FI59362C - SENSIBILIZER ARK FOER ETT TRYCKKAENSLIGT KOPIERINGSSYSTEM OCH FOERFARANDE FOER FRAMSTAELLNING AV DETSAMMA - Google Patents

Description

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Japan-Japan (JP) 97U30 / 72 (71) Sanko Chemical Company Ltd., 88,3-chome, Tooricho, Kurume-shi, Fukuoka-ken, Kanzaki Paper Manufacturing Company Ltd., 9 ~ 8, U-chome, Ginza , Chuo-ku,

Tokyo, Japan-Japan (JP) (72) Toranosuke Saito, Kobe-shi, Hyogo-ken, Jujiro Kohno, Takatsuki-shi, 0saka-fu, Daiichiro Tanaka, Kumamoto-ken, Shinichi Oda, Amagasaki-shi, Hyogo-ken The present invention relates to a photosensitive sheet and a method for the production of a light-sensitive sheet and a method for the production of a light-sensitive sheet and a method for producing a light-sensitive sheet and a method for producing a light-sensitive sheet and a method for its production. which sheet is intended for use in a pressure-sensitive copying system, and in particular a photosensitive sheet having a coating comprising an acceptor capable of forming a color when in contact with a colorless, color-generating compound.

Generally, a chemical reaction between a colorless electron-donating compound and an electron-receiving solid acid is used in a pressure-sensitive copying system.

Until now, different types of pressure-sensitive imaging sheets have been known. U.S. Patent No. 2,730 U56, for example, discloses a transfer-type pressure-sensitive replicating sheet characterized in that the top or top sheet is coated with a layer containing microcapsules containing an electron donating compound dissolved in an oily solvent (hereinafter referred to as a "color former") and the underlying sheet is made photosensitive by a surface layer containing an electron-receiving solid acid (hereinafter referred to as an "acceptor"). The color former moves to the sheet below when the microcapsules 2 59362 break and forms a visible color image. If more copies are desired, a spacer sheet with microcapsules on one side and an acceptor on the other side is inserted between the upper and lower sheets.

German patent no. 1,275 · 550 explains a pressure-sensitive reproduction plate »characterized in that a solution in liquid solvent containing copy-poisoning components is applied to the surface and / or inside of the backing sheet and said solvent is present isolated from at least one of the recording-leaking components by pressure-disintegrating time capsules.

Examples of color formers include leuko-type dye-generating compounds such as crystal violet lactone »benzoyl leukomethylene blue, nalachite green lactone, rhodaine B lactone, fluorone derivatives and spiropyrans.

Known acceptors include acid clay, activated clay, attapul-glitt coalin, and other inorganic solid acids, but the downside is that the evolved image is blurred by moisture and sunlight. A sensitive sheet coated with an organic solid acid such as phenolic resin is also used. However, such a plate tends to turn yellow in sunlight and the developed color image becomes less frequent or disappears over time due to heat and humidity.

Other examples of the organic solid acid are aromatic carboxylic acids (U.S. Pat. Bo. 5,022 * 557 and 5 * 446,207) and polyvalent metal salts of aromatic carboxylic acids (DT-OS 2,152,765). * For example, benzoic acid, O-nitrobenzoic acid, O-chlorobenzoic acid, 4-methyl-5-nitrobenzoic acid, p-isopropylbenzoic acid, p-tertiary ributylbenzoic acid, 5-1 tertiary butyl acid to give cyanic acid, 5-cyclohexylsalicylic acid, 5-acetyl-5-isoamylsalicylic acid, 5-acetyl-5-isoamylsalicylic acid, , 1-hydroxy-2-naphthoic acid, 5 * 5 methylene disalicylic acid and other similar aromatic carboxylic acids, as well as metals such as magnesium, calcium, zinc, cadmium, aluminum, gallium, tin, lead, chromium, molybdenum, cobalt and nickel salts with the above carboxylic acids. Such aromatic carboxylic acids and their polyvalent metal salts are excellent in resistance to sunlight compared to phenolic resins.

Some carboxylic acids and their polyvalent metal salts have annoying properties and therefore lose a sheet rendered photosensitive by a coating containing such acceptors over time as its color-forming ability. Since said acceptors are soluble in water and thus spread on the plate under the influence of high humidity or water, the color-forming ability of the surface of the plate is lost. These downsides tend to increase as the molecular weight of the carboxylic acid decreases. The reason why salicylic acid was mentioned earlier but not used is that in addition to the above-mentioned shadows, the weak point is the lower color density. Some aromatic carboxylic acids and their polyvalent metal salts show better resistance to heat and moisture as the molecular weight increases and their color-forming properties remain relatively stable at normal temperature and humidity. However, there is room for improvement in the properties required in practice for pressure-sensitive copy papers. It is unavoidable that copy papers are stored in humid conditions or directly exposed to water. For example, it often happens that rainwater or water spilled from glass gets on the sheet. In some cases, if a letter or image is offset printed on a pressure-sensitive sheet of paper above or below, the surface layer source solution is transferred to the surface of the sheet that is covered by the acceptor. If the organic acid substance is not sufficiently resistant to high humidity or water under such conditions, the color-forming ability of the photosensitive sheet is significantly reduced, or if the photosensitive sheet is in contact with a sheet having an encapsulated color former, the organic acid substance comes into contact with the color former. -wanted color called "stained".

Accordingly, the surface layer containing the acceptor must be sufficiently resistant to moisture or water in order to maintain the color-forming ability and the formed image and to avoid "staining".

On the other hand, a coating compound containing aromatic carboxylic acids and their polyvalent metal salts must be monitored very carefully during the storage and coating phase because it is extremely unstable at high temperatures. In particular, during the coating step, the coating compound is subjected to mechanical shear stress associated with an increase in temperature. Therefore, the coating compound will not be able to form a uniform layer on the base sheet if the mechanical and thermal stability are not good enough and in the worst case the coating must be stopped. The simplest and therefore most economical procedure is to perform the coating with a device mounted on a paper machine. In this case, since the coating compound is coated on the base sheet preheated, the requirements for mechanical and thermal stability are higher.

Therefore, the present invention relates to a photosensitive sheet for a pressure-sensitive copying system and to a method for manufacturing the same, which sheet has excellent heat, light and especially strong moisture and water resistance and is capable of maintaining its color formation stability.

The sensitized sheet according to the invention is mainly characterized in that it is made photosensitive by means of a coating in order to produce color upon contact with the color-generating agent, and in that said coating 11 59362 contains a finely divided mixture comprising (a) at least one acidic organic substance is selected from the group consisting of aromatic carboxylic acids and their salts with polyvalent metals, and (b) at least one high molecular weight compound.

The process according to the invention, in turn, is mainly characterized in that the support layer is coated with a suspension of a finely divided mixture comprising (a) at least one organic acidic substance selected from the group consisting of aromatic carboxylic acids and their polyvalent metal salts and (b) at least one organic macromolecular compound.

The mixture of organic acid and organic high molecular weight compound can be mechanically ground, for example in a ball mill, to a fine dust having a particle size of a few microns. This provides a coating layer in which the fine dust is evenly distributed. The organic acid used in the invention is selected from the group consisting of aromatic carboxylic acids and their polyvalent metal salts. The compounds are described by way of the non-limiting examples below, but of course other aromatic carboxylic acids and their polyvalent metal salts which are capable of forming colors upon contact with the color former may also be used.

One aromatic carboxylic acid used is shown in formula I.

COOH

f T (i) “(1" R 2 E 3 wherein R 1, R 2, R 1, R 2 and R 5 represent hydrogen, halogen or hydroxyl, amino, carbon, carbomyl, alkyl, cycloalkyl, alkoxyl) , an aryl, aryloxyl, aralkyl or alkylaryl group and any of the adjacent groups R 1, R 2 may be added to the ring with the carbon atoms to which they are attached The compounds of formula I in which or is a hydroxyl group are particularly important in embodiments of the invention. mentioned in detail.

