JPS5842460B2 - Manufacturing method of septic tank - Google Patents

Description

Detailed Description of the Invention The present invention relates to a photosensitive material, particularly a printing plate.
The present invention relates to a method for producing a light-sensitive material suitable for producing photosensitive plates.

The present invention provides polymers containing a plurality of epoxide groups, hydroxyl groups, or primary and/or secondary amino groups, which can be prepared by reacting a compound represented by the general formula:
R2 and R3 are the same or different hydrogen atoms or halogen atoms; R4 is a phenyl group substituted with an inactive group when a is 0, X is a .-rosulfonyl group; R4 is a carboxyl group or cyano group when a is 1, and X is a .-rosulfonyl group, to obtain a light-sensitive material.

When R4 is a halosulfonylphenyl group, an inert group such as a halogen substituent must be present on the aromatic group R to prevent the introduction of a halosulfonyl group at the R bridge between R and R4.

Similarly, when X is a halosulfonyl group and R4 is a phenyl group, R4 is an inert group.

Since this enhances the alkali solubility of the light-sensitive material, it is particularly preferable that R4 in the formula is a carboxyl group.

In order to increase the photosensitivity of the material in an unsaturated state, it is preferable that a in the formula be a value of 0 or more.

When the polymer contains multiple hydroxyl groups, the polymer may be, for example, an epoxy or phenoxy resin (derived from biphenol and epichlorohydrin); poly(vinyl alcohol); poly(vinyl alcohol acetate);
Partially hydrolyzed poly(vinyl esters) such as: naturally occurring substances such as cellulose or starch and derivatives produced by partial esterification or etherification, for example hydroxypropyl cellulose; poly(hydroxyethyl acrylate) or poly(hydroxyethyl methacrylate); partially hydrolyzed acetals and mixtures thereof, such as partially hydrolyzed poly(vinyl butyral), partially hydrolyzed poly(vinyl alcohol); condensations of phenol or substituted phenols with aldehydes, for example phenol formaldehyde resins, resorcinol-formaldehyde resins and '2,4 dihydroxy-
Benzoic acid-formaldehyde resins; or condensation products of substituted or unsubstituted phenoxyalkanols with aldehydes;
For example, there can be mentioned a resin produced by condensing 2-phenoxyethanol with formaldehyde.

The condensation products of phenols and phenoxyalkanols with aldehydes can be represented by the following molecular structure: where n is at least 2, R6 is 0 to 3 substituents selected from alkyl, halogen, alkoxy, hydroxy, aryl, and alkyl groups, and R7 represents hydrogen or a lower alkyl, aryl, or aralkyl group.

Where the polymer contains a plurality of primary and/or secondary amino groups, such polymers may include, for example, poly(ethyleneimine):poly(vinylamine)nitrile-formaldehyde resins or condensates of styrene-maleic anhydride copolymers or alkyl vinyl ether-maleic anhydride copolymers with excess aliphatic or aromatic diamines.

Such condensates have the repeating unit: where R8 represents an aliphatic or aromatic group and R9 represents an alkoxy or phenoxy group.

When the polymer contains epoxide groups, it is preferably an epoxy resin obtained by condensation of epichlorohydrin and, for example, bisphenol A, or a novolak-epoxy resin obtained by condensation of a phenol-(or cresol)formaldehyde novolak resin and epichlorohydrin.

Examples of suitable compounds containing a halosulfonyl group are as follows: *These compounds may be used alone or in combination with other compounds, or in combination with one or more halides of other aromatic sulfonic acids, or one or more halides of aliphatic and aromatic carboxylic acids.

These halides do not contain free carboxylic acid groups.

For example, the halosulfonyl group-containing compounds may be used in combination with a halide such as the chloride of p-toluenesulfonic acid, acetic acid, propionic acid, benzoic acid, p-azidobenzoic acid, or cinnamic acid.

