or textured.

For example, in the case of an aluminum plate backing, its surface can be treated with an alkali metal silicate, silicic acid or an equivalent compound which forms a hydrophilic surface on the metal.

Similarly, if desired, the substrate or backing can be provided with a resin film suitable for receiving a photosensitive coating.

For examples of such types of resin films, see U.S. Pat. No. 3,073.
No. 723, No. 3 1 6 1517 and No. 323
No. 2738, which is fully described.

Although the exact composition of the photosensitive coating solution can vary significantly, it is usually sufficient to deposit a film on the backing that can provide an image area of the required film thickness and toughness. It is necessary that a quantity of photoreactive substance be present in the solution.

Solvent solutions containing usually about 1/2 to 10 parts by weight of active photoreactive component have been found to be suitable for a large number of purposes, including the production of press plates.

Preferably, the concentration of the alcoquine aromatic glioquine substituted molecules of the present invention and other thermoplastic resins that may be included therewith is approximately 2 parts by weight of the total solution weight.

If additional photoinitiators or photosensitizers are added, their concentration will generally be about 0.1 to 20 parts by weight of the other photoreactive components.

A backing or support member is coated with a thin film containing a photoreactive substance according to the invention, which can then be dried and stored for an extended period of time before use.

If desired, heating can be applied to ensure that residual solvent is driven out to facilitate photoinsolubilization upon exposure of the lithographic plate to a controlled active light source.

In use, the photosensitive film is exposed to a controlled active light source, preferably 30
Expose to a water lamp with high light output from 0 to 500 nm.

However, depending on the particular structure of the photoreactive composition and whether or not additional sensitizers and/or initiators are used, a wide variety of different light sources can be used.

Exposure is through a stencil, negative, template or pattern to produce the desired exposed areas or images on the surface of the photoreactive film.

As a result of such exposure, photosolubilization occurs within the photoreactive film at locations exposed to light.

Of course, the exposure duration can vary widely depending on the intensity and type of light source, the exact composition of the photoreactive film, the thickness of the film, etc.

The unexposed areas remain soluble so that the image or image can be developed with a solvent.

If a water-soluble photoreactive composition is used, the unexposed areas can be washed away with a suitable water or alcohol-based solvent.

The resulting plate is then desensitized by known techniques.

The optionally exposed lithographic printing plates can be developed using emulsion developers of the type well known in the industry, thus allowing the exposed areas of the photoreactive film to be developed in a single operation. The exposed surface on the underside becomes hydrophilic, and the photoinsolubilized area due to exposure becomes lipophilic.

When such a developer is used, there is no need to desensitize the plate formed after development.

Although not required, the coated plate can be fired to further enhance the strength of the insoluble polymer image if desired.

For example, the coating composition and support member can be fired in an oven at a temperature that is below the softening temperature of the support member, such as less than about 100° C. when aluminum plate is used as the backing material.

Although the above description of the specific use of the materials according to the invention relates to the production of lithographic printing plates, the novel compositions of the invention may be used, for example, in other printing processes, in the production of electrical circuits by corrosion, in chemical milling, etc. They can likewise be used advantageously in other photochemical and photomechanical processes such as, for example, in the production of photocurable inks and coatings which can be made to have decorative or protective properties.

A preferred method for producing photoreactive compounds according to the invention includes:
Aromatic groups in compounds having two or more alcoquine atomistic groups per molecule are glyochinlated.

In this glyoxylation, in cases with a monomeric or oligomeric backbone structure, almost all the aromatic groups of Friederuknaft can be removed by reaction with ethyloxalyl chloride in the presence of the catalyst anhydrous aluminum trichloride. Preferably, glioquinone is used.

In examples having a polymeric backbone structure containing, for example, 5 to 10,000 repeating monomer units, it is not necessary to complete the glioquine rayon.

For example, 20 to 80 aromatic groups present in the spine structure.
If the glyoxylation is continued until the compound is glyoxylated, a very satisfactory composition is obtained.

The invention will be illustrated with reference to the following example.

Example 1 describes the preparation of non-heavy tetraalcoquine aromatic compounds, and Example 2 describes the preparation of polymeric alcoquine aromatic compounds.

