United States Patent (19) (11) 4,253,999 Okishi 45) Mar. 3, 1981 54 AGENT FOR PROTECTING THE SURFACE 56) References Cited OF LITHOGRAPHC PRNTNG PLATE U.S. PATENT DOCUMENTS COMPRSNG A PLASTCZER CONTAINING OL, PHASE AND A 3,615,791 10/1971 Thomas et al...... 101/.465 SURFACTANT AND A HYDROPHL CHGH 3,666,502 5/1972 Erikson ...... 101/.465 3,679,479 7/1972 Ray et al...... 101/466 MOLECULARWEIGHT COMPOUND 4,033,919 7/1977 Lawson ...... 260/29.6 TA CONTAINING AQUEOUS PHASE 4,116,896 9/1978 Garrett et al...... 260/17 R 75 Inventor: Yoshio Okishi, Shizuoka, Japan 4,162,920 7/1979 Gillich ...... 106/145 73) Assignee: Fuji Photo Film Co., Ltd., FOREIGN PATENT DOCUMENTS Minami-ashigara, Japan 1135334 12/1968 United Kingdom...... 101/465 21 Appl. No.: 52,048 Primary Examiner-Edward M. Woodberry - (22) Filed: Jun. 25, 1979 Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, (30) Foreign Application Priority Data Zinn and Macpeak June 23, 1978 JP Japan ...... 53-7664 57 ABSTRACT 51) Int. Cl...... C08L 3/02; C08L 5/04; An agent for protecting the surface of a lithographic CO8L 5/00 printing plate which is an emulsion comprising an oil 52 U.S.C...... 260/17 R; 101/465; phase containing a having a solidifying point 101/466; 106/2; 106/14.5; 252/312; 260/17.4 of 15 C. or less and a surfactant, and an aqueous phase ST; 260/9; 260/17.2; 260/17.3; 260/13; 260/14; having dissolved therein a hydrophilic high molecular 260/15; 260/16; 260/29.6 WB; 260/29.6 HN; weight compound. 260/29.6M; 260/29.6E, 260/31.2 R; 260/31.8 R; 427/144; 427/145 58) Field of Search ...... 260/17 R, 17.4 ST 73 Claims, No Drawings 4,253,999 1. 2 It is a further object of this invention to provide an AGENT FOR PROTECTING THE SURFACE OF odorless agent for protecting the surface of a litho LTHOGRAPHIC PRINTNG PLATE graphic printing plate. COMPRESINGAPLASTICZER CONTAINING OIL As a result of various studies in search for an emul PHASE ANDA SURFACTANT AND A sion type gumming solution which achieves the above HYDROPHC HIGH MOLECULARWEIGHT defined objects, it has been unexpectedly found that COMPOUND CONTAINING AQUEOUS PHASE these objects can be accomplished by substituting an oil phase containing a plasticizer having a solidifying point BACKGROUND OF THE INVENTION of 15° C. or less for the oil phase of the conventional 1. Field of the Invention O emulsion type gumming solution which comprises a This invention relates to an agent for protecting the petroleum fraction which has dissolved therein a lipo surface of a lithographic printing plate, especially to an philic substance. Therefore, this invention provides an emulsion type plate protective agent. agent for protecting the surface of a lithographic print 2. Description of the Prior Art ing plate which is an emulsion comprising an oil phase The final step of the process of making a lithographic 15 containing a plasticizer having a solidifying point of 15 printing plate is generally referred to as a gunming step C. or less and a surfactant, and an aqueous phase having since the plate is coated with a gumming solution to dissolved therein a hydrophilic high molecular weight protect the non-image area (which retains water and compound. repels the greasy printing ink). While the primary pur DETALED DESCRIPTION OF THE pose of gumming is to desensitize or increase the hydro INVENTION philicity of the non-image area of the lithographic print The plasticizer which is the most characteristic fea ing plate, it has other purposes. Namely, to prevent ture of the plate protective agent of this invention con possible deterioration of the lithographic printing plate stitutes the oil phase of an emulsion and is required to during the period between making the plate and print 25 solidify at a temperature lower than about 15 C. Such ing or during the period when printing is interrupted; to plasticizer can be selected from what are generally prevent the non-image area from becoming receptive to called low-molecular-weight . The plasticiz printing ink due to sebum on fingers and other foreign ers used in this invention boils at atmospheric pressure matter during handling of the lithographic printing at a temperature which is preferably at least about 200 plate such as when it is set on a printing machine; and to 30 C., more preferably at least 300 C. Examples of the prevent development of scratches and other flaws on preferred plasticizer include a phthalic acid diester such the non-image area or image-area (which repels water as dibutyl , diheptyl phthalate, di-n-octyl and accepts printing ink) during handling of the plate. phthalate, di(2-ethylhexyl)phthalate, dinonyl phthalate, Among gumming solutions of the conventional type, didecyl phthalate, dilauryl phthalate or butylbenzyl the most effective one is a gumming solution of an emul 35 phthalate; an aliphatic ester of a dibasic acid such as sion type which comprises an oil phase having dissolved dioctyl , butylglycol adipate, dioctyl azelate, in a petroleum fraction a lipophilic substance such as a dibutyl sebacate, di(2-ethylhexyl)sebacate, or dioctyl lipophilic surfactant soluble in an organic solvent and sebacate; an epoxidized triglyceride such as epoxidized an aqueous phase having a water soluble dextrin dis soybean oil; a phosphate ester such as tricresyl phos solved therein. When this type of gumming solution is phate, trioctyl phosphate or trischloroethyl phosphate; used to guma plate for lithographic printing, the image and a benzoic ester such as benzyl benzoate. Particu area is protected by the lipophilic substance in the oil larly preferred are dioctyl adipate, dibutyl sebacate and phase whereas the non-image area is protected by the dioctyl azelate which give off the least odor and can be water soluble dextrin in the aqueous phase. As a result, handled with maximum safety. the lipophilicity of the image-area decreases only 45 According to this invention, these plasticizers can be slightly even if it is in contact with the water soluble used independently or as a mixture and in either case, dextrin. they are used in an amount within the range of from However, this emulsion type gumming solution is about 0.1 to about 10 wt.