Examples of carboxylic acids of formula I in which and R 1. are not a hydroxyl group, include benzoic acid, o-toluic acid, m-toluic acid, pt art-butylbenzoic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, tetrachlorobenzoic acid, phthalic acid, phthalic acid, terophthalic acid, terophthalic acid, terophthalic acid , anthranilic acid, phthalic acid monoanide, phthalic acid aonoanilide, 3-tertiary butyl-4-hydroxybenzoic acid, 3- (α-methylethylbenzyl) -4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, tribasic acid, triacetic acid, pyroacetic acid, pyroacetic acid β-naphthoic acid, tetrachlorophthalic acid and 2,2-dlcarboxydiphenyl. Formula II defines open carboxylic acids of formula I wherein or E. is hydroxyl group 5

COOH

** vSr "II (n) * e B7 and wherein E6 - correspond to the formula I B1 - Such carboxylic acids include, for example, salicylic acid» o-creothic acid, p-cresotinic acid, 3-ethylsalicylic acid, 4-ethylsalicylic acid, 3-isopropylsalicylic acid »5- tertiary butylsalicylic acid »3-cyclohexylalicylic acid» 5-cyclohexylsalicylic acid, 3-phenylsalicylic acid, 5-phenylsalicylic acid, 3-benzylsalicylic acid, 5-benzylsalicylic acid 5- («- methylbenzyl) n-salicylic acid - (e-dimethylbenzyl) salicylic acid, 5-chlorosalicylic acid »5-butoxysalicylic acid and 5-otoxysalicylic acid.

Compounds of formula II »in which Bg and Rg are halogens» alkyls »cycloalkyls» aryls »aralkyls or alkylaryls» can be easily derived from commercial phenols »alkylphenols» arylphenols or halogenated phenols. Examples of such aromatic carboxylic acids include, but are not limited to, 3 ', 5-dichlorosalicylic acid, 3-chloro-5-tertiary butylsalicylic acid, 3-chloro-5-tertiary amylsalicylic acid, 3-chloro-5-tertiary octylsalicylic acid, -dimethylbenzyl) salicylic acid »3,5-dimethylsalicylic acid, 3-methyl-5-tert-butylsalicylic acid» 3-methyl-5-cyclohexylsalicylic acid, 3-methyl-5-tertiary octylsalicylic acid 5-methyl-octyl -benzyl) salicylic acid, 3-methyl-5-nonylsalicylic acid, 3-methyl-5- (α, α-dimethyl-benzyl) salicylic acid, 3,5-diisopropylsalicylic acid, 3,5-di-secondary butylsalicylic acid, 3-tertiary butyl-6-chlorosalicylic acid, 3-tertiary butyl 5-methylsalicylic acid, 3-tertiary butyl-5-ethylealicylic acid, 3,5-di-tertiary butylallylacylic acid, 6 59362 3-tertiary butyl-5-ethyl , 3-tertiary butyl-5-phenylsalicylic acid, 3-tertiary butyl over-5- (4'-tertiary-butyl-phenyl) -salicylic acid, 3-tertiary-allyl-5-chloro-salicylic acid, 3-tertiary-allyl-5-ethyl-allyl-acid, 3-tertiary-allyl-5-ethyl-salicylic acid, 3,5- di-tertiary allyl allyl acid, 3-tertiary allyl-5-cyclohexyl-aleacylic acid, 3-tertiary allyl-5-phenylalealyl acid, 3-tertiary allyl-5- (4'-tertiary allyl-3-yl) acylphenyl) allylphenyl -Cyclohexyl-5- * ethylsalicylic acid, 3-cyclohexyl-5-ethylalealic acid, 3,5-diethyllohexylalealyl acid, 3-cyclohexyl-5-phenylalylic acid, 3-cyclohexyl-5- (4'-cyclohexyl) hexohexyl 3-Phenyl-5-chloroaleacetic acid, 3-phenyl-5-leopropylsalicylic acid, 3-Ϊ9ηγγ1i-5-tert-butyl-allylic acid, 3-phenyl-5-tert-allyl-allyl-acid, 3-tert-butyl-3-yl-ethyl tert-amylallylacetic acid, 3-phenyl-5-cyclohexyl-allylic acid, 3-phenyl-5-benzylsalicylic acid, 3-phenyl over-5-tertiary octylalealic acid, 3'-phenyl-5- (n-methylbenzyl) salicylic acid, 3-phenyl-5-nonylalealylic acid, 3-phenyl-5- (α, α-dimethylbenzyl) salicylic acid, 3-benzyl-5-chloroacetic acid 3-Benzyl-5-ethyl-allyl-acid, 3-benzyl-5-ethyl-salicylic acid, 3-benzyl-5-cyclohexyl-salieylic acid, 3-benzyl-5-phenyl-salicylic acid, 3,5-dibenzyl-salicylic acid, 3-benzyl-3- tertiary salicylic acid, 3-benzyl-5-nonylsalicylic acid, 3-benzyl-5- (s, α-dimethylbenzyl) salicylic acid, 3-tertiary octyl-5-chlorosalicylic acid, 3-tertiary octyl-5- »ethylsalicylic acid, Octyl-5-otylsalicylic acid, 3-tertiary octyl-5-cyclohexylsalicylic acid, 3-tertiary octyl-5-phenylsalicylic acid, 3,5-di-tertiary octyl alicylic acid 3- (α-ethylbenzyl) -5-chloroealyl - (α-ethylbenz8yl) -5-methylsalicylic acid, 3 - («- ethylbenzyl) -5-ethylealicylic acid, 3 - (“ - ethylbenzyl) -5-cyclohexylalealyl acid, 3- (aa) Ethylbenzyl) -5-phenylalealyl acid, 3,5-di- (α-ethylbenzyl) salicylic acid, 3- (α-acetylbenzyl) -5 - ((, α-diaethylbenzyl) salicylic acid, 3- (α-ethylbenzyl) -5- (4 '- (((- astylbenzyl) phenyl) salicylic acid, 3-nonyl-5-chlorosalicylic acid, 3-nonyl-5-ethylsalicylic acid, 3-nonyl-5-ethylsalicylic acid, 3-nonyl-5-phenylsalicylic acid, 3,5-di -Nonylalealyl acid, 3- (α, α-dimethylbenzyl) -5-chlorazalylic acid, 3- (α, α-diaethylbenzyl) -5-methylsalicylic acid, 3- (O, α-diaethylbenzyl) -5-ethylsalicylic acid, 3- (e, α-diaethylbenzyl) -5-cyclohexylsalicylic acid, 3- (α, α-diaethylbenzyl) -5-phenylallylic acid, 3- (α, α-diaethylbenzyl) -5- (n-aotylbenzyl) allylic acid, 3,5-di- . N- («» «- dimethylbenzylphenyl} -5 - («, «- dimethylbenzyl) salicylic acid.