When these compounds are converted into glioquine, the polyalcoquine aromatic glioquine compound according to the present invention is produced.

Other examples describe the use of these compounds in various applications.

In Example 1, phenylgrindyl ether was combined with phenol in the presence of powdered potassium hydroxide to produce chrycerin-1.
, 3-diphenyl ether (GDE) was produced.

The above product is then esterified using terephthaloyl chloride in the presence of triethylamine catalyst to give bis(
1,3-diphenylglycetyl) terephthalate was produced.

This compound is a tetraalcoquine phenyl compound that was readily glyoxylated with ethyloxalyl chloride to yield the corresponding monomeric tetraglyochinate derivatives in accordance with the present invention.

In a second example, GDE was reacted with phenyl glycidyl ether in the presence of powdered potassium hydroxide to form a polymeric material.

This polymeric material had a polyethylene Oquinde polymer backbone structure with methoxyphenyl groups pendant from Etquin units.

The alkoxyphenyl group was glyocynlated using ethyloxalyl chloride in the presence of an anhydrous aluminum trichloride catalyst to produce the poly(p-glyoquinphenyl grindyl ether) compound of the present invention.

In the following examples, unless otherwise specified, all parts φ shall mean percent by weight relative to the mass of the composition.

Example 1 Part 1 Production of 1-glycerin-1,3-diphenyl ether In a flask equipped with a cooler, thermometer, stirrer and nitrogen inlet, 151 g of phenyl glycerin 1,3-diphenyl ether (
1 mol), 97.5 g (1.03 mol) of phenol and 0.6 g of powdered potassium hydroxide (approximately 0.2% of the total charge)
was loaded.

A slow flow of nitrogen gas was maintained over the reaction mixture during the reaction.

The mixture was slowly heated to 110-130°C and maintained at this temperature for 2 hours.

The reaction was further heated to 150° C. for 11/2 hours to complete the reaction.

The reaction mixture was then cooled to about 60° C. and poured into a large dish, whereupon crystallization occurred rapidly.

The product was ground, slurried in water, filtered and then washed with cold sodium hydroxide solution to remove excess phenol and several times with 1 l/time water to obtain the crude product.

Then, the crude product was recrystallized with 1 liter of a solution consisting of 80% alcohol and water to obtain 208 g of pure crystals with a melting point of 81-83.5°C.
(yield 85%).

Part 2 Preparation of 1-bis(1,3-diphenylglyceryl) terephthalate Pour 175 ml of benzene into a flask equipped with a cooler, thermometer, stirrer and dropping funnel, and add 75 ml of glycerin-1,3-diphenyl ether. .5 g (0.31 mol) and triethylamine 36.4 g (0.36 mol)
was added.

30.5 g (0.15 mole) of terephthaloyl chloride was slurried in 125 ml of benzene and placed in the addition funnel.

The reaction flask was cooled and the terephthaloyl chloride addition was carried out rapidly while maintaining the temperature below 15°C.

When the addition was complete, the mixture was heated to reflux for 11/2 hours and then cooled.

The reaction mixture was then evaporated to dryness in vacuo.

The resulting solid material was then slurried in water and washed with aqueous sodium carbonate, water, and 20% alcohol in water.

The yield of crude product was 67 g.

Dissolve this substance/cg in about 300 rnl of hot toluene,
Then, while stirring vigorously, pour this hot solution into a hexane 710
Injected into 00m7.

The product was then filtered off. The yield was 60.8 g, which was 66% of the theoretical amount.

The melting point was 142.5-144.5°C.

Part 3 -bis[1,3-di(p-glyoquinphenyl)]
Preparation of Glyceryl Terephthalate 90 ml of dry nitrobenzene was placed in a flask equipped with a condenser protected by a dryer, an exhaust port, a closed stirrer, a thermometer and a dropping funnel.

The flask was cooled and aluminum chloride 36'fl-
(0.27 mol) and stirred until it was dissolved.

To this was added ethyloxalyl chloride.

27.8 g of pis(1,3-diphenylglyceryl) terephthalate (0.04
5 mol) was dissolved and this solution was placed in the dropping funnel.

The apparatus was flushed with dry nitrogen gas for a short period of time.