The reaction of such non-free carboxylic acid group-containing acid halides with the polymer may occur not only simultaneously with the reaction of the halosulfonyl group-containing compound represented by the above formula, but also before or after such reaction.

The photosensitive material of the present invention is soluble in alkali and comprises a polymer backbone, in which a photosensitive side chain having a terminal carboxylic acid group is bonded via a sulfonyloxy group or a sulfonamide group.

When X is a .sulfonyl group and the polymer has many hydroxyl groups, the light-sensitive material contains a group represented by the formula: (wherein R, R1, R2, R3 and a have the same meanings as above, and R4 represents an alkyl group, an alkoxycarbonyl group, a carboxyl group, a phenyl group substituted with an inert group, or a hydrogen atom) bonded to a carbon atom of the polymer.

When X is a halosulfonyl group and the polymer has many primary and/or secondary amino groups, the photographic material of the present invention contains a group represented by the formula: (wherein R, R1, R2, R3 and a have the same meanings as defined above, and R4 represents an alkyl group, an alkoxycarbonyl group, a carboxy group, a cyano group, a phenyl group substituted with an inert group; or a hydrogen atom) bonded to a carbon atom of the polymer.

When R4 is a arylsulfonyl-substituted phenyl group and the polymer contains a plurality of hydroxyl groups, the light-sensitive material has a structure in which R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R38, R39, R41, R42, R43, R44, R45, R46, R47, R48, R49, R50, R51, R52, R53, R54, R55, R56, R57,
R3 and a have the same meanings as above, ph represents a phenyl group, and X represents an inactive group.

When R4 is a halosulfonylphenyl group and the polymer has several primary amino groups and/or secondary amino groups, the light-sensitive material in the present invention contains a group represented by the following formula (in which R, R1, R2, R3 and a are the same as defined above, ph is a phenyl group, and X is an inactivating group) bonded to a carbon atom of the polymer.

The photosensitive materials of the present invention having the above groups attached to carbon atoms are usually prepared by reacting a .sulfonyl compound with epoxide, hydroxyl or amino groups of a polymer, but can also be prepared by other methods as shown in Example 9.

The photosensitive material of the present invention is particularly valuable in the manufacture of photographic printing plates and the like.

The present invention can thus be directed to a photosensitive plate prepared by applying a layer of photosensitive material to a support material on which a film of photosensitive material is deposited, for example glass, paper, resin-impregnated paper, synthetic resin foil or a metal such as aluminum, zinc, magnesium or copper.

To apply the photosensitive layer to the support, the photosensitive material is dissolved in a suitable solvent, such as dimethylformamide, dioxane, 2-ethoxyethanol, 2-ethoxyethyl acetate or ethyl methyl ketone or a mixture of these solvents, and the resulting solution is applied to the support by conventional methods, such as dipping, spraying or whirler coating.

The solvent is then evaporated by air drying or heating to leave a layer of the photosensitive material on the support.

The coating weight per square meter is typically between 0.2 and 2.02.

For industrial coating purposes, the photosensitive material of the present invention may be dyed,
It may be desirable to add pigments, plasticizers, wetting agents, photosensitizers, stabilizers, inert polymers, and the like.

When used, a photosensitive plate formed using the photosensitive material obtained in the present invention is imagewise exposed for a certain period of time, which period of time depends on the composition of the photosensitive layer, the layer thickness, the support, the intensity of the light source, and the object.

The unexposed areas remain soluble in alkali, while the exposed areas become insoluble.

The image on the exposed plate can then be developed with alkali.

The aqueous alkaline solutions used to develop the exposed plates act as good solvents on the unexposed areas but have little effect on the photohardened image.

The alkaline developers preferably used are aqueous solutions of alkali metal phosphates or metasilicates.

To this solution, 5-30% of a water-miscible organic solvent, such as an alcohol, is added to facilitate complete removal of all unexposed material.

Preferred fields of use of the photosensitive material according to the invention are the production of lithographic printing plates, the production of etch resists, the production of printed circuits etc., etching and the production of decorative effects.