%, preferably from 0.5 to 5 unable to completely prevent a decrease in the lipo wit%, based on the total weight of the plate protective philicity of the image area, and it is not as effective in 50 agent. As the amount of the plasticizer to be used de desensitizing the non-image areas as expected. In addi creases to less than 0.1 wit%, the resulting plate protec tion, the lipophilic substance which precipitates as a tive agent will lose its stability as an emulsion and it also result of evaporation of the petroleum fraction stains the decreases the lipophilicity of the image area of a litho non-image area. Furthermore, since the petroleum frac graphic printing plate. On the other hand, as the amount tion is volatile, the gumming solution emits strong odors 55 of the plasticizer increases to greater than 10 wit%, which is intolerable in a working environment. more plasticizer will stick to the image area and, as a result, the image area becomes so greasy to the touch SUMMARY OF THE INVENTION that the lithographic printing plate coated with such It is therefore one object of this invention to provide protecting agent is difficult to handle. an improved emulsion type plate protective agent. The oil phase of the protective agent according to It is another object of this invention to provide an this invention preferably contains dissolved therein a agent for protecting the surface of a lithographic print lipophilic substance for the purpose of enhancing the ing plate which is highly effective in desensitizing the stability of the protective agent in the emulsified state non-image area and yet does not decrease the lipo and minimizing the potential decrease in the lipo philicity of the image-area of the printing plate. 65 philicity of the image area. A preferred lipophilic sub It is still another object of this invention to provide an stance is one which is conventionally used as a vehicle agent for protecting the surface of a lithographic print for a lithographic printing ink. Specific examples of the ing plate which does not stain the non-image area. suitable lipophilic substance include a novolak phenolic 4,253,999 3 4. resin such as a phenolformaldehyde resin, cresol-for ylcellulose or methylcellulose, polyvinyl alcohol, poly maldehyde resin or tertbutylphenol-formaldehyde vinyl pyrrolidone, polyacrylamide, a water soluble co resin; a xylene resin prepared by condensing phenol and polymer containing an acrylamide unit, a copolymer of xylene with formaldehyde; a resin prepared by condens vinyl methyl ether and maleic anhydride, or a copoly ing phenol and mesitylene with formaldehyde; polyhy mer of vinyl acetate and maleic anhydride. Particularly droxystyrene; brominated polyhydroxystyrene; cashew preferred are gum arabic, dextrin, polyvinyl pyrrol resin; partial esterified product of a copolymer of sty idone, carboxymethylcellulose and polyvinyl alcohol. rene and maleic anhydride; melamine resin; alkyd resin; Gum arabic is most preferred. These film-forming, hy resin; epoxy resin; rosin or modified rosin drophilic high molecular weight compounds are used such as hydrogenated rosin or rosin ester; and a petro O independently or as a mixture. Of special advantage is a leum resin such as gilsonite. A novolak phenolic resins, gum arabic and dextrin combination which is able to rosin or modified rosin are preferred. Other examples of enhance the hydrophilicity of the non-image area with suitable lipophilic substances include an aliphatic car out reducing the lipophilicity of the image area. While boxylic acid having 5 to 25 carbon atoms such as oleic these hydrophilic high molecular weight compounds acid, lauric acid, valeric acid, nonylic acid, capric acid, 15 may be contained in the aqueous phase in a wide range myristic acid and palmitic acid, as well as castor oil. of concentrations, they are generally used in an amount Whether used independently or as a mixture, these lipo within the range of from about 5 to about 40 wit%, philic substances are used in an amount within the range preferably from 10 to 30 wit%, based on the total weight of from about 0.05 to about 5 wt.%, preferably from 0.1 of the plate protective agent, and their concentration in to 1 wit%, based on the total weight of the protective 20 the aqueous phase is in the range of from about 6 to agent. about 60 wit%, preferably from 15 to 50 wit%. The oil phase of the plate protective agent of this The aqueous phase of the plate protective agent ac invention contains a surfactant which functions as an cording to this invention preferably contains a wetting emulsifying agent for providing a stable emulsion con agent for the purpose of enabling the aqueous phase to sisting of the oil phase and an aqueous phase which will 25 spread suitably to the non-image area of the litho be described hereafter. The surfactant is present in the graphic printing plate. A preferred wetting agent is a oil phase as it is substantially dissolved therein. A suit polyhydric alcohol, which is specifically exemplified by able surfactant can be selected from a wide range of ethylene glycol, diethylene glycol, triethylene glycol, surfactants which include a nonionic surfactant such as propylene glycol, butylene glycol, pentanediol, hexyl polyoxyethylene alkyl ether, polyoxyethylene alkyl 30 ene glycol, tetraethylene glycol, glycol, phenyl ether, polyoxyethylene ester of aliphatic acid, dipropylene glycol, tripropylene glycol, glycerin, sorbi sorbitan ester of aliphatic acid, polyoxyethylene sorbi tol or pentaerythritol. Glycerin is most preferred. These tan ester of aliphatic acid, or glycerin ester of an ali wetting agents are used in an amount of from about 0.5 phatic acid; an anionic surfactant such as an aliphatic to about 10 wit%, preferably from 1 to 5 wt.%, based on acid salt, a salt of alkylsulfate ester, alkylbenzenesulfon 35 the total weight of the plate protective agent. ate, alkylnaphthalenesulfonate, a salt of dialkylsulfosuc The aqueous phase of the plate protective agent ac cinate ester, a salt of alkyl phosphate ester, a condensate cording to this invention preferably contains a water of naphthalene sulfonic acid with formalin, or a salt of a soluble salt for the purpose of enhancing the hydrophi polyoxyethylene alkyl sulfate ester; and a cationic sur licity of the non-image area of a lithographic printing factant such as an alkylamine salt, quaternary ammo plate when it is coated with the plate protective agent. nium salt, or polyoxyethylene alkylamine salt. Preferred Advantageous water soluble salts include an alkali surfactants are polyoxyethylene alkyl ether, polyoxy metal salt and ammonium salt; particularly advanta ethylene alkylphenyl ether, a salt of a dialkylsulfosucci geous are water soluble alkali metal salts and ammo nate ester, a salt of an alkylphosphate ester and polyoxy nium salts of acids such as acetic acid, molybdic acid, ethylene alkylamine salt because, like the above men 45 boric acid, nitric acid, sulfuric acid, phosphoric acid and tioned lipophilic substances, these surfactants are capa polyphosphoric acid. Specific examples are ammonium ble of minimizing the decrease in the lipophilicity of the acetate, sodium acetate, potassium acetate, sodium mo image area of a lithographic printing plate. Polyoxyeth lybdate, potassium molybdate, sodium borate, ammo ylene alkylphenyl ether is particularly preferred. The nium borate, lithium nitrate, sodium nitrate, potassium above mentioned surfactants can be used independently 50 nitrate, sodium primary phosphate, sodium secondary or as a mixture. Of particular advantage is a combina phosphate, sodium tertiary phosphate, potassium pri tion of polyoxyethylene alkylphenyl ether and salt of mary phosphate, potassium secondary phosphate, po dialkylsulfosuccinate ester which exhibits the combined tassium tertiary phosphate, ammonium tertiary phos effect of stabilizing an emulsion and minimizing the phate, and sodium polyphosphate. Particularly pre decrease in the lipophilicity of the image area. The 55 ferred are potassium acetate, sodium borate, ammonium surfactants are used in an amount within the range of borate, potassium nitrate, sodium molybdate, potassium from about 0.5 to about 10 wit%, preferably from 1 to 5 molybdate and potassium sulfate. Whether used inde wit%, based on the total weight of the plate protective pendently or as a mixture, these water soluble salts are agent. used in an amount of from about 0.05 to about 2 wt %, The hydrophilic high molecular weight compound preferably from 0.1 to 1 wt.