Addition of the base material to the flask was then started while maintaining the reaction temperature between 0 and 10<0>C.

The reaction mixture thickened significantly when approximately half of the substrate was added to the reaction flask.

No more of the substrate was added as it appeared that adding more solvent would only swell the reaction mixture.

The reaction mixture was heated to 30°C and stirring continued during the day.

The next day, the reaction mixture was removed from the reaction flask and poured into a mixture of ice and dilute hydrochloric acid to hydrolyze the reaction product.

The hydrolyzed reaction mixture was then subjected to steam distillation to remove the solvent nitrobenzene.

The suspended residue remaining after steam distillation was dissolved in ethyl acetate.

The ethyl acetate was separated from the aqueous phase in a separatory funnel, and the aqueous phase was then washed several more times with ethyl acetate.

The desired product was present in the ethyl acetate solution, and most of the impurities and salts from the reaction mixture remained.

The ethyl acetate solution was then extracted several times with near saturated sodium bicarbonate solution.

The product was converted to its sodium salt form and dissolved in the aqueous phase.

Further ethyl acetate was then added to the aqueous phase to acidify the solution to pH1.

Upon acidification, the product converted to its acid form and redissolved in the ethyl acetate layer.

The ethyl acetate layer was dried over anhydrous sodium sulfate to remove water, then evaporated to about 150 ml, which was poured into several volumes of hexane to precipitate the product.

The product was distributed and dried.

Yield was 10.8g. Example 2 Part 1 Preparation of poly(phenyl grindyl ether) Into a flask equipped with a cooler, stirrer and nitrogen inlet, 200 ml of xylene was added to kf lycerin-1,3- produced in Example 1. Diphenyl ether 14.7. P(o
．． o6 mol), phenylcricidyl ether 270.4
@ (1.8 mol) and powdered potassium hydroxide 0.65 fl
- (approximately 0.2% of the total charge).

A slight nitrogen gas flow was maintained during the entire reaction.

The mixture is rapidly heated to about 110-120°C, held at this temperature for several hours, and then heated to reflux temperature, i.e. about 145°C.
heated to.

The condenser was then reversed and the xylene was distilled out of the reaction mixture.

Slowly heat the remaining reaction mixture to 160°C while continuing the nitrogen flow.
and then vacuum was applied to remove excess phenyl glycidyl ether remaining in the polymer.

The reaction mixture was cooled and poured into jars.

The yield of polymer was almost quantitative.

This polymer was used without further purification.

This polymer had a theoretical degree of polymerization of about 30.

The reason for this is phenylgrindyl ether okrycerin.
This is because 1.3-diphenyl ether was used at a 30 times higher concentration.

Part 2 Production of poly(p-glyoquine phenyl grindyl ether) Motor-driven stirrer, nitrogen inlet, cooler, exhaust port,
A flask equipped with a 250 ml addition funnel and a thermometer was charged with 300 ml of dry nitrobenzene and 26.6 g (0.18 equivalents) of poly(phenyl grindyl ether).

The apparatus was flushed with nitrogen gas, the reaction vessel was then cooled with ice, and ethyloxalyl chloride 2El (0.18 mole) was added.

A solution of 39 g (0.29 moles) of anhydrous aluminum chloride in approximately 120 ml of nitrobenzene was placed in the dropping funnel.

A flow of dry nitrogen gas was maintained during the reaction.

The reaction vessel was then cooled to 0-5°C and addition of the aluminum chloride solution was started.

This solution was added over a period of about 20 minutes with continued stirring.

After completing the addition of the aluminum chloride solution, the reaction mixture was slowly warmed to room temperature.

Shortly after finishing the addition of the above solution, the reaction mixture thickened into a soft gel, but stirring was continued during the day and then overnight and a small amount of the gelled reaction mixture was added into the mixture with dilute hydrochloric acid. It was dripped one by one.

The resulting solution was then subjected to steam distillation to remove all of the nitrobenzene.

Ethyl acetate was then added to the hot solution remaining after steam distillation to dissolve the suspended polymer.

After the polymer was completely dissolved, the resulting solution was placed into a separatory funnel and then separated into two layers.