The open aromatic carboxylic acids of formula II can be derived from, for example, metacresol, metapropylphenol, metaphenylphenol, 2,3-xylene, 2,5-xylenol, 3,4-xylenol and 3 → 5-xylenol. Examples of such acids are 3,4-dimethylsalicylic acid, 4,5-dimethylsalicylic acid, 4,6-dimethylsalicylic acid, 4-ethyl-5-isopropylsalicylic acid, 4-methyl-5-secondary tert-butylsalicylic acid, 4- * ethyl tert-butylsalicylic acid, 4-ethyl-5-tertiary amylsalicylic acid, 4-methyl-5-cyclohexylsalicylic acid, 4- [5-style-5-benzylsalicylic acid, 4-methyl-5-tertiary octylsalicylic acid, 4-methyl - (α-methylbenzyl) salicylic acid, 4-O-ethyl-5-nonylsalicylic acid, 4-methyl-5- (α-methylbenzyl) salicylic acid, 3,6-dimethylsilicylic acid, 3-tert-butyl-6-methylsalicylic acid, 3-tertiary amyl-6-methylsalicylic acid, 3-cyclohexyl-6-methylsalicylic acid, 3-tertiary octyl-6-methylsalicylic acid, (α-ethylbenzyl) -6-ethylsalicylic acid, 3,6-diisopropylsalicylic acid , 3-tert-butyl-6-isopropylsalicylic acid, 3-tertiary-octyl-6-isopropylsalicylic acid, 3 - (N, α-dimethylbenzyl) -6-isopropyl isalicylic acid, 3-tert-butyl-6-phenylsalicylic acid, 3-tertiary-amyl-6-phenyl-salicylic acid, 3-cyclohexyl-6-phenyl-salicylic acid, 3-tert-octyl-6-phenyl-salicylic acid 6-phenyl-azalyl-3- phenylsalicylic acid or 3- (α, α-dimethylbenzyl) -6-phenylsalicylic acid.

Carboxylic acids of the formula II in which at least one of the groups Rg to R1 is a hydroxyl group are represented by the formula III

COOH

(III) (*) n «®>.

Wherein R is an alkyl, cycloalkyl or aralalkyl group. Examples of these carboxylic acids include 3-hydroxysalicylic acid, 3-hydroxy-5-tertiary butylsalicylic acid, 3-hydroxy-5-tertiary amylsalicylic acid, 3-hydroxy-5-cyclohexylsalicylic acid, 3-hydroxyisocryloxy-5-terroxy-5-hydroxy 5- (o-Methylbenzyl) saicylic acid, 3-hydroxy-5- (dimethylbenzyl) salicylic acid, 3-hydroxy-4- [6-dicyclohexylsalicylic acid, 4-hydroxysalicylic acid, 4-hydroxy-5-tert-butylsalicylic acid] 4-Hydroxy-5-tert-allyl-allylic acid, 4-hydroxy-5-cyclohexyl-salicylic acid, 4-hydroxy-5-tert-octyl-salicylic acid, 4-hydroxy-5- (α-ethyl-benzyl) -salicylic acid, 4-hydroxy-5- ( α, α-diaethylbenzyl-salicylic acid, 3,5-diisopropyl-6-hydroxysalicylic acid, 3,5-di-tert-butyl-6-hydroxy-salicylic acid, 3,5-di-tert-allyl-6- hydroxyalcylic acid, 3,5-di-cyclohexyl-6-hydroxyalkylleyl acid, 3,5-di (α-methyl-benzyl) -6-hydroxysalicylic acid, 3,5-di (α, α-diaethylbenzyl) ) -6-hydrocalalicylic acid, 5-hydroxysalicylic acid, 4-tert-butyl-5-hydro-salicylic acid, 4-tert-allyl-5-hydroxysalicylic acid, 4-cyclohexyl-5-hydroxysalicylic acid, 4- (α-methyl) benzyl 5-Hydroxysalicylic acid, 3,6-diisopropyl-5-hydroxyalealyl acid, 3,6-dicyclohexyl-5-hydroxyalalylic acid or 3,6-di (α-methylbenzyl) -5'-hydroxyealicylic acid.

In the event that one of the adjacent rhythms anodizes together with the carbon atom to which they are attached, naphthalene derivatives are formed. They are represented by formulas IV, V and VI

H'8 COOH

't r jT x <w> *' 5 * '2 *' · ** 4

R »JL X COOH

I 1 (7) H’5 * ’l fe?’> “VVV ** I II JL <ti> *’ i e® **

E · .0H

5 v * s 59362 where H * lt H'g, H'y R '^, R' ^ t R * g, Η'γ and R'e are hydrogen, halogen or hydroxyl, alkyl, cycloalkyl - or an aralkyl group. Examples of such naphthalene rings are 1-hydroxy-2-carboxynaphthalene, 1-hydroxy-2-carboxy-4-leopropylnaphthalene, 1-hydroxy-2-carboxy-4-cyclohexylnaphthalene, 1-hydroxy-2-carboxy-4-benzylnaphthalene , 1-hydroxy-2-carboxy-4- (α-methylbenzyl) naphthalene, 1-hydroxy-2-carboxy-7-io-propylnaphthalene, 1-hydroxy-2-carboxy-7-tert-butylnaphthalene, 1-hydroxy- 2-Carboxy-7-tert-butylnaphthalene, 1-Hydroxy-2-carboxy-7'-cyclohexylnaphthalene, 1-hydroxy-2-carboxy-7-tertiary octylnaphthalone, 1-hydroxy-2-carboxy-7- (a -ethylbenzyl) naphthalene, 1-hydroxy-2-carboxy-7- (α, α-diaethylbenzyl) naphthalene, 1-hydroxy-2-carboxy-4 * 7-diopropylnaphthalene, 1-hydroxy-2-carboxy- 4,7-di-tertiary-butylnaphthalene, 1-hydroxy-2-carboxy-4,7-di-tert-butylnaphthalene, 1-hydroxy-2-carboxy-4,7-dicyclohexylnaphthalene, 1-hydroxy-2-carboxy- 4,7-Dibenzylnaphthalene, 1-hydroxy-2-carboxy-4,7-di-tertiary octylnaphthalene, 1-hyd roxy-2-carboxy-4,7-di (n-methylbenzyl) naphthalene, 1-hydroxy-2-carboxy-4,7-di (aza-diethylbenzyl) naphthalene, 1-carboxy-2-hydroxynaphthalene, 1-carboxylic acid 2-hydroxy-3,6,8-tri-tert-botylnaphthalene, 2-hydroxy-3-carboxynaphthalene, 2-hydroxy-3-carboxy-6,8-di-tert-butylnaphthalene, 2-hydroxy-3- carboxy-6,8-di-tert-butylnaphthalene, 2-hydroxy-3-carboxy-6,8-dicyclohexylnaphthalene, 2-hydroxy-3-carboxy-6,8-tertiary octyl-1-naphthalene, 2-hydroxy -3-carboxyl-6,8-di (α-ethylbenzyl) naphthalene and 2-hydroxy-3-carboxy-6,8-di (α, α-diaethylbenzyl) naphthalene *

Aromatic carboxylic acids derived from the precursor of bisphenol Asta, 4,4-dihydroxyecyclohexyldibiphenyl, 4,4-dihydroxynethylenebiphenyl and 2,2-dihydroxydiphenylocyclylacidyl 5- (3'-Carboxy-4'-hydroxybenzyl) salicylic acid (ethylene-bis-salicylic acid), 3-tert-butyl-3- (3 ', 5'-di-tert-butyl-4-hydroxybenzyl) salicylic acid, 3 “(Α, β-diaothylbenzyl) -5- [3 *» 5'-di (e, α-diaethylbenzyl) -4-hydroxybenzyl] salicylic acid, 3-tert-butyl-5- («, ct-dimethyl-3 *, 5'-di-tert-butyl-4'-hydroxy-benzyl) salicylic acid, 5 - ((, «- - dimethyl-3-carboxy-4'-hydroxybenzyl) salicylic acid, 5 - (* * * - dimethyl-4'- hydroxybenzyl) salicylic acid, 3- (2'-hydroxyphenoxy) salicylic acid, 3- (2'-hydroxy-3'-carboxyphenoxy) salicylic acid, 3 '(2'-hydroxy-3-carboxy-5-tert-butylphenoxy) -5-tertiary- butylsalicylic acid, 3— (2 * -hydroxy-3 ', 5'-di-tert-butylphenoxy) -5-tert-butylsalicylic acid, 3- (2'-hydroxy-3'-carboxy-5 * - ((, (, - - dimethylbenzyl) phenoxy)] -3 - ((,, «- dimethylbenzyl) salicylic acid, 3- (2 * - - 10 59362 hydroxy-3 ', 5 * -di («, α-dimethylbenzyl) phenoxy -5- (α »« - dimethylbenzyl) salicylic acid and 3- (2'-Hydroxy-3 ', 5'-dicyclohexylphenoche-5-cyclohexylsalicylic acid *