%, based on the total weight contained in the aqueous phase of the plate protective of the plate protective agent. agent according to this invention functions to protect If gum arabic is used as the hydrophilic high molecu the non-image area of a lithographic printing plate and lar weight compound to be dissolved in the aqueous it is preferably a film-forming water-soluble resin. Ex phase of the plate protective agent, the pH of the aque amples of the suitable film-forming hydrophilic high 65 ous phase is controlled to be acidic, preferably in the molecular weight compounds are dextrin, gum arabic, range of from 1 to 5, more preferably from 1 to 3. an alginate such as sodium alginate, a water soluble Therefore, if the aqueous phase is not acidic, an acid is cellulose such as carboxymethylcellulose, hydroxyeth used to render it acidic. Acids used for pH adjustment 4,253,999 5 6 include a mineral acid such as phosphoric acid, sulfuric drophilic but also for the purpose of preventing any acid or nitric acid, and an organic acid such as citric adverse reaction with the photosensitive composition acid, tannic acid, malic acid glacial acetic acid, lactic placed on the substrate and providing strong bond be acid, oxalic acid or p-toluene sulfonic acid. Phosphoric tween the substrate and photosensitive layer. acid is particularly advantageous because it not only Preferred examples of the composition that makes the functions as an agent to adjust the pH of the aqueous photosensitive layer to be formed on these aluminum phase but it also prevents staining of the non-image area. substrates include the following: These acids are used in an amount of from 0.1 to 8wt%, preferably from 0.5 to 5 wt.%, based on the total weight (1) Compositions composed of diazo resins of the aqueous phase. 10 Diazo resins which are typified by a condensate of A typical example of the method of preparing the p-diazodiphenylamine and paraformaldehyde may be plate protective agent of this invention will hereunder water soluble or insoluble, and they are preferably in be described. soluble in water and soluble in conventional organic First, a hydrophilic high molecular weight com solvents. Particularly preferred diazo compounds are pound is dissolved in water to form an aqueous phase. If 15 salts of a condensate of p-diazophenylamine and formal necessary, a wetting agent, water soluble salt and/or dehyde or acetaldehyde, such as a compound having acid is added to the aqueous phase. Separately, a surfac two or more diazo groups in its molecule in the form of tant is dissolved in a plasticizer to form an oil phase. If a phenolate, fluorocaprate or salts of sulfonic acids such necessary, a lipophilic substance is added to the oil as triisopropylnaphthalenesulfonic acid, 4,4-biphenyldi phase. Dropwise the oil phase is added to the aqueous 20 sulfonic acid, 5-nitro-ortho-toluenesulfonic acid, 5-sul phase under stirring. A homogenizer is used to promote fosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2 emulsification of the mixture until the protective agent nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic of this invention is prepared. acid, 3-bromobenzenesulfonic acid, 2-chloro-5-nitro While the plate protective agent of this invention can benzenesulfonic acid, 2-fluorocaprylnaphthalenesul be used with a variety of lithographic printing plates, it 25 is applied with advantage to a lithographic printing fonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4- plate prepared by performing imagewise exposure and hydroxy-5-benzoylbenzenesulfonic acid and paratolu development of a presensitized lithographic printing enesulfonic acid. Other preferred diazo resins include a plate (which is hereinafter referred to as PS plate) condensate of 2,5-dimethoxy-4-p-tolylmercaptoben which comprises an aluminum substrate coated with a 30 Zenediazonium and formaldehyde in the form of the photosensitive layer. salts illustrated above. PS plates which are of particular advantage to the Another preferred example is the diazo resin de object of this invention will hereunder be described in scribed in British Pat. No. 1,312,925. detail. While these diazo resins may individually serve as a Aluminum plates which are advantageously used as a 35 photosensitive material to be used for preparing a resist, substrate include a pure aluminum plate and aluminum they are preferably used in combination with a binder. alloy plate as well as a film laminated or metal A variety of polymers can be used as the binder. A lized with aluminum. These aluminum plates are prefer preferred binder contains a hydroxy, amino, carboxylic ably subjected to surface treatment such as graining, acid, amido, sulfone amide, active methylene, thioalco immersion in an aqueous solution of sodium silicate, 40 hol, epoxy and other groups. Examples of such pre potassium fluorozirconate orphosphate, or anodization. ferred binders are: shellac of the type described in Brit Other advantageous substrates are an aluminum plate of ish Pat. No. 1,350,521; a polymer of the type described the type described in U.S. Pat. No. 2,714,066 which is in British Pat. No. 1460,978 and U.S. Pat. No. 4,125,276 grained and thereafter immersed in an aqueous solution which contains a hydroxyethyl acrylate or hydroxy of sodium silicate, and an aluminum plate of the type 45 ethyl methacrylate unit as the predominant repeating described in U.S. Pat. No. 3, 181,461 which is anodized unit; a resin of the type described in U.S. Pat. before it is immersed in an aqueous solution of an alkali No. 3,751,257; a phenolic resin and a polyvinyl acetal metal silicate. The anodization is carried out using an resin such as polyvinyl formal resin or polyvinylbutyral aluminum anode in an electrolyte comprising one or which are of the type described in British Pat. No. more aqueous or non-aqueous solutions of an inorganic 50 1,074,392; a linear resin, polyvinyl alcohol acid such as phosphoric acid, chromic acid, sulfuric resin esterified with phthalic acid, an epoxy resin pre acid or boric acid, or an organic acid such as oxalic acid pared by condensing and epichlorohydrin, or sulfamic acid, or salts thereof. a polymer containing an amino group such as The technique of electrodeposition with silicate as polyaminostyrene or polyalkyl amino (meth)acrylate, described in U.S. Pat. No. 3,658,662 can also advanta 55 cellulose such as cellulose acetate, cellulose alkyl ether, geously be employed in this invention. cellulose acetate phthalate, which are of the type de Another example of the advantageous substrate is an scribed in U.S. Pat. No. 3,660,097. aluminum plate of the type described in U.S. Pat. No. These binders are suitably contained in the photosen 4,087,341, Japanese Patent Publication No. 27481/71 sitive resist forming composition in an amount of from and Japanese Patent Application (OPI) No. 30503/77 60 40 to 95 wt.