Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
  • B41M5/128—Desensitisers; Compositions for fault correction, detection or identification of the layers

Definitions

• R represents a hydrogen atom or an alkyl group, and R, and R each represents a straight or branched chain alkylene residue, or (b) the reaction product of said spiroacetal diamine compound with a compound having at least one oxirane ring.
• the present invention relates to a desensitizer composition and, more particularly, it relates to a desensitizer composition which reduces or cuts down the function of a color developer capable of changing a colorless colorformer into a colored form.
• 29546/71 (monoalkylamines, aralkylamines or tertiary amines wherein ethylene oxide groups are chemically connected to ethanol amine), Japanese patent publication No; 35697/71 (urea resin prepolymer), and others (secondary alkylamines such as didodecylamine; tertiary alkylamines such as triethylamine; primary arylamines such as aniline; aralkylamines such as benzylamine; polyhydroxy compounds such as polyethylene glycol and glycerin).
• secondary alkylamines such as didodecylamine
• tertiary alkylamines such as triethylamine
• primary arylamines such as aniline
• aralkylamines such as benzylamine
• polyhydroxy compounds such as polyethylene glycol and glycerin
• these desensitizers have the disadvantage that'the desensitizing action thereof is insufficient or, if sufficient, a practical effect cannot be obtained unless they are used in a large amount. Therefore, some desensitizers are not sufficiently effective to prevent coloring at the desensitized areas even when they are used in a large amount, while other desensitizers will permit a similar phenomenon unless used in a large amount. In particular, these disadvantages tend to become more serious with improvements in the color for- Therefore, the advantageous properties of these color developers'(for example, color images obtained by using these color developers are not erased with water) are effectively limited. Another disadvantage of conwith a desensitized color developer,
• ventional desensitizers is that, when a color former solution enclosed in a wall film is brought into contact the nondesensitized areas of the color developer become colored with the lapse of time (the formation of the socalled desensitization fog).
• Another object of the present invention is to provide a desensitizer composition having excellent coating properties and capable of being used regardless of whether the coating solution is aqueous or oily.
• a further object of the present invention is to provide a desensitizer composition which causes less desensitization fog.
• Still a further object of the present invention is to provide a desensitizer composition which exerts no detrimental influences on the color former, the color developer and the system containing these materials.
• R represents a hydrogen atom or an alkyl group
• R and R each represents-a straight or branched chain alkylene residue or of the reaction product thereof with a compound having at least one oxirane ring.
• Spiroacetal diamines are known compounds and readily be synthesized according to the processes described in, e.g., German patent No. 1,092,029, U.S. Pat. No. 2,996,517, etc. I
• substituents R, R and R are not especially limited in any way.
• Illustrative examples of these sub-' stituents are as alkyl groups for R, those having 1 to 20 (particularly 1 to 5, especially l to 2) carbon atoms, such as methyl, ethyl, propyl or the like.
• the straight or'branched chain alkylene residues represented by R and R are those having 1 to 20 (particularly 1 to 6)' ane, 3,9-bis(2-aminoethyl)-2,4,8, l -tetraoxaspiro[ 5,- ]undecane, 3 ,9-di-ethyl-3 ,9-bis( 2-aminoethyl 2,4,8,l0-tetraoxaspiro[5,5]undecane, 3,9-bis(3- aminopropyl)-2,4,8 l 0-tetraoxaspiro[5 ,5 ]undecane, 3,9-bis(4-aminobutyl )-2 ,4,8 1 0-tetraoxaspiro[ 5 ,5 ]undecane, 3,9-bis( S-aminopentyl )-2,4,8, 1 0-tetraoxaspiro[5,5 ]undecane, or 3,9-
• the compounds of the present invention include both the spiroacetal diamine compounds per se and the reaction products thereof with a compound having at least one oxirane ring.
• the spiroacetal compounds per se show a desensitizing effect when used in a lower amount as compared with conventional desensitizing compounds.
• the compounds of the invention exhibit sufficient desensitizing effect in an amount at least A; (by weight) that of the amount required for conventional desensitizers.
• the desensitizing compounds of the present invention can be used in greater amounts.
• the compounds of the invention provide desensitizing effect.
• the aforesaid value of V; the amount used for conventional desensitizing compounds is based only on economic considerations.