In addition, a large number of formula II-opened carboxylic acids have been listed, which are difficult to chew on the Keaian nomenclature. It is shown esiaerkiksi sekapolyaerisatiotuotteita formaldehyde, salicylic acid or a ring-substituted salicylic acids and phenol »salicylic acid or propylene polymer or isobutyleenipolyaeerin ring-substituted salicylic acid derivatives, salicylic acid or polycondensate benzyl ring-substituted salicylic acid derivative" styreenipolyneerien ring-substituted salicylic acid or salicylic acid derivative "of salicylic acid or a metyylisty reenipolyneerien-salicylic acid derivative" or salicylic acid in the context of the above-mentioned proprietary salts of salicylic acid condensates of aldehydes or acetone, salicylic acid or ketones of nuclear salicylic acid and compounds of salicylic acid or unsaturated bonds, such as "aromatic carboxylic acids", mentioned, condensates lt and polymers and their polyvalent salts.

All of the above carboxylic acids can form salts with polyvalent metals.

The polyvalent metals associated with the acceptors of this invention include all salt-forming metals except lithium, sodium, potassium, rubidium, sesame, and francium. Useful polyvalent metals include magnesium, aluminum, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, strontium, yttrium, zirconium, niobium, molybdenum, silver, cadmium, indium tin, antinani, barium, tungsten, mercury, lead and bismuth.

Furthermore, the most suitable metals in practice are magnesium, aluminum, calcium, titanium, manganese, zinc and tin.

Among the above-mentioned aromatic carboxylic acids and their polyvalent metal salts, preference is given to compounds having at least one hydroxyl group in the benzene ring, especially with the hydroxyl group in an ortho position to the carbon group. In view of the heat and test resistance as well as the compatibility with the organic macromolecular compound, aromatic carboxylic acid and its polyvalent net salt with a high molecular weight of 11 5 9 3 6 2 are preferred, which means that it has at least 10 phosphorus over 17 carbon atoms in total. Excellent color formation properties, excellent water resistance and compatibility with organic high molecular weight compounds »are especially present for compounds of formulas II, III, IT, T and TI in which the choleacarboxylic group aceaa has been replaced by isopropyl, secondary spherylhexyl, tertiary butyl, -, phenyl, substituted phenyl, benzyl, n-methyl-benzyl, α-diaethylbenzyl, tertiary octyl, nonyl and au with groups having at least 3 carbon atoms. Compounds of formulas II, III, IT, T and TI with a total of at least 17 carbon atoms are preferred.

Ionic metal salts of aromatic carboxylic acids are obtained by reacting aromatic carboxylic acids with oxides, hydroxides, carbonates and silicates of ionic metals, although they can be readily prepared with an alkali metal salt of an aromatic carboxylic acid and an alkali metal ethanol. In this case, the aromatic carboxylic acid and the water-soluble ionic acid salt can also be used alone or in a mixture of two or more substances. Ionic metal salts of aromatic carboxylic acid are usually precipitated in the form of crystalline powders, as aforphic fine powders or as pasty liquids.

The organic high molecular weight compound used in the invention should be difficult to flow in the normal temperature and should be selected from among the compounds having a molecular weight of more than 400 in the downstream furnace. The following are examples of organic high molecular weight compounds! polybutadiene, butadieenisekapolyaeerit such as butadiene-isopreenlsekapolyaeeri and butadlee-ni styreenisekapolyaeeri, syklopentadieenipolyaeerlt, syklopentadieeniseka-polyaeerit, polystyrenes, styreenisekapolyaeerit, a aetyylistyreenipoly-aeerit, α-aetyylistyreenisekapolyaeerit, polyvinyl chlorides, vinyyliklorldl-sekapolyaeerit, vinylideenikloridisekapolyaeerit, polykloropeeni (Heopreeni) akryyliesteripolyaeerit, akryyliesterlsekapolyaeerit , akryylihapposekapoly-aeerit, aetakryyliesteripolyaeerit, aetakryyllesterisekapolyaeerit, aetakryy-lihapposekapolyaeerit, vinyyliasetaattisekapolyaeerity vinyyliasetaattiseka-polyaeerit as etyleenivinyyllasetaattisekapolyaeerit, acrylonitrile-sekapolyaeerit, akryyliaaidisekapolyaeerit, alkyylialkohollsekapolyaeerit, bentsyyliklorldipolykondensaatlotuotteet, bentsyylikloridlsekapolykondensaa-adducts, aetaksyleeni-foraaldehydikondensaatit, diphenyl-fornaldehydi condensates, diphenyl-aetaksyleenirfornaldehydisekapolykondensaatiotuottee t, i2 59 3 62 phenol-formaldehyde condensates, substituted phenol-foms. , daaaar resin. Preference is given to styrene polyols, styrene copolymers, α-methylstyrene polymers, α-methylatyrene copolymers and substituted phenol-phthalaldehyde polyesterization condensation products. The high molecular weight compounds are well compatible with various organic acid substances, so that they can be easily ground to a fine dust and their good color-forming ability is maintained.

It is desirable that the above-mentioned high molecular weight compound be selected from compounds having good compatibility with the acid substance to be added thereto. As used herein, the term "compatibility" refers to the fact that two or more chelic compounds are soluble in each other and also the case where the solubility occurs only in one because the other is crystalline.

In many cases, the compatibility of a chemical substance can be explained in relation to the polarity of the substance. Suitable compounds of the organic acid substance and the high o-alkyl compound can be defined in this invention by taking this aspect into account. In general, the polarity of a chemical substance can be qualitatively understood in the light of the inorganophilic and organophilic equilibrium. The organophilic aromatic carboxylic acid usually increases and its polarity decreases, the number of hliatons becomes high. In the case where the number of carbon atoms in the aronate carboxylic acid is a word, the polarity of the polar radicals introduced into the molecule, such as hydroxyl, carboxyl, nitron, cyano and halogen, increases. The polarity may also vary depending on the type of radicals and the time of their position in the molecule. Different types of polyvalent metals have an effect on compatibility, which can be explained in terms of polarity. Several polyvalent metals, for example, so-called ones that tend to yield aionic metal salts with high inorganophilicity or polarity, are acetals with a relatively low atomic weight, such as magnesium, aluminum, calcium and titanium. In contrast, zinc and tin tend to form aionic metal salts with low inorganophilicity or polarity. If, on the other hand, organic high molecular weight compounds are attached, in which case polyethylene and polypropylene are considered to have the most polarity, double bonds or are replaced by halogens, benzene rings or hydroxyl, carboxyl, ether, polar, ester, and the number.

Because islets »of the same polarity are compatible or miscible · a powder mixture of a powdered acid is obtained · comprising an organic acid substance and an organic macromolecular compound · by choosing an organic eurin-molecular compound» having the word polarity as an aromatic carboxylic acid and its polyhydric metal salt.

An organic high molecular weight compound "compatible with a relatively high polar organic acid" is selected from a high polar substance having a polar radical in the molecule. However, if radicals such as -C »H» -C0- »-H-, -SO ,, -, -SO-» -8- »-PO ·» -P-, -CS- and -O- are present in large to an extent in the molecule, they inhibit the color-forming reaction of the colorant and it is therefore desirable to limit the presence of such radicals to the minimum required. The halogen and phenyl radicals do not form an obstacle to the color reaction. Hydroxyl and carboxyl radicals do not interfere with the color reactor and increase the polarity when present to a small extent.