%. Higher binder content (in other words, (the term "OPI" as used herein refers to a "published lower diazo resin content) of course results in greater unexamined Japanese patent application') which is first sensitivity but this is compromised by low time-depend electrograined and then anodized in the manner de ent stability. Optimum content of the binder is in the scribed above. A further example is an aluminum plate range of from about 70 to 90 wt %. of the type described in U.S. Pat. No. 3,834,998 which 65 Compositions composed of these diazo resins may is grained, chemically etched and anodized as described optionally contain other additives such as phosphoric above. The surface treatments are applied not only for acid, a dye and a pigment as described in U.S. Pat. No. the purpose of making the surface of the substrate hy 3,236,646. 4,253,999 7 8 dien-1-one, 1-(4-azidophenyl)-5-(4-methoxyphenyl)- (2) Compositions composed of o-quinonediazide penta-1,4-dien-3-one, 1-(4-azidophenyl)-3-(1-naphthyl)- compounds propen-1-one, 1-(4-azidophenyl)-3-(4-dimethylamino A particularly preferred o-quinonediazide compound phenyl)-propan-1-one, 1-(4-azidophenyl)-5-phenyl-1,4- is an o-naphthoquinonediazide compound of the type pentadien-3-one, 1-(4-azidophenyl)-3-(4-nitrophenyl)-2- described in U.S. Pat. Nos. 2,766,118; 2,767,092; propen-1-one, 1-(4-azidophenyl)-3-(2-furyl)-2-propen 2,772,972; 2,859,112; 2,907,665; 3,046,110; 3,046,111; 1-one, 1,2,6-tri(4'-azidobenzoxy)hexane, 2,6-bis-(4- 3,046,115; 3,046,118; 3,046,119; 3,046,120; 3,046,121; azidobenzylidyene-p-t-butyl)cyclohexanone, 4,4'- 3,046,122; 3,046,123; 3,061,430; 3,102,809; 3,106,465; diazidobenzalacetone, 4,4'-diazidostilbene-2,2'-disul 3,635,709; 3,647,443 and many other publications. Par 10 fonic acid, 4'-azidobenzalacetophenone-2-sulfonic acid, ticularly preferred are and o-naphthoguinonediazido 4,4'-diazidostilbene-a-carboxylic acid, di-(4-azido-2'- sulfonic acid ester or an o-naphthoquinonediazidocar hydroxybenzal)acetone-2-sulfonic acid, 4-azidoben boxylic acid ester of an aromatic hydroxy compound, zalacetophenone-2-sulfonic acid, 2-azido-1,4-diben and an o-naphthoquinonediazidosulfonamide oro-naph Zenesulfonylaminonaphthalene, or 4,4-diazide-stilbene thoquinonediazidocarboxylic acid amide of an aromatic 15 2,2'-disulfonic acid anilide. amino compound. Very effective compounds are a con These low-molecular-weight aromatic diazide com densate of pyrogallol and acetone esterified with o pounds may advantageously be replaced by the azido naphthoquinonediazidosulfonic acid as described in containing polymer which is illustrated in Japanese U.S. Pat. No. 3,635,709; a polyester having a terminal Patent Publications Nos. 9047/69; 3.387/69; 96.13/70; hydroxy group esterified with o-naph 20 24915/70; 25713/70; Japanese Patent Application (OPI) thoquinonediazidosulfonic acid O o-naph Nos. 5102/75; 84.302/75; 84303/75; and 12984/78. thoquinonediazidocarboxylic acid as described in U.S. The above defined photosensitive azide compounds Pat. No. 4,028, 111 and; a homopolymer of p-hydroxys are preferably used in combination with a polymer tyrene or a copolymer thereof with another copolymer which works as a binder. A preferred binder is an alkali 1zable monomer which is esterified with o-naph 25 soluble resin. Examples of the alkali-soluble resin in thoquinonediazidosulfonic acid O o-naph clude: a natural resin such as shellac or rosin; a novolak thoquinonediazidocarboxylic acid as described in U.S. type phenolic resin such as phenol-formaldehyde resin Pat. No. 4,139,384. or m-cresol-formaldehyde resin; a homopolymer of an While these o-quinonediazide compounds can be used unsaturated carboxylic acid or a copolyner thereof independently, they are preferably used as a mixture 30 with another copolymerizable monomer, such as poly with an alkali-soluble resin. A suitable alkali-soluble acrylic acid, polymethacrylic acid a, methacrylic acid resin includes a novolak type phenolic resin such as a styrene copolymera, methacrylic acid-methyl acrylate phenolformaldehyde resin, o-cresol-formaldehyde resin copolymer or a styrene-maleic anhydride copolymer; a or m-cresolformaldehyde resin. More preferably, these resin produced by reacting a partial or complete saponi phenolic resins are used in combination with a tert 35 fication product of polyvinyl acetate with an aldehyde butylphenol-formaldehyde resin which is a condensate such as acetaldehyde, benzaldehyde, hydroxybenzalde of formaldehyde and phenol or cresol substituted by an hyde or carboxybenzaldehyde or form partial acetal; alkyl group having 3 to 8 carbon atoms, as described in and polyhydroxystyrene. Other suitable examples of the U.S. Pat. No. 4,123,279. These alkali-soluble resins are binder are organic solvent soluble resins such as cellu contained in the photosensitive resist forming composi lose alkyl ethers typified by cellulose methyl ether and tion in an amount of from about 50 to 85 wt.%, prefera cellulose ethyl ether. bly from 60 to 80 wit%, based on the total weight of said The binder is preferably contained in an amount of composition. from about 10 to about 90 wit% based on the total Photosensitive compositions composed of these o weight of the composition composed of the photosensi quinonediazide compounds may optionally contain 45 tive azide compound. other additives such as pigment, dye and plasticizer. Compositions composed of the photosensitive azide (3) Compositions composed of photosensitive azide compound may optionally contain a dye, pigment, a compounds plasticizer such as a phthalate ester, phosphate ester, aliphatic carboxylic acid ester, glycol or sulfonamide, A suitable photosensitive azide compound is an aro 50 and a sensitizer such as Michlers ketone, 9-fluorenone, (natic azide compound wherein an azido group is 1-nitropyrene, 1,8-dinitropyrene, 2-chloro-1,2-benzan oonded to the aromatic ring either directly or through a thraquinone, 2-bromo-1,2-benzanthraquinone, pyrene carbonyl group or sulfonyl group. Upon exposure to 1,6-quinone, 2-chloro-1,3-phthaloylnaphthalene, or light, the azido group of the compound is decomposed cyanoacridine. to form nitrene which enters into various reactions that 55 While the basic structure of the PS plate that is suit insolubilize the compound. A preferred aromatic azide able for the purpose of this invention is composed of an compound contains one or more