The aqueous layer was then combined with two more extracts of ethyl acetate, the mixture was dried over anhydrous sodium sulfate, and the aqueous layer was discarded.

The ethyl acetate was filtered to remove the desiccant sodium sulfate, then 80% saturated sodium bicarbonate solution was added and stirred together vigorously.

The resulting solution was poured into a separatory funnel and the aqueous layer was separated from the ethyl acetate layer.

The ethyl acetate layer was then washed two more times with sodium bicarbonate solution.

The sodium bicarbonate solutions were then combined and evaporated in vacuo to remove all ethyl acetate.

The aqueous layer was then cooled with ice and enough hydrochloric acid to bring the pH to 1 was added to precipitate the polymer from the aqueous solution.

The polymer was filtered off and washed with deionized water.

The yield of the polymer was 27.42, and its neutralization equivalent was 294.

Calculations from this showed that the percentage of glyochine was 67% and the yield of polymer from the above reaction was 78 times theoretical.

Example 3 Solution A is obtained by mixing the components shown in Table 4, respectively.
, B and C were manufactured.

In Table 1, PGEPGA indicates the photosensitive polymer prepared in Example 2, poly(p-glyoxyphenyl grindyl ether).

Nitrogen gas was bubbled through these three solutions and the solutions were then irradiated with a black light fluorescent lamp for 20 seconds.

Precipitate was observed only in solution B, indicating that sterene was polymerized.

Example 4 Solution D was prepared by mixing the components shown in Table 2, respectively.
, E and F were manufactured.

Solutions D and E were irradiated as in Example 3 for 150 minutes.

No formation of polystyrene was observed in solution D.

A precipitate formed in solution E, which was collected and analyzed and determined to be essentially polystyrene.

As a result of irradiating solution F without flowing nitrogen gas, a yellow precipitate was generated.

Since no styrene was present in this case, only the photopolymer was cross-linked.

Example 5 A coating solution was prepared by dissolving 1 t of the polymer prepared in Example 2 in a solvent consisting of 25 t of acetone and 24 f of methyl ethyl ketone.

Pre-process the polished aluminum plate according to the plan to make the surface hydrophilic, pour the Toi solution on it, remove the excess solution, dry it at room temperature, and then dry it in a heated oven for several minutes. did.

The produced plate was then processed into a Nu-arc FT 40 flip top plate maker (Nu-arc F T 40
Flip Top Platemaker)
Pictured above. It was exposed through a true negative to a pulsed xenon light source with an input of 4000 watts for 8 minutes.

The exposed plate was then developed by applying a standard lithographic disensitizer to the exposed plate and then a standard rubber asphalt etchant.

Next. The generated plate was mounted on a printing press.

The plate was exposed so that 7 solid steps were printed on the lithographic sensitivity guide.

As a result of continued printing, it was only after 38,000 prints that 300 lines of image damage were observed on the 20% screen.

Example 6 Polymer PGEPGAO. produced in Example 2. A coating agent solution was prepared by dissolving 3T of 2-ethynethyl acetate, 29T of 2-ethynethyl acetate, 39T of acetone, and 3T of high molecular weight polymethyl methacrylate resin.

This coating solution was used to make a lithographic printing plate as described in Example 5.

The plate was exposed for 8 minutes and then developed using a developer consisting of 70 volumes of standard lithographic disencentizer, 29 parts by volume of 2-ethynethyl acetate, and 1 part by volume of emulsifier.

The result of attaching the generated plate to a printing machine and printing, 1000
It was not until after printing 0 times that the image line wear was observed.

Example 7 High molecular weight polymethyl methacrylate resin 6t and the compound PGEPGA4 produced in Example 2. ? A coating solution was prepared by dissolving 2-ethoxyethyl acetate 57.

A lithographic printing plate was prepared using this coating solution in a manner similar to that used for gB in Example 5.

The plate was exposed for 8 minutes and then developed using a developing composition similar to that described in Example 7.

When this plate was attached to a printing press and printed, wear and tear on the image lines was observed for the first time after 37,000 prints.

Example 8 An unsaturated polyester resin was prepared from 2 parts maleic anhydride, 1 part phthalic anhydride, and 3 parts 1,2-propanediol using standard polycondensation techniques.