The amount of the organic macromolecular compound in the lattice relative to the organic acid substance is not particularly limited, and the desired resistance to heat, light, and especially high humidity or water, cannot be achieved if the amount of the former is too small. It is desirable that the amount of the organic high molecular weight compound be at least 5 parts by dry weight, preferably 15 parts by weight based on 100 parts of organic acid by dry weight. There are many methods for providing a powder mixture comprising an organic acid substance and an organic high molecular weight acid substance. for example, the simplest and most preferred method involves lies in which an organic high molecular weight compound and an organic acid substance are mixed and melted simultaneously while heating, after which it is solidified by cooling and ground. The second method of the paint comprises the steps of dissolving the organic acid substance and the high molecular weight compound in an organic solvent and mixing thereto, after which the solution is dried by evaporation and triturated. Grinding can be performed by a dry method or by a wet method, e.g. with water. In this case, the presence of surfactants as well as fine and hard powders such as silicic anhydride and kaolin can be allowed to increase the grinding efficiency.

In the above-mentioned methods, preference is given to an organic high molecular weight compound having a relatively high transition point (side transition point) and a relatively low molecular weight, generally saying that the molecule of the organic high molecular weight compound has a large number of ring structures. sivunuutospiste high * The examples given are polystyrene, styrene, styrene-a-metyylistyreenisekapolymeerit, a-me-tyylistyreenipolymeerit, syklopentadieenisekapolymeerit, aliphatic unsaturated cyclic hydrocarbon, benzyl-difenyylipoly condensates, metaksyleeni-formaldehydipolykondensatiotuote, netaksy-alkylene-diphenyl-formaldehydisekapolykondensatiotuotteet, alkyl-metaksyleeni lifenol-formaldehyde mixed polycondensation products, metaxylene-diphenyloxy-di-formaldehyde mixed polycondensation products, diphenylalkylphenol mixed polycondensation products, eubstituted phenol-diphenyloxide-formaldehyde mixed polycondensation primary products, methacrylic ester polymers, acrylonitrile-styrene copolymers, nitrocellulose, ethylcellulose, polyester resins and polycarbonate resins having a molecular weight of about 600-5000.

Alternatively, a specific water-dispersed mixture is obtained by liquefying an organic acid and a high molecular weight compound by heating or adding an organic solvent and dispersing the result in water and cooling or, if necessary, removing the organic solvent.

Furthermore, there is an alternative method of mixing an organic acid substance and a polymerization initiator and regulator with a vinyl monomer capable of dissolving an organic acid substance such as styrene, α-methylstyrene, ethyl acrylate and methyl methacrylate to provide a suspension or emulsion polymerization, an organic acid substance and an organic high molecular weight compound.

In order to obtain a particular mixture, a process is further used which comprises adding an early metal or ammonium salt of aromatic carboxylic acids to an emulsion of a high molecular weight organic compound, for example a polystyrene emulsion and a styrene-butadiene copolymer emulsion, followed by heating to promote the mixing of the second polyvalent metal salt of the aromatic carboxylic acid with the eaulsified organic high molecular weight compound particles. In this way a fine mixture in the form of an aqueous emulsion or dispersion is obtained.

In many cases, according to the invention, the organic acid substance and the organic euro-molecular compound are soluble in each other and form a homogeneous phase, but although there are insoluble parts in the homogeneous phase, this does not detract from the object of the invention. The particle size of the fine powders obtained is usually kept a few microns smaller, preferably about 0.5 microns * 15 59362

In some processes, in the preparation of a special mixture «comprising an organic acid substance and an organic high molecular weight compound» the special mixture may additionally contain at least one water-insoluble substance »such as oxides» hydroxides and metal pigments and other mineral pigments and organic matter in powder form »such as starch powder pigments * When, for example, an organic acid substance is combined with a large organic molecule compound in heat, »a water-insoluble inorganic particulate substance» such as clay »kaolin» activated carbon »zinc oxide» calcium carbonate and aluminum hydroxide which solidifies and grinds on cooling. Thus, a special substrate is formed in which a mixture of an organic acid substance and an organic high molecular weight compound is absorbed into inorganic powders. The presence of inorganic or organic powders in a particular substrate causes it to have better extensibility as well as better flowability of the coating mixture. In particular, the presence of the inorganic powders mentioned below enhances the improvement of the color-forming properties of the organic acid substance as well as the sunlight resistance of the photosensitive sheet. The amount of inorganic or organic powders present is not particularly limited »as long as the nature of the organic acid substance el suffers from it. It is generally preferred to combine inorganic powders with less than 2000 dry parts by weight to 100 parts by dry weight of organic acid.

In order to improve the compatibility between the organic acid substance and the organic macromolecular compound, as well as the color-forming ability, it is preferred to additionally add an aliphatic carboxylic acid and / or a polyhydric salt thereof to the particular substrate.

Examples of the aliphatic carboxylic acid include the saturated monocarboxylic acid represented by the formula CgI monocarboxylic acid represented by aC00H »where n is an integer and a is an integer of 1, 3, 3» 7 or 9 »for example acrylic acid, crotonic acid» oleic acid, elaidic acid »linoleic acid» linolenic acid wax lactic acid, oleostearic acid, phenylacetic acid, naphthylacetic acid, naphthacetic acid, or naphthoic acid castor oleic acid or oxystearic acid, halogenated fatty acid »such as α-dichloropalitic acid and α, α-dichlorostearic acid, poly-fatty acid» such as oxalic acid, malonic acid, succinic acid, succinic acid, azalic acid, adipic acid, cork Sakonic acid, glutaconic acid, citric acid and their halogenated products, phenoxyacetic acid, copolymers of malic acid, 16 59362 polymer of unsaturated fatty acids or copolymers of unsaturated carboxylic acid and resin *

The metal salt of the above aliphatic carboxylic acids can also be used for the above purpose. Wedding compounds include salts of all metals that can form salts with the above fatty acids. The aliphatic carboxylic acid and its metal salt are preferably used in an amount of less than 100 parts by dry weight per one hundred parts by dry weight of the total amount of the organic acid substance and the organic euryl molecular compound.

The coating composition according to the invention is obtained by dispersing, if necessary, a specific mixture of an organic acid substance and an organic macromolecular compound in water or a suitable organic solvent which readily dissolves the organic acid substance and the macromolecular compound. Examples of such an organic solvent are methanol, ethanol, isopropanol, ethylene glycol and propylene glycol which can be used mixed with water. As the binder, for example starch, casein, gelatin, gum arabic, polyvinyl alcohol, polyacrylamide, akryylianidi-methylol-acrylate acrylamide copolymer, acrylamide-acrylonitrile copolymer, methylol acrylamide-acrylic ester copolymer, acrylamide-acrylic ester-eekapolymeeriä, acrylic acid-acrylic ester copolymer, methyl cellulose, melamine resins, urea resins, sodium polyacrylate, karbokslmetyyliä, karboksietyyllsellulooaaa, natural rubber, synthetic rubber, polyakryyllhapon ester, polymethacrylic ester, polyvinyl acetate, vinyl acetate-etyleenisekapolymeeriä, polypropylene, polystyrene, polyisobutylene, vinyl acetate copolymer, methyl cellulose, ethyl cellulose, nltroselluloosaa, cellulose acetate resins, phenolic resins, butyraalihartseja, alkyd resins, and petroleum pitch.

Chemical binders can be added to the binders, especially water-soluble binders, whereby the reaction results in the formation of water-insoluble binders.

Joe prefers an aqueous coating composition, using a water-insoluble binder in the form of an aqueous suspension or emulsion.