groups such as azido aluminum substrate overlaid with a photosensitive layer phenyl, azidostyryl, azidobenzal, azidobenzoyl and made of the photosensitive materials described above, azidocinnamoyl; specific examples are 4,4'-diazidochal the photosensitive layer may optionally be coated with cone, 4-azido-4'-(azidobenzoylethoxy) chalcone, N,N- one or more resin layers such as specifically described bis-p-azidobenzal-p-phenylenediamine, 1,2,6-tric4'- in U.S. Pat. No. 3,136,637 wherein the substrate is over azidobenzoxy)hexane, 2-azido-3-chloro-benzoquinone, laid with, in the order written, a photosensitive layer, a 2,4-diazido-4'-ethoxy-azobenzene, 2,6-di(4'-azidoben lipophilic resin layer, a hydrophobic resin layer a, water Zal)-4-methylcyclohexane, 4,4'-diazidobenzophenone, insoluble resin layer and another layer of resin which is 2,5-diazido-3,6-dichlorobenzoquinone, 2,5-bis(4-azidos 65 softened by a solvent. A PS plate of similar structure is :yryl)-1,3,4-oxadiazole, 2-(4-azidocinnamoyl)thiophene, described in British Pat. Nos. 1,478,333 and 1,478,334 2,5-di(4-azidobenzal)cyclohexanone, 4,4'-diazido and this structure is also included within the scope of phenylmethane, 1-(4-azidophenyl)-5-furyl-2-penta-2,4- this invention. 4,253,999 9 10 The following description illustrates how the plate ing solution of the following formulation at room tem protective agent of this invention is applied to a PS perature for a period of 1 minute, and the surface of the plate in one preferred embodiment. plate was lightly rubbed with absorbent cotton to re First, a PS plate is subjected to imagewise exposure move the unexposed area. The product was a litho and development to make a lithographic printing plate. graphic printing plate. The resulting plate is washed with water, the water on the plate removed with a squeegee, a suitable amount of the protective agent is poured on the plate, and a sponge Developer Solution is used to spread the agent to cover the entire surface of Benzyl alcohol 3.0 g the plate. As a result of these procedures, the non-image 10 Sodium isopropyl- 1.0 g area of the plate is protected in such a manner that the naphthalenesulfonate lithographic printing plate can withstand extended stor Sodium silicate (40% aqueous solution) 1.0 g age. The plate is washed with water to remove the gum Water 95 g before the conventional printing procedure starts. The plate protective agent of this invention hardly 15 An aqueous solution A of the following formulation decreases the lipophilicity of the image of a lithographic printing plate whereas it is capable of enhancing the was prepared, a solution B of another formulation set hydrophilicity of the non-image area. In addition, unlike forth below as gradually added to the aqueous solution the protective agent of conventional type which uses a A under vigorous stirring, and the resulting emulsion petroleum fraction as a solvent for the oil phase, the was subjected to further emulsification using a homoge protective agent of this invention does not spoil the nizer until the plate protective agent of this invention non-image area of a lithographic printing plate nor does was produced. it emit the odor characteristic of a petroleum fraction. The protective agent of this invention works most Aqueous Solution A effectively when it is applied to a lithographic printing 25 Gum arabic 4g plate prepared from the PS plate described in either Dextrin 16 g British Pat. Nos. 1,460,978 or 1,505,739. Phosphoric acid (85%) 0.2g This invention will hereunder be described in greater Water 75g detail by reference to the following Examples wherein Solution B all percents are by weight. Sodium dilauryl sulfosuccinate 1.0 g 30 Rosin ester (a product of 0.5g EXAMPLES 1 TO 4 AND COMPARATIVE Arakawa Chemical Co., Ltd.) EXAMPLES 1 TO 5 Solvent (see Table 1 below) 3.0 g A 0.24 mm thick aluminum substrate was degreased by immersion in a 7% aqueous solution of sodium ter The previously prepared lithographic printing plate tiary phosphate at 60 C., and after water washing, a 35 was washed with water, the excess water was removed suspension of pumice in water was poured on the sub with a squeegee, a small amount of the protective agent strate while it was grained by rubbing with a was poured dropwise thereon and a sponge was used to brush. After washing with water, the grained substrate spread the agent so as to cover the entire surface of the was immersed for a period of 30 to 60 seconds in a 5% printing plate. Subsequently, the plate was washed with aqueous solution of sodium silicate JIS No. 3 (molar water to remove the protective agent from its surface ratio of SiO2 to Na2O=3.1 to 3.3) which was controlled and set on a printing machine for printing. The plate at 70 C. protective, agent was checked for any odor it would After thorough washing with water, the substrate emit when it was applied to the lithographic printing was dried and coated with a sensitive solution of the 45 plate and for any stain that would be formed on the following formulation. resulting printed matter. The results of the checking are indicated in Table 1 below. Photosensitive Composition TABLE A copolymer of 2-hydroxyethyl methacrylate 0.87 g Run No. Solvent Odor Stain (as synthesized according to the method SO described in Example 1 of U.S. Pat. Example 1 Dioctyl phthalate ce e No. 4,123,276) Example 2 A. F Salt of 2-methoxy-4-hydroxy-5-benzoyl- 0.1 g Example 3 Epoxidized soybean oil FF r benzenesulfonic acid with a condensate Example 4 Benzyl benzoate faint P of p-diazodiphenylamine and paraformal Comparative dehyde 55 Example 1 n-Amyl alcohol yes light Oil Blue #603 (C.I. 74350, a product of 0.03 g Comparative Orient Chemical industries Co., Ltd.) Example 2 Benzyl alcohol 2-Methoxyethanol 6g Comparative Methanol 6 g Example 3 n-Amyl acetate strong Ethylene dichloride 6g Comparative Example 4 K-Solvent light stained The sensitive solution was applied such that the dry Comparative coating weight was 1.0 g/m. The thus prepared photo Example 5 Toluene fit lightly sensitive lithographic printing plate was exposed to stained seasonal conditions for a period of 1 year during which it was subjected to the effect of heat and moisture. The 65 Table 1 indicates that the plate protective agent of plate was exposed imagewise for a period of 40 seconds this invention emits little or no odor and that the litho to a metal halide lamp of 3 KW placed at a distance of graphic printing plate treated with it can provide un 1 m. Subsequently, the plate was immersed in a develop stained printed matter. 4,253,999 11 12 EXAMPLE 5 TABLE 2 A mechanically grained 2S aluminum substrate was Comparative artially etched by immersion in a 2% aqueous solution Protective agent Solution A Example 2 Example 2 of sodium hydroxide at 40 C. for a period of 1 minute. 