• the compound of the present invention is used in an amount less than A: that employed for conventional desensitizers, the effect thereof is reduced proportionally to the decrease in the amount, but more excellent effects can still be provided in such case as compared with the same amount of known desensitizers, such as the conventional desensitizers as disclosed in U.S. Pat. No. 2,777,780.
• the compound of the present invention is applied in an amount of from about 0.5 to glm preferably l to 5 g/m found that the desensitizing effect of the spiroacetal diamine compound per se can be further improved and the desensitization fog can be removed by reacting the spiroacetal diamine with a compound having at least one oxirane group in its molecule.
• mixtures of the spiroacetal diamine compound per se and the reaction product of the spiroacetal compound with the compound having at least one oxirane ring can be used where desired.
• alkyl glycidyl esters such as propyl glycidyl ether, butyl glycidyl ether, etc.; allyl glycidyl ethers such as Epikote 828, 834 or 1001 (trade name, made by Shell International Chemicals Corp.), etc.; alkylene oxides such as octylene oxide, styrene oxide, ethylene oxide, propylene oxide, epoxidized polybutadiene, etc.; alicyclic epoxides such as vinyl-cyclohexene dioxide, 3,4-epoxy-6-methylcyclohexylmethyl, 3,4-epoxy-6-methylcyclohexanecarboxylate, etc.; epoxidized vegetable oil fatty acids such as epoxidized oleic acid, epoxidized linoleic acid and epoxidized linolenic
• the reaction between the spiroacetal diamine and the oxirane group-containing compound can be conducted by mixing both reactants, e.g., in a 1:1 molar ratio, and heating the mixture to a temperature higher than the melting point of the spiroacetal diamine component, c.g., 30 to 150C, preferably 100 to 130C.
• a temperature higher than the melting point of the spiroacetal diamine component c.g., 30 to 150C, preferably 100 to 130C.
• it is not necessary to react the oxirane group and the amino group in equivalent amounts and the reaction can be conducted using one or other of the reactants in excess and the product can also be employed in this invention, e.g., since the spiroacetal diamine compound per se is a desensitizer, an excess of this compound can be present in the reaction product mixture.
• the reaction product obtained of the spiroacetal diamine and the compound having at least one oxirane ring has preferably a molecular weight of 200 to 3,000.
• the reaction can be conducted both in the presence or absence of a solvent. Since both reactants are liquid, the reaction proceeds both in the presence and absence of a solvent. If a solvent is used, organic solvents having a boiling point of to 120C are preferred. When the solvent has a boiling point of lower than C, it is dangerous from a practical standpoint. When the solvent has a boiling point of higher than C, evaporation of it and solvent removal becomes extremely difficult.
• Suitable solvents are methanol, ethanol, benzene, toluene, xylene, etc.
• the composition contain at least one of the above described spiroacetal diamines as the desensitizing component.
• the other components of the composition are not particularly limited at all.
• the other components as used herein include those which are incorporated in conventional desensitizer compositions.
• the composition can contain natural or synthetic high molecular weight compounds (e.g., ketone resins, polyamide resins, maleic acid resins, fumaric acid resins, phenol resins, epoxy resins, alkyd resins, melamine resins, urea resins, acryl resins, nitrocellulose, butyral resins, methyl cellulose, cellulose acetate butyrate, casein, gelatin, polyvinyl alcohol, etc.).
• these high molecular weight materials are used as a binder, but the purpose thereof is not necessarily be limited thereto.
• the composition also can contain pigments (e.g., titanium oxide, zinc oxide, barium sulfate, magnesium carbonate, calcium carbonate, barium carbonate, magnesium hydroxide, talc, etc.) to improve printing property, whiteness and hiding power; glycols (e.g., ethylene glycol, diethylene glycol, glycerin, polyethylene glycol, polypropylene glycol, etc.); solvents (e.g., alcohols, etc.); fats and oils (e.g., paraffin, Japan wax, etc.) to improve friction resistance; drying oils (e.g, linseed oil, tung oil, soybean oil, etc.); semi-drying oils (e.g., cotton seed oil, rapeseed oil, rice bran oil, etc.); and, in some cases, conventionally known additives such as starch or like off settingpreventing agents, other desensitizers, etc.