The carboxyl-modified polymer emulsion is considered to be particularly good because it is quite stable in coatings and has sufficient adhesion even when used in small amounts. Examples of such an emulsion are a carboxylated styrene-butadiene copolymer emulsion, a carboxylated methyl acetacrylate-butadlene emulsion and a vinyl acetate-crotonic acid mixed polyol with a non-aqueous solvent emulsion.

The coating composition of the invention may contain water-insoluble oxides · hydroxide and carbonates of polyvalent metal and / or other mineral pigments, in particular polyvalent metal compounds · such as oxides · hydroxides and carbonates have excellent color-forming ability · when combined with aromatic carboxylic acids.

Therefore, these metal compounds are quite effective for use with some aromatic carboxylic acids, which are considered to be disadvantageous in practice due to their inactive color reaction and low color density. Oxides, hydroxides and carbonates of metals such as magnesium, calcium, barium, zinc, titanium, aluminum, nickel, cobalt, manganese, iron, tin, chromium and palladium are suitable compounds and magnesium oxide, calcium oxide, barium oxide, zinc oxide, zinc oxide, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, tin hydroxide, magnesium carbonate and carbonate carbonate are particularly preferred.

The above-mentioned inorganic metal compounds, which generally belong to a group called Mminer pigments, have in themselves little color-forming ability, but in one chicken of aromatic carboxylic acids their color-forming ability becomes particularly good. The metal compounds defined herein are specifically referred to herein as "inorganic metal compounds" and must be distinguished from conventional mineral pigments. Examples of mineral pigments to be used which are not inorganic metal compounds include activated clay, acid clay, aluminosilicate, zinc silicate, tin silicate, colloidal aluminum hydrosilicate, seollite, bentonite, kaolin and talc. It is simply called "mineral pigments".

The coating compound may contain 1 to 10,000, preferably 5 to 1,000 dry parts by weight per 100 parts by dry weight of aromatic carboxylic acid and / or polyvalent metal salt of the inorganic metal compound as defined above.

It will be appreciated that the inorganic metal compound and the mineral pigment may be present in the coating compound in whole or in part in a specific substrate comprising an organic acid substance and an organic high molecular weight compound, as previously mentioned.

The coating compounds of some self-adjusting copaper papers still contain fine capsules that contain a color former.

The coating compound is applied to the support surface by conventional coating means such as air sweeps, rollers, blades and a gluing machine 18 59362 or · printed on the support surface in a printing press, for example a printing machine and a flexographic method. If the coating compound contains an organic solvent, the printing method is preferred, and the coating compound may further contain a plasticizer such as tributyl phosphate, dibutyl phthalate, dioctyl phthalate, butyl adipate and castor oil.

Paper made of natural or synthetic fibers or synthetic polymer film can be used as the substrate, although natural fiber paper is usually used. The substrate may, if necessary, have a barrier layer made of natural or synthetic macromolecular material.

The photosensitive sheet according to the cooking has the advantages mentioned below. An organic acid can maintain a stable color-forming ability for a long time and prevent overall staining "due to the inability of heat, light, and especially moisture or water in the organic, high molecular weight compound, to result in a relatively low molecular weight organic acid such as salicylic acid or its metal salt, which was unsuitable in practice, can now be used.

Because the mechanical and thermal retention of the coating compound are excellent, it can be stored in a perfectly flawless condition and the coating work can be performed easily. In addition, it is possible to apply it with a coating device mounted on a paper machine so that pressure-sensitive copying sheets can be produced very economically.

A particular mixture comprising an organic acid substance and an organic high molecular weight compound can be mechanically ground to a fine powder having a uniform particle size of a few microns, for example by ball milling. Therefore, it is possible to form a coating layer in which the fine powders are evenly dispersed so as to obtain clear images without color loss.

The coating compound is generally used in amounts of more than 2 g / m2 and the upper limit is determined by purely economic reasons.

The invention is illustrated by the following non-limiting examples. Quantities in the formulas are given in parts by dry weight, unless otherwise stated.

Example 1 100 parts of a thermoplastic modified crystalline resin having a softening point of 110 ° C (Mitsubishi Gas Chemistry Co., Japan, sold as Nikanol S-100) was heated to 180 ° C, 90 parts of zinc-3.9'- di (α, α-dimethylbenzyl) allycylate with stirring and dissolved. A mass was obtained by cooling and solidifying the mixture. The mass was coarsely crushed and ground for 15 hours in a ball mill, in which 200 parts of kaolin and 30 parts of ground silicic anhydride (sold by Shionogi-Pharmaceutical Co., Japan, sold as Carplex No. 60) were added. This gave a special mixture with an average particle size of about 3 / * · The total contents of the ball mill were added to 40 oea of soluble starch And 100 parts of styrene hutadiene pre-polymerization latex (solids $ 50) And 600 parts of water And thoroughly stirred. In this way, a coating compound was obtained. The photosensitive sheet was prepared by applying the coating compound to a continuously moving paper weighing 50 g / m in an amount Λ of a dry weight of 10 g / m, using an experimental paper machine (Mitsubishi Kokoki Co., Japan, sold as a Biisan paper machine) equipped with a similar device that is used commercially on a large scale.

The coating compound was applied to the surface of the preheated paper and recycled during the coating work. As a result, the coating compound was exposed to shear and at the same time had a maximum temperature of 70 ° C, but its flow remained apparently stable without an increase in viscosity. Example 2-1 "2-14 * 100 parts of a methyl-styrene-styrene copolymer having a molecular weight of about 1500 and obtained by polynerizing 60% by weight of α-methylstyrene and 40% by weight of styrene in the presence of thioglycolic acid were combined with 200 parts of each of the following 150 organic acids. At -190 ° C and melted therein to form a homogeneous liquid phase, and upon cooling the liquid phase, an easily crushable mass was obtained.

Example No. Organic acid 2-1 3,5-di- (α-ethylbenzyl) salicylic acid 2-2 zinc 3'-phenyl-5- (α, α-dimethylbenzyl) allylate 2-3 aluminum 3-phenyl-5- (α , α-dimethylbenzyl) salicylate 2-4 zinc 3-cyclohexyl-5- (u, α-dimethylbenzyl) salicylate 2-5 zinc salt 3-cyclohexyl-5- (α, β-dimethylbenzyl) salicylic acid 70 wt% its aluminum salt 30 wt 2-6 zinc 3,5-di - (n, e-dimethylbenzyl) salicylate 2-7 zinc salt 3 * 5-di- (α, α-dimethylbenzyl) salicylic acid 70 wt. And its aluminum salt 30 by weight p2-Θ zinc 3- (α-methylbenzyl) -5- (*, α-dimethylbenzyl) salicylate 2-9 zinc salt 3- (α-methylbenzyl) -5 - («» «- 70% by weight of dimethylsalicylic acid and 30% by weight of its aluminum salt ^ 20 5 S 3 6 2

Example Ho. Organic acid 2-10 zinc 3,3-di - (n, α-dimethylbenzyl) salylate 2-11 zinc 3- (α, n-dimethylbenzyl) -3-phenylsalicylate 2-12 aluminum 3- (α, α- dimethylbenzyl) -5-phenylsalicylic acid 2-13 zinc salt 3 - ((,, α-dinethylbenzyl) -5-phenylalicylic acid 70 wt% and its aluminum salt 30 wt. ^ 2-14 zinc 3,3-dicyclohexyl alicylate 200 one part of each mass thus made was crushed to an average particle size of about 200 μ, 1 part of formaldehyde-sodium naphthalene sulfonate condensate (sold by Koo Atlas Cot in Japan as Benol-H), 600 parts of water and 20 parts of soluble starch were added, followed by grinding * Finally, 40 parts of ethylene-butadiene copolymerization latex (solids £ 30) were added to obtain various coating compounds.