5 No. of wasted sheets 15 3 5 After washing with water, the aluminum substrate was Stain Ole Ole some mmersed in a mixture of sulfuric acid and chromic acid or a period of about 1 minute to expose the surface of The above results show that the protective agent of pure aluminum. The substrate was then immersed in this invention does not decrease the lipophilicity of the 0% sulfuric acid at 30° C., and subjected to anodiza- 10 image area of the printing plate while enhancing the ion at a D.C. voltage of 1.5V and a current density of hydrophilicity of the non-image area nor does it pro A/dm2, followed by washing with water and drying. duce any stain on the non-image area. Subsequently, a roll coater was used to coat continu usly the substrate with a sensitive solution of the fol EXAMPLE 6 owing formulation until the dry coating weight was 2 15 The procedure of Example 1 was repeated to prepare g/m2. lithographic printing plates. The plates were gummed with three plate protective agents of the following for mulations, washed with water, and used for printing Photosensitive Solution according to the conventional procedures. The number Naphthoguinone-1,2-diazide(2)-5-sulfonic 20 of wasted sheets was counted and any stain formed on acid ester of acetone-pyrrogallol resin (as synthesized according to the method the non-image area was checked. In addition, each pro described in Example 1 of U.S. Pat. No. tective agent was left to stand in a container for the 3,635,709) purpose of evaluating the stability of the emulsion. The PR-50530 (tertiary-butylphenol/ results of counting, checking and evaluation are given formaldehyde resin manufactured in Table 3 below. by Sumitomo Durez Co., Ltd.) Hitanol #3110 (cresol/formaldehyde resin Plate Protective Agent Formulation manufactured by Hitachi Chemical Co., Ltd.) No. 1: the same as used in Example 2. Methyl ethyl ketone 50 g No. 2: the same as No. 1 above except that the sodium Cyclohexanone 40 g 30 dilaurylsulfosuccinate of Solution B was replaced by an equal amount of polyoxyethylene nonylphenyl The plate dried at 100° C. for a period of 2 minutes ether. had the performance of a PS plate which could be No. 3: the same as No. 1 above except that half the tored in a cool dark place for a period of 1 year without sodium dilaurylsulfosuccinate of Solution B was re iny significant deterioration in its quality. The thus 35 placed by 0.5 g of polyoxyethylene nonylphenyl presensitized lithographic printing plate was set in a ether. acuum printing frame and exposed to a Fuji Film PS TABLE 3 light (having the 3 KW light source from Toshiba Protective agent No. 1 No. 2 No. 3 Metal Halide Lamp MU 2000-2-OL and sold by Fuji No. of wasted sheets 10 10 5 Photo Film Co., Ltd.) through a positive film for a Stain none de Othe period of 30 seconds. Subsequently, the plate was im Emulsion stability partial partial remained mersed in a developing solution of the following formu phase phase stable ation. separation separation at the end occurred in occurred in of the 20th day 45 2 days 2 days Developer Solution Sodium silicate JIS No. 3 10 g The above results show that an emulsifying agent Aerosol OS (sodium isopropylnaphthalene- 20 g consisting of a mixture of sodium dilaurylsulfosuccinate sulfonate manufactured by American and polyoxyethylene nonylphenyl ether provides an Cyanamide Co.) 50 Benzyl alcohol 30 g emulsion which is more stable by far than independent Water added to make 1000 m use of individual emulsifiers and which does not de crease the lipophilicity of the image area of a litho graphic printing plate. The resultant lithographic printing plate was washed with water, the water was removed by squeegee the 55 EXAMPLE 7 late, gummed with one of the three protective agents The procedure of Example 1 was repeated to prepare indicated in Table 2 below and dried at 80 C. for a lithographic printing plates. The plates were gummed period of 5 minutes. The three printing plates were with three plate protective agents of the same formula lowed to stand at a temperature of 20° C. for a period tion as Example 1 except for the dibutylsebacate con of 7 days, washed with water to remove the protective tent. Each protective agent was prepared by emulsify gent from their surface, used to print according to ing a mixture of the following two solutions in the same :onventional procedures, and the number of sheets manner as in Example 1. pent before printed matter having satisfactory density of printing ink was obtained (the number will hereunder be referred to as the number of wasted sheets) was 65 Aqueous Solution A Gum arabic 4g :ounted and any stained non-image area of the printed Dextrin 16 g matter was checked. The results of evaluation are Phosphoric acid (80%) 0.2g hown in Table 2. Water 75g 4,253,999 13 14 resin; epoxy resin; rosin or modified rosin; and a petro -continued leum resin. Solution B 9. The agent of claim 7, wherein said lipophilic sub Sodium dilaurylsulfosuccinate 1.0 g stance is an aliphatic carboxylic acid having 5 to 25 Rosin ester (a product of Arakawa 0.5g 5 carbon atoms. Chemical Co., Ltd.) Dibutyl sebacate See Table 4 below for its content. 10. The agent of claim 1, wherein said surfactant is at least one of a nonionic surfactant, an anionic surfactant

and a cationic surfactant. Each protective agent was checked for stickiness of a 11. The agent of claim 10, wherein said surfactant is gummed plate as well as for the number of wasted selected from the group consisting of polyoxyethylene sheets and stain on the non-image area as in Example i. 10 alkyl ether, polyoxyethylene alkylphenyl ether, a poly The results are shown in Table 4 below. oxyethylene ester of an aliphatic acid, a sorbitan ester of TABLE 4 an aliphatic acid, a polyoxyethylene sorbitan ester of an Protective Agent No. No. 2 No. 3 aliphatic acid, a glycerin ester of an aliphatic acid, an Dibutyl sebacate content (g) 0.05 3.0 20.0 15 aliphatic acid salt, an alkyl sulfate ester, an alkylben Stickiness hone none yes zenesulfonate, an alkylnaphthylenesulfonate, a dialkyl No. of wasted sheets 5 3 3 sulfosuccinate ester, an alkylphosphate ester, a conden Stain One none light sate of naphthalenesulfonic acid with formalin, a poly oxyethylene alkylsulfate ester, a quaternary ammonium The above results show that higher content of the 20 salt, an alkylamine salt, and a polyoxyethylene alkyla plasticizer results not only in a sticky gummed plate but mine salt. in stained printed matter, whereas lower plasticizer 12. The agent of claim 11, wherein said surfactant is content is accompanied by a decrease in the lipo selected from the group consisting of polyoxyethylene philicity of the image area of a lithographic printing alkyl ether, polyoxyethylene alkylphenyl ether, dialkyl plate. 25 sulfosuccinate ester, alkyl phosphate ester and polyoxy While the invention has been described in detail and ethylene alkylamine salt. with reference to specific embodiments thereof, it will 13. The agent of claim 1, wherein said surfactant is be apparent to one skilled in the art that various changes present in an amount of about 0.5 to 10 weight % based and modifications can be made therein without depart on the weight of said agent. ing from the spirit and scope thereof. 