A coating solution containing 6 parts of this polyester resin, 4 parts of the polymer of Example 2, and 57 parts of acetone was prepared.

This coating solution was used to expose a lithographic printing plate as described in Example 5.

After exposure, the plate was developed using a developer consisting of 69 parts by volume of standard lithographic Disencentizer, 30 parts by volume of ethyl acetate, and 1 part by volume of emulsifier.

This plate was attached to a lithographic printing machine at the same time as the plate made in Example 5, and as a result, it was not until after 36,000 prints that wear and tear on the image lines on the 300-line, 30-dot screen was observed.

Example 9 The polymer prepared in Example 2 was slurried in a small amount of water.

To this was added dilute sodium hydroxide solution to adjust the pH to 7 to form the sodium salt of the acidic polymer.

Water was then added to adjust the polymer concentration to about 5%.

The solution was applied onto a bran-sanded aluminum plate as described in Example 5.

This plate was exposed to light from two 15 watt blacklight fluorescent lamps placed at a distance of 50.4 am (2 inches).
Exposure was made for 0 minutes.

The resulting cured thin film did not peel off even after vigorous rubbing with water, ethyl alcohol, or acetone.

A second plate was coated with a 2% acetone solution of the polymer prepared in Example 2.

The coated plate was exposed to ammonia vapor for about 5 minutes to convert the acidic polymer to its ammonium salt.

This plate was exposed as described above and was found to be similarly solvent resistant.

Example 10 A printed circuit was made by the following method. A 5% solution of the polymer prepared in Example 2 in acetone was added to a copper layer with a thickness of 0.
．． It was applied to the copper-clad side of a 0.36 mm (1.4 mil) copper-clad zenol-based laminate.

The coated plate was exposed through a suitable photographic negative in an exposure apparatus similar to that described in Example 5.

The exposed plate was then developed with a 5% aqueous sodium bicarbonate solution to remove any polymer that was not photocured.

The bare copper exposed to such processing was etched away in a 40% aqueous ferric chloride solution for 18 minutes to yield an excellent reproduction of the original lithographic negative.

The corrosion resist was removed from the remaining copper by applying a dilute sodium silicate solution having a pH of about 11 to the plate.

Example 11 This example describes the use of the polymer prepared in Example 2 as a metal protection coating.

Part A High Molecular Weight Polymethyl Methacrylate Homopolymer 3g, Example 2
A solution consisting of 2 grams of the polymer prepared above and 55 grams of acetone was applied to an aluminum plate for lithographic printing.

76.2 x 127. from this plate after coating. Omm(3
Two sections (×5 inches) were cut and weighed on an analytical balance.

One of the plates was exposed to light from two 15 watt black light fluorescent lamps for 30 minutes.

The exposed plate was immersed in warm acetone for 21/2 hours, dried and reweighed so that 4 of the total coating weight was
It was found that only mg was lost.

From the weight of the unexposed sample 7 6.2 x 127. Omm
The total coating weight for the (3 x 5 inch) plate was found to be 89 m,@.

Therefore, there was only about a 5% weight loss in the exposed plate.

Part B A section of brass plate was partially coated with a 2% solution of the polymer prepared in Example 2 and exposed to a xenon arc lamp as described in Example 5 for 8 minutes.

Although this film protected the brass from corrosion by concentrated hydrochloric acid for 20 minutes, the uncoated areas of the brass plate were corroded.

Although such a protective coating was able to prevent corrosion of the brass by a 40% ferric chloride solution for 3 minutes, the uncoated areas quickly faded.

Similarly, an exposed film of a 2% solution of the polymer prepared in Example 2 on a brass plate completely prevented corrosion of the brass when exposed to a 40% ferric chloride solution for 15 minutes. did.

The membrane also resisted the effects of 10% nitric acid on the acid for about 15 minutes.

A 2% and a 10% solution of the polymer of Part C Example 2 was partially applied to a copper piece, the coated plate was exposed to light, and then the jade plate was partially placed in a vigorously stirred hot salt solution. Soaked in for 1 hour.

The uncoated areas were significantly affected by the salt solution, while the coated areas were not.

A 2% solution of the polymer prepared in Part D Example 2 was applied onto a section of aluminum metal plate.