Photosensitive sheets were obtained by applying each coating compound to the sheet at 7 g / m dry weight, calculated word for word, as in Example 1. All coating compounds showed excellent mechanical and thermal resistance during coating.

Example 3-1 / -3-14 200 parts of each mass obtained in Example 2 were crushed to an average particle size of about 200, mixed with 200 parts of kaolin, 30 parts of zinc oxide, 600 parts of water, 40 parts of soluble starch and one part of Denol-N (see Example 2), after which it was ground in a sand mill. Finally, 100 parts of carboxylated styrene-butadiene copolymer ethiolatex (solids 30) were added to obtain various coating compounds.

Photosensitive sheets were made by applying each coating compound to a sheet at 10 g / m dry weight calculated in the same manner as in Example 1. All coating compounds showed similar mechanical and thermal resistance as in the example.

Example 4

The coating compound was made by the same method as in Example 1, except that 3 parts of zinc styrene were added to a further part of Nikonol S 100 and 30 parts of zinc 3,3-di (α, α-diaethylbenzyl) salieylate.

The photosensitive sheet was made of the coating compound in the same manner as in Example 1.

21 59362

Example 5 100 parts of an α-methylstyrene polymer having a molecular weight of about 1100 »were heated together with 10 parts of zinc stearite and 60 parts of zinc 3- (4- (α, α-diaethylbenzyl) phenyl) -5- (β-dimethylbenzyl) allylylate. to 180 ° C, melted and stirred. The obtained result was cooled and coarsely crushed. 40 parts of ground zinc silicate »20 parts of polyacrylamide (degree of polymerization about 1000) and 500 parts of water were added to all the crushings and ground in a porcelain ball mill for 20 hours. Finally, 60 parts of styrene-butadiene polymerization latex was added thereto to form a coating compound.

The Finnoint compound was made into a photosensitive sheet in the same manner as in Example 1. The mechanical and thermal resistance of the coating compound during the coating work was good.

Example 6-1 "V 6-14 100 parts of a novelak-type p-phenylphenol-formaldehyde polycondensation product (molecular weight about 800) were mixed and melted in 150 parts of each of the organic acids mentioned below at a temperature of 100 ° / v, 200 ° C. When this liquid was cooled and solidified »a mass was born.

Example no. Organic acid 6-1 salicylic acid 6-2 zinc salicylate 6- 5 3-hydroxy-5- (α-α-dimethylbenzyl) saicylic acid 6-4 zinc 3-hydroxy-5 -> (α-α-dimethylbenzyl) perm - silylate 6-5 zinc 3-phenyl-5- (α-α-dimethylbenzyl) allylylate 6-6 zinc 3,5-dl- (α-methylbenzyl) salicylate 6-7 zinc 3-5-di- (oc -methylbenzyl) allyl8ylate 6-7 zinc 3,5-di-tertiary butyl salicylate 6-8 zinc 4-otoxyl benzoate 6-9 zinc 3-phenylsalicylate 6-10 4-tert-butylbenzoic acid 6-11 zinc 5- (5 '** lcarboxy- 4, (Hydroxybenzyl) 8α-silylate 6-12 5- (3 * -carboxy-4'-hydroxylbenzyl) ssylic acid 6-13 magnesium 3,5-di-tertiary butyl salicylate 6-14 1-carboxy-2 * 3 * * dihydroxy-6- (α-dimethylbenzyl) naphthalene 50 wt.% and 1-carboxy-2,3-dihydroxy-7- (n-α-dimethylbenzyl) naphthalene 50 wt.% 59362

The pulps of Ktik were marinated into a powder »with a particle size of about 200 μ · 200 oaa each of the ground material was combined with 50 oa of zinc oxide. 600 parts water and 40 parts soluble starch and ground in a sand grinder. Finally, 100 parts of carboxylated styrene-hutadiene copolymer latex (solids $ 50 6) was added to form a coating compound. · A photosensitive sheet was made by applying a coating compound to a backing sheet in the same manner as in Example 1. The mechanical and thermal resistance of each coating compound was the same as in Example 1.

Example 7 100 parts of polystyrene having a molecular weight of about 1000, 50 parts of aluminum 3- (α, α-dimethylbenzyl) -5-cyclohexyl salicylate and 300 parts of kaolin were heated to 180 degrees C, melted and stirred. The mass was obtained by cooling and solidifying the above mixture. The mass was crushed and mixed with 520 parts of an aqueous solution containing 20 parts of polyvinyl alcohol, after which it was ground in a ball mill for 20 hours. Finally, 20 parts of styrene-butadiene copolymer latex (solids 50 #) were added to form a coating compound.

The coating compound was made into a photosensitive sheet in the same manner as in Example 1. The mechanical and thermal resistance of the coating compound was the same as in Example 1.

Example 8 100 parts of an α-methylstyrene polymer having a molecular weight of about 1000, 50 parts of 3-cyclohexyl-5- (N, N-dimethylbenzyl) salicylic acid, 3 parts of stearic acid and 30 parts of zinc oxide were heated to 170 ° C, melted and stirred. The resulting mixture was cooled and solidified to form a mass. The obtained mass was coarsely crushed, 500 parts of an aqueous solution containing 20 parts of starch were added, after which it was ground in a ball mill for 10 hours. Finally, 50 parts of styrene-butadiene copolymer latex (solids $ 50 ¢) were added to form a coating compound ·

The photosensitive sheet was made of the coating compound in the same manner as in Example 1. The mechanical and thermal resistance of the coating compound was the same as in Example 1.

Example 9 100 parts of polystyrene having a molecular weight of about 2000, and obtained by polymerization as carbon tetrachloride, and 100 parts of aluminum 3,5-di- (α-methylbenzyl) salicylate were mixed and melted at a temperature of about 150 ° C, followed by Cooling And Solidification.

t 59362 23

The resulting mass was crushed into granules having a size of less than 1000 μ, 400 parts of coalin and 100 parts of zinc oxide were added thereto, followed by grinding in a ball mill for 10 hours. The shelved products were dispersed in a solution comprising 200 parts of water, 800 parts of ethanol and 100 parts of ethylcellulose to form an ink compound.

o

The photosensitive sheet was made by pressing the ink compound at 7 g / m, calculated on a dry paper!, On a support sheet weighing 30 g / m using a standard printing press.

Example 10 100 parts of a styrene-alkyl alcohol copolymer (monomer weight ratio 90x10, molecular weight about 3000) and 200 parts of zinc 3,5-di- (α-methylbenzyl) salicylate were dissolved in 200 parts of acetone. The acetone was then evaporated to give a mass. The pulp was crushed to a particle size of about 200 μ, and 200 parts of the crushed product were mixed with 1 part of Denol-ff (see Example 2), 600 parts of water and 20 parts of soluble starch, after which it was ground in a grinder (sold by Mitsui Miike Seisokusha, Japan) ). Finally, 40 parts of styrene-butadiene copolymer latex (solids £ 30) were added to form a coating compound. The photosensitive sheet was made using the coating compound in the same manner as in Example 1.

Example 11 100 parts of a styrene alkyl alcohol copolymer (monomer weight ratio 85x15 → molecular weight about 1500) and 300 parts of zinc 3,5-di- (α-methylbenzyl) salicylate were dissolved in 300 parts of acetone. The resulting solution was gradually added to a dispersion of 2,500 parts of water, 30 parts of Denol-N and 500 parts of kaolin, while stirring, to give a dispersion of a special substrate comprising a styrene-alkyl alcohol copolymer and zinc 3,5-di- (α-methylbenzyl) salicylate. The photosensitive sheet was made by applying a 7 g / m dispersion, calculated as dry weight, to a support sheet weighing 50 g / m 2.