30 14. The agent of claim 1, wherein said hydrophilic What is claimed is: high molecular weight compound is selected from the 1. In an agent for protecting the surface of a litho group consisting of dextrin, gum arabic, an alginate, a grapic printing plate which is an emulsion comprising water soluble cellulose, polyvinyl alcohol, polyvinyl an oil phase comprising a surfactant, and an aqueous pyrrollidone, polyacrylamide, an acrylamide copoly phase having dissolved therein a hydrophilic high mo-35 mer, a vinylmethyl ether-maleic anhydride copolymer lecular compound, the improvement wherein said oil and a vinyl acetate-maleic anhydride copolymer. phase further comprises a plasticizer having a solidify 15. The agent of claim 14, wherein said hydrophilic ing point of 15 C. or less, which is present in an amount high molecular weight compound is selected from the of from about 0.1 to at 10 wit% based on the total group consisting of gum arabic, dextrin, polyvinyl pyr amount of said agent. rolidone, carboxymethyl cellulose and polyvinyl alco 2. The agent of claim 1, wherein said plasticizer boils hol. at a temperature at least about 200 C. at atmospheric 16. The agent of claim 15, wherein said hydrophilic pressure. high molecular weight compound is gum arabic. 3. The agent of claim 1, wherein said plasticizer is 17. The agent of claim 14, wherein said hydrophilic selected from the group consisting of phthalic acid 45 high molecular weight compound is a combination of diesters, aliphatic esters of dibasic acids, epoxidized gum arabic and dextrin. triglycerides, phosphate esters, and benzoic esters. 18. The agent of claim 1, wherein said hydrophilic 4. The agent of claim 1, wherein said plasticizer is high molecular weight compound is present in an selected from the group consisting of dibutyl phthalate, amount of about 5 to 40 weight %. diheptyl phthalate, di-n-octyl phthalate, di(2-ethylhex 50 19. The agent of claim 1, wherein said aqueous phase yl)-phthalate, dinonyl phthalate, didecyl phthalate, additionally contains a wetting agent capable of enhanc dilauryl phthalate, and butylbenzyl phthalate. ing the spreadability of the aqueous phase. 5. The agent of claim 1, wherein said plasticizer is 20. The agent of claim 19, wherein said wetting agent selected from the group consisting of dioctyl adipate, is a polyhydric alcohol. butylglycol adipate, dioctyl azelate, dibutyl sebacate, 55 21. The agent of claim 1, wherein said aqueous phase di(2-ethylhexyl)sebacate, and dioctyl sebacate. additionally contains a water soluble salt. 6. The agent of claim 5, wherein said plasticizer is 22. The agent of claim 21, wherein said water soluble selected from the group consisting of dioctyl adipate, salt is an alkali metal salt or an ammonium salt. dibutyl sebacate, and dioctyl azelate. 23. In a gumming process which comprises coating a 7. The agent of claim 1, wherein said oil phase addi protective solution on a lithographic printing plate con tionally contains a lipophilic substance. sisting of a non-image area which retains water and 8. The agent of claim 7, wherein said lipophilic sub repels a greasy printing ink, and an image-area which stance is selected from the group consisting of a novolak repels water and accepts said greasy printing ink, phenolic resin, a xylene resin, a resin prepared by con wherein said protective solution comprises an oil phase densing phenol and mesitylene with formaldehyde; 65 comprising an organic solvent which dissolves a surfac polyhydroxystyrene; brominated polyhydroxystyrene, tant and an aqueous phase having dissolved therein a cashew resin; partially esterified styrene maleic anhy hydrophilic high molecular weight compound, the im dride copolymer; melamine resin; alkyd resin; polyester provement wherein the said organic solvent comprises 4,253,999 S 5 a plasticizer having a solidifying point of 15 C. of less, alkyl ether, polyoxyethylene alkylphenyl ether, a dialk which is present in an amount of from about 0.1 to about ylsulfosuccinate ester, alkyl phosphate ester and poly 10 wt.% based on the total amount of said agent. oxyethylene alkylamine salt. 24. The process of claim 23, wherein said lithographic 38. The agent of claim 26, wherein said surfactant is printing plate is prepared from a presensitized plate. present in an amount of about 0.5 to 10 wt.% based on 25. The agent of claim , wherein said surfactant is the weight of said agent. - present in an amount from 0.5 to 5 wt.% based on the 39. The agent of claim 26, wherein said hydrophilic total weight of the agent. high molecular weight compound is selected from the 26. In an agent for protecting the surface of a litho group consisting of dextrin, gum arabic, an alginate, a graphic printing plate which is an emulsion comprising O water soluble cellulose, polyvinyl alcohol, polyvinyl an oil phase containing a solvent and a surfactant, and pyrrolidone, polyacrylamide, an acrylamide copoly an aqueous phase having dissolved therein a hydro mer, a vinylmethyl ether-maleic anhydride copolymer philic high molecular weight compound, the improve and a vinyl acetate-maleic anhydride copolymer. ment wherein said solvent consists of a plasticizer hav 40. The agent of claim 39, wherein said hydrophilic ing a solidifying point of 15 C. or less which is present 15 high molecular weight compound is selected from the in an amount of from about 0.1 to about 10 wt.% based group consisting of gum arabic, dextrin, polyvinyl pyr on the total amount of said agent. rolidone, carboxymethyl cellulose and polyvinyl alco 27. The agent of claim 26, wherein said plasticizer hol. boils at a temperature at least about 200 C. at atmo 45. The agent of claim 40, wherein said hydrophilic spheric pressure. 20 high molecular weight compound is gum arabic. 28. The agent of claim 26, wherein said plasticizer is 42. The agent of claim 39, wherein said hydrophilic selected from the group consisting of phthalic acid high molecular weight compound is a combination of diesters, aliphatic esters of dibasic acids, epoxidized gun arabic and dextrin. triglycerides, phosphate esters, and benzoic esters. 43. The agent of claim 26, wherein said hydrophilic 29. The agent of claim 26, wherein said plasticizer is 25 high molecular weight compound is present in an selected from the group consisting of dibutyl phthalate, amount of about 5 to 40 wt.%. diheptyl phthalate, di-n-octyl phthalate, di(2-ethylhex 44. The agent of claim 26, wherein said aqueous phase yl)-phthalate, dinonyl phthalate, didecyl phthalate, additionally contains a wetting agent capable of enhanc dilauryl phthtalate, and butylbenzyl phthalate. ing the spreadability of the aqueous phase. 