The invention will now be illustrated by the following examples.

Example 1 (a) Chlorsulfonyl cinnamyrthene malonic acid (
Preparation of Formula I) Cinnamaldehyde and malonic acid were condensed in acetic acid at 100°C.

The condensate was recrystallized from ethanol and the melting point was confirmed to be 206°C.

The condensate was reacted with chlorosulfonic acid at 60°C, and the reaction mixture was slowly poured into ice water with stirring to isolate chlorosulfonylcinnamyrthenemalonic acid.

(b) Preparation of Resorcin/Formaldehyde Resin Resorcin, excess formaldehyde and sodium sulfate were dissolved in water and heated on a water bath with stirring.

As soon as the solution began to turn cloudy, the reaction was terminated by adding a large amount of cold water.

The precipitate was separated, washed with water and dried at room temperature.(e) Preparation of Photosensitive Material Equal amounts of the chlorosulfonylcinnamyrthenemalonic acid and resorcinol-formaldehyde resin prepared as described above were dissolved in acetone, and sodium carbonate was added.

The mixture was stirred at 20° C. for 1 hour.

The photosensitive ester formed was separated, redissolved in water and then precipitated by the addition of hydrochloric acid.

(d) Preparation of a printing plate A 3% solution of the above-mentioned photosensitive material in a mixture of dimethylformamide and 2-ethoxyethanol was applied by means of a warper to the surface of an electrically roughened and anodized aluminum sheet to obtain a coating having a weight of about 0.5 P/m.

After drying the product, the resulting plate was exposed to a 4000 watt xenon flash tube in negative contact at a distance of 0.65 m for 2 minutes.

The exposed plate was developed in a 2.5% trisodium phosphate solution to remove the areas of the photosensitive coating not exposed to light during exposure.

The plate was then washed with water and 2% sulfuric acid and stained with oil inks.

Example 2 (aJ) Preparation of Photosensitive Material Ehoquint Resin Epicoat 1009 (trade name, manufactured by Shell Chemicals) (prepared by polycondensing 2,2-bis(p-hydroxyphenyl)propane with an excess of epichlorohydrin in the presence of sodium hydroxide).

6.35' of dimethylformamide (molecular weight about 3750) was dissolved in 33 ml of anhydrous dioxane and 11.9 fI of chlorosulfonylcinnamylidenemalonic acid prepared as described above was added with stirring.

The mixture was heated under reflux for 8 hours, cooled, diluted with an equal volume of dioxane, and added dropwise to 1500 mL of water.

The precipitated resin was separated and washed with more water on a filter.

(b) Manufacture of a printed circuit board Using the photosensitive material manufactured as described above, Example 1
The procedure of (d) was repeated.

However, the developer for the exposed plates consisted of a mixture of 4 parts 12% sodium metasilicate and 1 part 2-ethoxyethanol.

Example 3 (a) Preparation of a photosensitive material 2-phenoxyethanol-formaldehyde resin 42 prepared by condensation of 2-phenoxyethanol and formaldehyde in the presence of an acid catalyst was reacted with 15f? of chlorosulfonylcinnamylidenemalonic acid prepared as described above in dioxane at reflux temperature for 8 hours.

The product was isolated by dropwise addition of the cooled reaction mixture into 1 L of water.

(b) Manufacture of printed circuit board The procedure of Example 1(d) was repeated.

However, the exposure time was 5 minutes and a developer consisting of 3 parts of a 15% aqueous solution of trisodium phosphate and 1 part of 2-ethoxyethanol was used.

Reference Example (a) Preparation of d-(chlorosulfonylphenyl)-chlorocinnamic acid.
f phenylacetic acid, 801rLl acetic anhydride, and 40
Triethylamine in ml was refluxed for 5 hours.

Unreacted 4-chlorobenzaldehyde was removed by steam distillation and the residue was dissolved in aqueous alcohol and treated with decolorizing carbon.

Acidification of the solution gave crystals of .alpha.-phenyl-4-chlorocinnamic acid.