Example 12 To 200 parts of a polystyrene emulsion (solids $ 50) was added 100 parts of a 30% aqueous solution of sodium 3- (α, α-dimethylbenzyl) -5-methylalicylate, heated to 80 ° C and gradually added to 500 parts of a 40% aqueous solution of stannous chloride with stirring. . Stirring was then continued for about an hour while maintaining the temperature of the solution at 90 ° C. The emulsified polystyrene particles thus obtained contained tin-3- (α-α-dimethylbenzyl) -5-BaliBylate. next, 150 parts of kaolin, 100 parts of water, t 24 59362 and 50 parts of soluble starch were added to the above emulsion by word while stirring the mixture vigorously to obtain a coating compound.

The photosensitive sheet was made using the coating compound by the same procedure as in Example 1 «

Example Ι3-ΙΛ / Ι3-9 100 parts of zinc 3,5-di- (α-methylbenzyl) salieylate were mixed and melted together with 50 parts of each of the organic high molecular compounds listed below. The result obtained was cooled and solidified to give a mass.

Example no. Organic High Molecular Compound 13-1 Styrene-α-methylstyrene copolymer (monomer weight ratio 60140, molecular weight 5000) I3-2 Polystyrene (molecular weight 1500) 13-3 S-styrene acrylic nitrile glass 85 »15 * molecular weight 5000) 13-5 Styrene-methyl methacrylate copolymer (monomer weight ratio 80:20, molecular weight 2000) 13-6 Phenyl-formaldehyde dipoly polycondensation product (molecular weight 600) 13-7 Shellac 13-8 Polystyrene and effervescent phenol-formaldehyde poly condensation product (molecular weight 800) 30 weight-56 13-9 Paraphenylphenol-formaldehyde polycondensation product (molecular weight 700) 60 wt.% and isophthalic acid ethylene glycol poly-condensation product 1800 (molecular weight)

Each of the above pulps is coarse crushed. 150 parts of each crushed product were mixed with 75 parts of kaolin, 35 parts of active clay with 450 parts of water and 30 parts of soluble starch and compacted in a sand-mill. Finally, 75 parts of styrene-butadiene copolymer latices (solids 50) were added to form a coating composition. The photosensitive sheet was made using the coating compound in the same manner as in Example 1. The mechanical and thermal resistance of the coating compound was good as in Example 1.

M

* * «59362

For comparison with the above examples, aqueous dispersions of organic acid substances containing the following compounds were separately prepared.

Amendment 1

Compound Weight Part

Salicylic acid 100

Denol-N (see Example 2) 1

Polyvinyl alcohol 5

Amendment 2

Compound Weight Part

Salicylic acid 100

Zinc oxide 300

Denol-H 4

Polyvinyl alcohol 20

Amendment 3

Compound Weight Part

Zinc 3-phenylsalicylate 100

Denol-H 1

Styrene - butadiene copolymer latex (solids £ 30) 16

Amendment 4

Compound Weight Part

Zinc 3,5-di-tertiary butyl salicylate 100

Active clay 300

Denol-H 4 Starch 9

Styrene - butadylene copolymer latex (solids 30) 36

The photosensitive sheet was made by applying each of the above dispersions / 2 to a support sheet weighing 30 g / m, calculated as a dry weight of 7 g / m, according to the same method as in Example 1.

In order to ascertain the effects of the photosensitive sheets according to the invention, an upper sheet coated with microcapsules containing a color former was prepared. Microcapsules can be prepared, for example, from U.S. Pat. Patent no. In accordance with 2,800,437. An embodiment for manufacture is given below.

26 5 9 3 6 2 30 parts of acid-treated gelatin were added to 470 parts of water and dissolved at 60 ° C. 3 parts of crystal violet lactone were dissolved in 100 parts of isopropylnaphthalene, heated to $ 0 ° C and the above aqueous gelatin solution was added, which was then emulsified and dieperged with stirring to form small oil droplets with an average diameter of 4-5. 300 parts of a 10% aqueous solution of gum arabic were added to said emulsion, followed by the addition of 200 parts of water and the pH of the dispersion was adjusted to 4-4 * 5 with acetic acid. The dispersion was cooled to 10 ° C to coagulate the co-servate film and 10 parts of formaldehyde were added. After 10 hours of curing, a capsule dispersion had formed. The previous sheet was made by applying a dispersion calculated on a dry weight of 3 g / m to a support paper weighing 30 g / m.

The effects of the photosensitive sheet according to the invention were observed as follows. A photosensitive sheet which had been treated as described below and a photosensitive sheet which had not been treated in a similar manner were placed under an upper sheet on which the top sheet was encapsulated with a color former so that the coated surface was in contact with the microcapsules and the sheets were pressurized. Color fastness, heat, light, and moisture resistance were considered based on the difference in the density of the resulting color image between treated and untreated sheets.

a) The photosensitive sheet was allowed to stand at 90 ° relative humidity and 30 ° C for 10 hours.

b) The photosensitive plate was allowed to stand at 100 ° C for 3 hours.

c) The photosensitive plate was allowed to be exposed to direct sunlight for 3 hours.

In addition to the above tests, the photosensitive sheet was placed in close contact with the upper sheet so that the coated surface and the microcapsules were facing each other. After immersion in water, the sheets were dried and separated. In the case that the water resistance of the photosensitive sheet is poor, the upper sheet forms a color, resulting in a "stained surface".

The results of the above test are shown in Table 1.

In order to determine the light, heat, moisture, and water resistance of the resulting color image, the following experiments were performed. The previous sheet was placed on top of the photosensitive sheet so that the coated surface and the microcapsules were facing each other and the marking pressure was applied to the sheets by means of a typewriter.

After 24 hours, the photosensitive sheet was treated in the following ways and the decrease in color density was taken into account.

a) The photosensitive sheet was kept at 90 56 relative humidity and 27 59362 at 50 ° C for 10 hours.

b) The photosensitive sheet was kept at 100 ° C for 5 hours.

c) The photosensitive sheet was exposed to direct sunlight for 3 hours.

d) The photosensitive sheet was immersed in water and dried at normal temperature.

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Explanation: Color rendering durability A: retained its original color rendering ability B: slightly degraded C: significantly degraded D: completely degraded (color images could not be generated)

Durability of the resulting color image: A: color did not change at all B: slightly changed C: significantly changed D: faded or faded Color density of the image: A: good B: medium C: very poor.

Claims (9)

1. Sensitized sheet for use in a pressure sensitive copying system, characterized in that it is sensitized with a coating to effect color upon contact with a chromogenic material, and that the coating contains a finely divided mixture comprising (a) at least one acidic organic substance selected from the group consisting of aromatic carboxylic acids and their salts with polyvalent metals, and (b) at least one high molecular weight compound. 2. Sensitized sheet according to claim 1, characterized in that the acidic ice-cold substance has at least either a 5-membered or 6-membered carbon ring as a substituent, and 17 or more carbon atoms in its chemical structure. Sensitized sheet according to claim 1, characterized in that the acidic organic substance has a hydroxyl group in ortho position to the carboxyl group in the aromatic ring. U. Sensitized sheet according to claim 1, characterized in that the coating further contains at least one water-insoluble inorganic material in the form of particles of inorganic metal compounds and / or mineral pigments. Sensitized sheet according to claim 1, characterized in that at least one aliphatic carboxylic acid or a site thereof with a polyvalent metal is further present in that this component is incorporated in the atomized mixture comprising this organic acid substance and the high molecular compound. A method of producing the sensitized sheet for use in a pressure sensitive copying system according to claims 1-5, characterized in that the method comprises applying a support layer to a suspension of a finely divided mixture, comprising at least one of the following: organic compound selected from the group consisting of aromatic carboxylic acids and polyvalent metal salts thereof, and (b) at least one organic high molecular weight compound.