30. The agent of claim 26, wherein said plasticizer is 30 45. The agent of claim 44, wherein said wetting agent selected from the group consisting of dioctyl adipate, is a polyhydric alcohol. butylglycol adipate, dioctyl azelate, dibutyl sebacate, 46. The agent of claim 26, wherein said aqueous phase di(2-ethylhexyl)sebacate, and dioctyl sebacate. additionally contains a water soluble salt. 31. The agent of claim 30, wherein said plasticizer is 47. The agent of claim 46, wherein said water soluble selected from the group consisting of dioctyl adipate, 35 salt is an alkali metal salt or an ammonium salt. dibutyl sebacate, and dioctyl azelate. 48. The agent of claim 26, wherein said surfactant is 32. The agent of claim 26, wherein said oil phase present in an amount of from 0.5 to 5 wt.% based on the additionally contains a lipophilic substance. total weight of the agent. 33. The agent of claim 32, wherein said lipophilic 49. The process of claim 23, wherein said piasticizer substance is selected from the group consisting of a boils at a temperature at least about 200 C. at atmo novolak phenolic resin, a xylene resin, a resin prepared spheric pressure. by condensing phenol and mesitylene with formalde 50. The process of claim 23, wherein said plasticizer is hyde; polyhydroxystyrene; brominated polyhydroxys selected from the group consisting of phthalic acid tyrene, cashew resin; partially esterified styrene maleic diesters, aliphatic esters of dibasic acids, epoxidized anhydride copolymer; melamine resin; alkyd resin; 45 triglycerides, phosphate esters, and benzoic esters. polyester resin; epoxy resin; rosin or modified rosin; and 51. The process of claim 23, wherein said plasticizer is a petroleum resin. selected from the group consisting of dibutyl phthalate, 34. The agent of claim 32, wherein said surfactant is diheptyl phthalate, di-n-octyl phthalate, di(2-ethylhex at least one of a nonionic surfactant, an anionic surfac yl)-phthalate, dinonyl phthalate, didecyl phthalate, tant and a cationic surfactant. 50 dilauryl phthtalate, and butylbenzyl phthalate. 35. The agent of claim 26, wherein said surfactant is 52. The process of claim 23, wherein said plasticizer is at least one of a nonionic surfactant, an anionic surfac selected from the group consisting of dioctyl adipate, tant and a cationic surfactant. butylglycol adipate, dioctyl azelate, dibutyl sebacate, 36. The agent of claim 35, wherein said surfactant is di(2-ethylhexyl)sebacate, and dioctyl sebacate. selected from the group consisting of polyoxyethylene 55 53. The process of claim 52, wherein said piasticizer is alkyl ether, polyoxyethylene alkylphenyl ether, a poly selected from the group consisting of dioctyi adipate, oxyethylene ester of an aliphatic acid, a sorbitan ester of dibutyl sebacate, and dioctyl azelate. an aliphatic acid, a polyoxyethylene sorbitan ester of an 54. The process of claim 23, wherein said oil phase aliphatic acid, a glycerin ester of an aliphatic acid, an additionally contains a lipophilic substance. aliphatic acid salt, an alkyl sulfate ester, an alkylben 55. The process of claim 54, wherein said lipophilic zenesulfonate, an alkylnaphthylenesulfonate, a dialkyl substance is selected from the group consisting of a sulfosuccinate ester, an alkylphosphate ester, a conden novolak phenolic resin, a xylene resin, a resin prepared sate of naphthalene sulfonic acid with formalin, a poly by condensing phenol and mesitylene with formalde oxyethylene alkylsulfate ester, a quaternary ammonium hyde; polyhydroxystyrene; brominated polyhydroxys salt, an alkylamine salt, and a polyoxyethylene alkyla 65 tyrene, cashew resin; partially esterified styrene maleic mine salt. anhydride copolymer; melamine resin; alkyd resin; 37. The agent of claim 36, wherein said surfactant is polyester resin; epoxy resin; rosin or modified rosin; and selected from the group consisting of polyoxyethylene a petroleum resin. 4,253,999 17 18 56. The process of claim 54, wherein said surfactant is 62. The process of claim 61, wherein said hydrophilic at least one of a nonionic surfactant, an anionic surfac high molecular weight compound is selected from the tant and a cationic surfactant, group consisting of gum arabic, dextrin, polyvinyl pyr 57. The process of claim 23, wherein said surfactantis rolidone, carboxymethyl cellulose and polyvinyl alco at least one of a nonionic surfactant, an anionic surfac 5 hol. tant and a cationic surfactant. 63. The process of claim 62, wherein said hydrophilic 58. The process of claim 57, wherein said surfactant is high molecular weight compound is gum arabic. selected from the group consisting of polyoxyethylene 64. The process of claim 61, wherein said hydrophilic alkyl ether, polyoxyethylene alkylphenyl ether, a poly high molecular weight compound is a combination of oxyethylene ester of an aliphatic acid, a sorbitan ester of 10 gum arabic and dextrin, an aliphatic acid, a polyoxyethylene sorbitan ester of an 65. The process of claim 23, wherein said hydrophilic aliphatic acid, a glycerin ester of an aliphatic acid, an high molecular weight compound is present in an aliphatic acid salt, an alkyl sulfate ester, an alkylben amount of about 5 to 40 wt.%. zenesulfonate, an alkylnaphthylenesulfonate, a dialkyl 66. The process of claim 23, wherein said aqueous sulfosuccinate ester, an alkylphosphate ester, a conden 15 phase additionally contains a wetting agent capable of sate of naphthalene sulfonic acid with formalin, a poly enhancing the spreadability of the aqueous phase. oxyethylene alkyl sulfate ester, a quaternary ammonium 67. The process of claim 66, wherein said wetting salt, an alkylamine salt, and a polyoxyethylene alkyla agent is a polyhydric alcohol. mine salt. 68. The process of claim 23, wherein said aqueous 59. The process of claim 58, wherein said surfactant is 20 phase additionally contains a water soluble salt. selected from the group consisting of polyoxyethylene 69. The process of claim 68, wherein said water solu alkyl ether, polyoxyethylene alkylphenyl ether, a dialk ble salt is an alkali metal salt or an ammonium salt. ylsulfosuccinate ester, alkyl phosphate ester and poly 70. The process of claim 23, wherein said surfactant is oxyethylene alkylamine salt. present in an amount of from 0.5 to 5 wt.% based on the 60. The process of claim 23, wherein said surfactant is 25 total weight of the agent. present in an amount of about 0.5 to 10 wt.% based on 71. Th process of claim 23, wherein said organic the weight of said agent. solvent consists of a plasticizer having a solidifying 61. The process of claim 23, wherein said hydrophilic point of 15° C. or less. high molecular weight compound is selected from the 72. The agent of claim 1, wherein said oil phase con group consisting of dextrin, gum arabic, an alginate, a 30 sists essentially of said surfactant and said plasticizer. water soluble cellulose, polyvinyl alcohol, polyvinyl 73. The process of claim 23, wherein said oil phase pyrrolidone, polyacrylamide, an acrylamide copoly consists essentially of said surfactant and said plasti mer, a vinylmethyl ether-maleic anhydride copolymer cizer. and a vinyl acetate-maleic anhydride copolymer. t h 35

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