The product was recrystallized from alcohol and had a melting point of 202-204.
It was confirmed that the temperature was °C.

The chlorosulfonyl derivative was prepared by the method described in Example 1.

(b) Preparation of a Photosensitive Material 24 g of the resorcinol-formaldehyde resin prepared as in Example 1 was dissolved in 400 mL of dimethylformamide, to which was added the α-
(Chlorosulfoxylphenyl)-chlorocinnamic acid 36
f and chlorosulfonylcinnamylidenemalonic acid 322 prepared in the same manner as in Example 1 were added.

The resulting mixture was cooled to about 50° C. and a saturated solution of sodium carbonate was added dropwise until the pH was 8-10.

After standing for 4 hours, the solid was separated, dissolved in water and reprecipitated by acidifying the resulting solution with hydrochloric acid.

(e) Manufacture of printed circuit board The procedure of Example 1(d) was repeated.

However, the developer consisted of a 7.5% trisodium phosphate solution.

Example 4 (a) Preparation of Photosensitive Material 10.6P Uresinoid R
751 (phenol formaldehyde resin manufactured by Resinous Chemicals Ltd.) was dissolved in 401111 of anhydrous dioxane and added to 4,2? of p-azidobenzoyl chloride.

2.5 ml of pyridine was added and the resulting mixture was diluted with 50
The mixture was heated at 4° C. for 4 hours.

The ester was precipitated by the addition of water and the product, air-dried at room temperature, was dissolved in 200 mA of dimethylformamide and 241 of chlorosulfonylcinnamylidenemalonic acid (prepared as in Example 1) was added with stirring.

The solution was cooled to 5° C. and saturated sodium carbonate solution was added dropwise until the pH was 8-10.

The solution was allowed to stand for about 8 hours, after which the solid was filtered off, redissolved in water and the product precipitated by acidifying the solution with hydrochloric acid.

(b) Manufacture of printed circuit board The procedure of Example 1(d) was repeated.

However, the developer consisted of a 7.5% trisodium phosphate solution.

Example 5 (a) Preparation of chlorosulfonylcinnamylidenecyanoacetic acid (formula 3).

The product obtained by condensation of cinnamaldehyde with cyanoacetic acid was converted to the corresponding chlorosulfonyl derivative using the method described in Example 1(a).

The acid thus obtained melted at 210-212°C.

(b) Manufacture of photosensitive materials.

To a solution of 1.09 mL of dimethylpoly(2-fluoro-formaldehyde) resin (prepared in the same manner as in Example 1) was added a solution of 3.0 mL of the above-mentioned chlorosulfonylcinnamylidene cyanoacetic acid in 201 mL of dimethylformamide.

The rice mixture was cooled to 5° C. and the pH was adjusted to about 9 with saturated sodium carbonate solution.

After standing for 8 hours the mixture was acidified and the product separated.

(e) Preparation of printing plates The process of Example IQd) was repeated except that the developer contained a 0.5% trisodium phosphate solution.

Example 6 (a) Preparation of chlorosulfonyl-δ-chlorocinnamyrthene malonic acid (formula II).

80 g of phosphoryl chloride was added dropwise to chilled 80 ml of dimethylformamide.

48f? of acetophenone was added over 45 minutes,
The mixture was stirred at 0° C. for an additional 60 min.

After standing overnight at room temperature, the mixture was poured into a solution of 6001 sodium acetate in 15007711 water.

β-Chlorcinnamaldehyde separated out as a red oil.

The mixture was extracted with ether and the ethereal solution was dried over anhydrous sodium sulfate.

Evaporation of the ether afforded 441-dichloromethane.

Condensation of β-chlorocinnamaldehyde with malonic acid gave δ-chlorocinnamylidenemalonic acid which was converted to the corresponding chlorosulfonyl derivative using the method described in Example 1(a).

(b) Manufacture of photosensitive materials.