After exposure, this film substantially prevented corrosion of aluminum by a composition consisting of 5 g of ferric chloride, 5 g of cuprous chloride, 0.25 g of concentrated hydrochloric acid, 75 g of ethyl telcohol, and 90 g of water.

The membrane also formed a polymer that exhibited satisfactory paper resistance to the corrosion and copper coating solutions commonly used in intaglio printing.

Example 12 Phthalocyanine puruni pigment 0.5. An ink composition for gravure printing was prepared from P, 0.7 g of nitrocellulose resin and 0.8 g of the polymer prepared in Example 2.

The composition contains 1.7 g of ethyl alcohol and 0.0 g of toluene.
5 g and 2.8 g of methyl ethyl ketone.

Since the phthalonanine blue pigment was previously mixed with the nitrocellulose resin and ground, there was no need for further grinding to improve pigment dispersion.

The ink composition was applied onto a metal plate using a coating rod wrapped with wire to form a thin film.

Two such thin film samples were made, and one of them was used as Example 5.
The sample was exposed for 10 minutes to a xenon arc lamp as described in .

The exposed sample had much greater solvent resistance to methyl ethyl ketone than the unexposed sample.

Furthermore, although the exposed sample was completely solvent resistant to ethyl alcohol, the unexposed portions of the sample had low solvent resistance to alcohol.

Example 13 A presented zinc plate for photolithography was made in the following manner: 152.4X152.4X1.68mm (6x6X0
．． A 64-inch) photolithographic grade zinc plate (RICH plate manufactured by Richertson Co.) was phosphatized, washed, and dried.

The plate was then flow coated with a 15% by weight PGEPGA (poly(p-glyoquinphenylgrindyl ether)) monoacetone solution and then dried at 60°C for 15 minutes.

Film thickness is approximately 0.08mg/cm2 (0.5mg/In2)
Met.

This edition was published by Perkiascore Addalux ( Berk
The negative was exposed for 30 minutes in a 5000 watt vacuum printing frame.

A visible image appears after exposure.

The plate was then developed in a sink with a 5% sodium silicate solution (pH=11.0) containing 1% nonionic surfactant.

The properties of the generated lines were excellent.

The thin skin of this plate was placed in the above sink without intermediate drying.
It was removed using a 0% sulfuric acid solution, then a 1o% nitric acid solution, then a 1o% sulfuric acid solution.

The plate from which the thin skin was removed was coated with a Protect-o-Plate manufactured by Richardson.
-ete) A coating agent was applied.

The plate was then installed in a 129 g capacity Master DM-35 etcher.

Richardson's New Setch (trade name,
News Etch) Bath additives 3.5% by volume and 4
It contained 23% by volume of 0° Baume nitric acid.

The temperature of the bath was maintained at 94'F.

The scraper speed was 600 rpm.

0.7 after 7 6~0.8 9ynx (0.030~
A relief of 0.035 inch) was observed.

The properties of this relief drawing were excellent, and the shoulder structure was also excellent.

A sharp halftone of 100 lines per 25.4 mm (1 inch) was well formed.

Example 14 A PGEPGA zinc plate as described in Example 13 was passed negative through a pulsed xenon 8000 watt light source in a vacuum frame.
It was exposed for 5 minutes.

As a result, a visible image was observed.

After removing the film and applying the Protect-o-plate coating, the plate was coated with Master D as described in Example 13.
Installed on M-35 corrosive machine.

The corrosive bath consisted of 12% 40° Baume nitric acid and vitagard corrosive oil (manufactured by Richardson).

The temperature was maintained at 26.7°C (80'F) and the scraper speed was 450 rpm.

After 20 minutes, 0.76~0.89mx(0
．． A relief plate of 0.030 to 0.035 inches was formed.

Example 15 254X254X1. Oho( 1 0XI OX0.0
40 inch) photolithographic quality magnesium plate,
Phosphate by immersion in 5% phosphoric acid solution for 30 seconds, wash and dry.

PGEP-GA was then dissolved in methyl cellosol acetate and a 25 W/% solution was spin-coated onto the plate.

The film thickness was approximately 0.006 mm (2.50 microinches).