• pigments e.g., titanium oxide, zinc oxide, barium sulfate, magnesium carbonate
• the binders are generally used in an amount of 5 to 30 wt%, pigments in an amount of 5 to 50 wt%, glycols, solvents, fat and oils, drying oils, semi-drying oils each in an amount of 5 to 40 wt% and off-set preventing agents in an amount of 0.5 to 5 wt%.
• the composition of the present invention can be used in various forms such as an aqueous solution, an organic solvent solution (e.g., alcohol solution), an aqueous dispersion, a paste, a solid, and the like and coated in the amount hereinbefore described. lt should be noted that the action of the composition of this invention is not dissipated regardless of the kind and the amount of the other components incorporated therein or the form of the composition employed.
• the desensitizer composition which can be readily prepared by those skilled in the art as described above is applied on a color developer layer by printing such as relief printing, gravure printing or the like, spraying, or by handwriting e.g., as a solid in the form of a crayon.
• the color developers to which the desensitizer com position of the invention is applicable are electron acceptive materials or proton donating solid acids. These color developers are extremely well known in the art. Illustrative specific examples are clay minerals such as acid clay, active clay, attapulgite, etc.; organic acids such as tannic acid, gallic acid, propyl gallate, etc.; acid polymers such as phenol-formaldehyde resins, phenolacetylenc condensation resins, condensates between an organic carboxylic acid having at least one hydroxy group and formaldehyde, etc.; metal salts of aromatic carboxylic acids such as zinc salicylate, tin salicylate, zinc 2-hydroxynaphthoate, Zinc 3,5-di-tert-butylsalicylate, etc.; and mixtures thereof.
• clay minerals such as acid clay, active clay, attapulgite, etc.
• organic acids such as tannic acid, gallic acid, propyl gallate, etc.
• the color developer is applied to asupport such as paper, plastic film-laminated papers, etc. together with a binder such as styrene-butadiene latex, in an amount of l to 90, preferably 5 to 80, parts by weight per 100 parts by weight of the color developer composition calculated on a solids basis.
• asupport such as paper, plastic film-laminated papers, etc. together with a binder such as styrene-butadiene latex, in an amount of l to 90, preferably 5 to 80, parts by weight per 100 parts by weight of the color developer composition calculated on a solids basis.
• the color developer composition may contain a binder such as latex, polyvinyl alcohol, maleic anhydride-styrene copolymer, starch and gum arabic. It is to be understood that all binders wel1known as filmforming materials can be used in the invention.
• the binders can be classified into three groups, i.e., (l) a water soluble or hydrophilic binder, for example, a natural compound such as proteins (e.g., gelatin, gum arabic, colloid albumin, casein), celluloses (e.g., carboxymethyl cellulose, hydroxyethyl cellulose) saccharoses (e.g., agar, sodium alginate, starch, carboxymethyl starch), and a synthetic compound such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylate, polyacrylamide; (2) a water-dispersible binder, for example, latex such as.styrene-butadiene copolymer latex, styrene-maleic anhydride copolymer latex; and (3) an organic solvent-soluble binder such as nitrocellulose, ethyl cellulose or polyester.
• a water soluble or hydrophilic binder for example, a natural compound such as proteins (e
• the color formers which generate a color on reaction with the color developer are substantially colorless electron donating or proton accepting organic compounds.
• Illustrative color formers are triarylmethane compounds, diphenyl-methane compounds, xanthene compounds, thiazine compounds, spiropyran compounds, etc.
• Specific examples of the triarylmethane compounds include 3,3bis(pdimethylaminophcnyl )-6-dimethylaminophthalide, i.e., crystal violet lactone (hereinafter referred to as CVL"), 3,3-bis(p-dimethylaminophenyl)-phthalide,
• diphenylmethane compounds include 4,4- bis-dimethylaminobenzhydrinbenzyl ether, N- halophenyl-leuco auramine, N-2,4,5-trichlorophenyl leuco auramine, and the like.