The resorcinol-formaldehyde resin 1.09f prepared by the method described in Example 1 was condensed with the δ-chlorosulfonylcinnamylidenemalonic acid 3.33P prepared as described above according to the method described in Example 5(a).

(C) Manufacture of printed circuit boards.

The procedure of Example 5(e) was repeated.

Example 7 (a) Preparation of a Photosensitive Material The product 3.3f obtained by condensation of Lytron 822, a styrene-maleic anhydride copolymer available from Monsanto, with an excess of ethylenediamine.
and chlorosulfonylcinnamylidenemalonic acid 5-Of?, prepared as described in Example 1, were dissolved in aqueous N
Reaction in the presence of aoH gave a pale yellow, alkali-soluble resin.

The product was isolated by pouring the mixture into water, separating the precipitate and drying in air at room temperature.

(b) Manufacture of printed circuit boards.

The procedure of Example 1(a) was repeated except that the developer contained a 12% sodium metasilicate solution.

Example 8 (a) Preparation of photosensitive material.

The light-sensitive material of Example 7 was prepared by reacting a condensation product of chlorosulfonylcinnamylidenemalonic acid with an excess amount of ethylenediamine with a styrene-maleic anhydride copolymer.

This was confirmed by the reaction of 240r of chlorosulfonylcinnamylidene malonic acid 12r prepared as described in Example 1.
A solution of 600 ml of ethylenediamine dissolved in 240 ml of dioxane was added to a solution of 600 ml of ethylenediamine dissolved in 240 ml of dioxane.
Addition was performed with vigorous stirring.

The resulting yellow solid was dissolved in water and dilute hydrochloric acid was added until precipitation of aminoethylsulfonamide cinnamylidene malonic acid hydrochloride was complete.

2i of Lytron 822 were dissolved in anhydrous dimethylformamide to obtain a 20% solution, and a solution of 2.41 of the hydrochloride in 10 TrLl of dimethylformamide was added.

The mixture was shaken to obtain a clear solution.

1.0 ml of triethylamine was added and the mixture was stirred for an additional 30 minutes.

The product was isolated by pouring the mixture into water, separating the precipitated material, and drying it in air at room temperature.

(b) Manufacture of printed circuit boards.

The procedure of Example 7(b) was repeated.

Example 9 (a) Preparation of photosensitive material.

1.41' of polyethyleneimine having a molecular weight of 50-100.times.103, available from The Dow Chemical Company, was dissolved in 30771 L of 2N sodium hydroxide and 10.5 F of chlorosulfonylcinnamylidenemalonic acid (prepared as described in Example 1) in 50 rl of cyclohexanone was added.

The mixture was shaken for 30 minutes and acidified.

The product was separated and washed with water.

(b) The above product 2i was stirred with a hot mixture of dimethylformamide and dimethylsulfoxide and the insolubles were removed by filtration.

Neozapon Blue FLEO, Ir, Phthalocyanine Blue Dye and 5-Nitroacenaphthene 0, manufactured by BASF Corporation
1 was added to the solution with stirring.

This solution was then used to prepare a photographic plate in the same manner as described in Example 1, and the photographic plate was exposed and processed in the same manner as described in Example 1.

Example 10 (a) Chlorosulfonyl-α-(chlorophenyl)
- Preparation of cinnamic acid (formula II) A mixture of 42.2f of benzaldehyde, 67.8F of chlorophenylacetic acid, 80ml of acetic anhydride and 40ml of triethylamine was refluxed for 5 hours.

Unreacted benzaldehyde was removed by steam distillation and the residue was dissolved in aqueous alcohol and treated with decolorizing carbon.

Acidification of the solution gave crystals of α-(chloro)cinnamic acid, which was then recrystallized from alcohol.

The chlorosulfonyl derivative was prepared by the method described in Example 1.

(b) Preparation of a Photosensitive Material The procedure of Example 1(c) was repeated using dichlorosulfonyl-.alpha.-(chlorophenyl)-cinnamic acid instead of chlorosulfonylcinnamylidenemalonic acid.