After infrared drying, the negative was exposed to an 800 watt pulsed xenon light source for 15 minutes in a vacuum printing frame.

A visible image appeared after exposure.

The plate was then developed with the developer described in Example 14 and then de-skinned with 5% 42° Baume nitric acid solution.

Hunt Superbead Magnosol (Hunt Su
perspsed Magno-so1) 4.5% by volume
The plate was etched in a Master DM-35 etcher using an etching bath containing 20% by volume of 42° Baume nitric acid.

The temperature was maintained at 40.6° C. (below 105) and the scraper speed was 600 rpm.

Excellent relief lines of 0.76 order (0.030 inches) were observed after 3 minutes.

Example 16 A printed circuit was created using the following method: PGE-PGA
A solution of the polymer dissolved in acetone was added to a copper layer with a thickness of 0.5 mm.
It was coated onto the copper-clad side of a 0.36 mm (1.4 mil) copper-clad cyphenolic laminate.

The coated plates were exposed for 8 minutes through a suitable photographic negative in a Nuark FT-40 flip-top plate power.

The exposed plate was then developed with a 5% aqueous sodium bicarbonate solution to remove any non-photocured polymer.

The bare copper exposed by the processing process was etched in a 40% aqueous ferric chloride solution for 18 minutes to obtain an excellent replica of the original photographic negative.

Corrosion resistance was removed from the remaining copper by coating the plate with a dilute sodium silicate solution having a pH of about 11.

Example 17 The PGEPGA polymer described in Example 5 could be applied to an aluminum plate.

After exposure and development as described in Example 13, the resulting plate could be etched with a ferric chloride solution to obtain an aluminum relief plate.

Example 18 The PGEPGA polymer described in Example 5 could be applied to a bimetallic (copper on aluminum) offset printing plate.

The plate produced after exposure and development as described in Example 13 was etched in a ferric chloride solution to remove copper in unwanted areas and yield a plate of excellent quality.

In implementing the present invention, the following terms can be set as conditions for implementation.

(1) The composition according to claim 1, wherein M represents an H atom.

(2) The composition of item 1, which contains, in addition to an effective amount of the poly(p-glyoquinphenyl grindyl ether) compound, a solvent selected from the group consisting of water and organic solvents.

(3) The effective amount is sufficient to bring the concentration of the poly(p-glyoquine phenyl grindyl ether) compound to a range of 0.5 to 10 parts by weight based on the total weight of the compound and the solvent. The composition described in the preceding paragraph.

(4) An effective amount of a poly(p-glyoquinphenyl grindyl ether) compound is added to a saturated resin, an unsaturated resin, and a poly(p-glyoquinphenyl grindyl ether) to form a photoinsolubilized product. 2.) A composition according to claim 1, wherein the composition is dispersed in a solvent together with a substance selected from the group consisting of a polymeric precursor that binds to the compound.

(5) The above-mentioned substance is dispersible in the above-mentioned solvent, and the above-mentioned substance is an acrylic polymer, an acrylic ester resin, a copolymer of methyl methacrylate and butyl methacrylate, a polyurethane resin, an alkyl cellulose, an epoxy resin,
Phenoxy resin, vinyl acetate-vinyl chloride copolymer, vinyl modified polyethylene, partially hydrolyzed vinyl acetate resin,
The composition according to the preceding item, which uses a substance selected from the group consisting of phenolic resins, acrylamide and modified acrylamide polymers, water-soluble cellulose derivatives, and water-soluble polyether resins.

(6) The composition of item 4, wherein the poly(p-glyoquine phenyl glycidyl ether) compound is present in an amount of at least 5 parts by weight relative to the weight of the reactive material in the composition.

(7) A poly(p-glyoquine phenyl grindyl ether) compound is allowed to coexist with a polymerizable monomer to form a poly(p-glyoquine phenyl grindyl ether) compound.
The amount of the glyoquine phenyl grindyl ether) compound is from about 0.01 to about 0.01 to
The composition according to claim 1, wherein the content is 10% by weight.

Claims (1)

[Scope of Claims] 1 Represented by the following general formula; A photosensitive composition comprising a poly(P-glyoxyphenyl glycidyl ether) compound consisting of a basic unit represented by the following group.