(e) Manufacture of printed circuit boards The process of Example 1(a) was repeated.

In carrying out the present invention, the following conditions can be met.

(1) The method of claim 1, wherein the polymer contains multiple hydroxyl groups and the polymer is an epoxy resin, a phenol/aldehyde resin, a phenoxy resin, a poly(vinyl, alcohol), a cellulose, a cellulose derivative, a partially hydrolyzed poly(vinyl ester), a poly(hydroxyethyl acrylate), a poly(hydroxyethyl methacrylate), a partially hydrolyzed acetal, or a condensation product of a phenoxy alcohol with an aldehyde.

(2) The method according to claim 1, wherein the phenol/aldehyde resin is a resorcinol-formaldehyde resin.

(3) The process of claim 1, wherein the polymer contains a plurality of primary and/or secondary amines, such polymer being a poly(vinyl amine); an aniline/formaldehyde resin; a condensation product of a styrene/maleic anhydride polymer or an alkyl vinyl ether/maleic anhydride copolymer with an excess of an aliphatic or aromatic diamine; or a poly(ethyleneimine).

(4) The method of claim 1, wherein the polymer contains a plurality of epoxide groups, and the polymer is an epoxy resin or a novolak/epoxy resin.

(5) In the formula, a is 1, R4 is a carboxyl group, and X is a halosulfonyl group.

(6) The method according to the above item 5, wherein the compound is chlorosulfonyl cinnamylidene malonic acid.

(7) The method according to any one of claims 1 to 4, wherein the compound is chlorosulfonyl-delta-chlorocinnamylidene malonic acid, chlorosulfonylcinnamylidene cyanoacetic acid or chlorosulfonyl-δ-(chlorophenyl)-α-cinnamic acid.

(8) In the formula, R4 is a halosulfonyl phenyl group and X is an inactive group.
The method described in section .

(9) Compound δ-(chlorosulfonyl phenyl)★
The method according to claim 8, wherein the compound is chloro-cinnamic acid.

10. The process of claim 1, further comprising reacting the polymer with a halide which is derived from an aromatic sulfonic acid, an aliphatic carboxylic acid or an aromatic carboxylic acid and which does not contain a free carboxylic acid group.

01) A method for producing a light-sensitive material containing a group represented by the formula: (wherein R is an aromatic group; a is 0 or 1; R1, R2 and R3 are the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyl group or an aralkoxy group; ** and R4 represent an alkyl group, an alkoxycarbonyl group, a carboxyl group, a cyano group, a phenyl group substituted with an inactive group, or a hydrogen atom) bonded to a carbon atom of a polymer.

(1) a formula attached to a carbon atom of a polymer; (wherein R
is an aromatic group; a is O or 1; R1, R2 and R3 are the same or different and each is a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkoxy group,
aryloxy, aralkyl or aralkoxy; ph is a phenyl group; and X is an inert group;
A method for producing a light-sensitive material containing a group represented by

A photosensitive plate comprising a support coated with a layer of a photosensitive material as described in paragraphs 11-12 above.

α-energy: The photosensitive plate described in paragraph 13 is imagewise exposed to light (i
maga-wise exposing) L,
A method of making a printing plate in which the plate is developed to remove the unexposed areas of the layer, leaving behind a portion of the layer formed by the exposed areas of the layer on the support.

Claims (1)

[Claims] 1 A compound having a plurality of epoxide groups, hydroxyl groups or first and/or second aryl groups.
or a method for producing a light-sensitive material, comprising reacting a polymer containing a secondary amino group with a compound containing a nitrosulfonyl group and represented by the general formula (wherein R is an aromatic group; a is O or 1; R1, R2 and R3 are the same or different hydrogen atoms or halogen atoms; R4 is a phenyl group substituted with an inactive group when a is O, and X is a halosulfonyl group; R4 is a carboxyl group or cyano group when a is 1, and X is a halosulfonyl group).