• xanthene compounds include rhodamineB- anilinolactam, rhodamine-(p-nitroanilino)lactam, rhodamine B-(p-chloroanilino)lactam, 7-dimethylamino 2-methoxyfluoran, 7-diethyl-a'mino2 methoxyfluoran, 7-diethylamino3-methoxyfluoran, 7-diethylamino-3- chlorofluoran, 7-diethylamino-3-chloro-2-methylfluoran, 7-diethylamino-2,3-dimethylfluoran, 7- diethylamino-( 3-acetylmethylamino)-fluoran, 7- diethylamino-( 3-methylamino )fluoran, 3,7-
• diethylaminofluoran diethylaminofluoran, 7-diethylamino-3- (dibenzylamino )fluoran, 7-diethylamino-3-( methylbenzylamino )fluoran 7-diethylamino-3-( chloroethylmethylamino)fluoran, 7diethylamino-3- (diethylamino)-fluoran, and the like.
• Specific examples of the thiazine compounds include benzoyl leuco methylene blue, p-nitrobenzoyl leuco methylene blue, and the like.
• spiro compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spirodinaphtho -pyran, 3,3-dichloro-spiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methyl-naphtho-(3 methoxy-benzo)-spiropyran, 3-propyl-spirodibenzopyran, and the like.
• the color formers are applied to a support together with a binder by dissolving the color formers in a synthetic or natural oil such as chlorinated diphenyl, chlorinated terphenyl, alkylated diphenyl, alkylated terphenyl, chlorinated paraffin, chlorinated naphthalene, alkylated naphthalene, kerosene, paraffin and naphthene oil, or by encapsulating it according to the process as described in US. Pat. No. 2,800,457 and the like together with, if desired, additives such as starch particles.
• the color former solution can be coated only on certain specific areas.
• the color former and the color developer can be used in any form suitable for use, such as in a pressure sensitive recording paper, a heat sensitive recording paper or the like.
• the color developer sheet, the color former sheet and the desensitizing ink, used in the Examples for demonstrating the effects of the desensitizers of the invention were produced as follows.
• Coating Solution B was applied to a 50 g/m paper in an amount of 2 g/m on a solids basis, followed by drying. Thus, Color Developer Sheet B was obtained.
• Coating Solution C was applied to a 50 g/m paper in an amount of 2 g/m on a solids basis and dried. Thus, Color Developer Sheet C was obtained.
• PREPARATION OF COLOR FORMER SHEET A 10 Parts of acid-processed gelatin having an isoelectric point of 8.0 and 10 parts of gum arabic were dis solved in 60 parts of water at 40C, and 0.2 part of sodium dodecylbenzenesulfonate was added thereto as an emulsifier. Then, 50 parts of a color former oil was emulsified therein.
• the color former oil used above was prepared by dissolving 2.5% by weight of crystal violet lactone (CVL) and 2.0% by weight of bcnzoyl leucomethylene blue in an oil comprising 4 parts of diisopropylbiphenyl and 1 part of kerosene.
• PREPARATION OF COLOR FORMER SHEET B 1% by weight of CVL, 4% by weight of 3- diethylamino-7-diethylaminofluoran, 4% by weight of 3-diethylamino-7-phenylaminofluoran, 3% by weight of 3-diethylamino-7,8-benzofluoran, 0.5% by weight of 3,6-bismethoxyfluoran and 2% by weight of benzoyl leuco methylene blue were dissolved in an oil comprising 1 part of diisopropylnaphthalene, 1 part of diisop'ropylbiphenyl and 2 parts of l-(dimethylphenyl)-lphenylethane to prepare a color former oil.
• Color Former Sheet B was obtained using 50 parts of the above-described color former oil.
• the resulting ink composition was printed on each of the above-described color developer sheets in an amount of 2 g/m TESTING METHOD
• the thus prepared desensitizer was printed on the individual color developer sheet, and color-formation was obtained by applying a load of 600 kg/cm and facing the desensitized areas and the color former sheet toward each other. After 24 hours, the density was measured using a microdensitometer to obtain reflection visual density (Vis. D). The desensitizing effect was rated in terms of the Vis. D.
• an epoxy equivalent of 182 194 a viscosity of 110 150 poises at C, a specific gravity of 1.167 at 20C, a molecular weight of about 355, an epoxy content of 0.51 0.55 epoxy groups per 100 g of the condensation product and a hydroxy content of 0.06 hydroxy groups per 100 01' the condensation product.
• the compounds of the present invention provide the desensitizing effect about 100 times that of the desensitizer-free composition (Comparative Example 1) and about 20 times that of the conventional desensitizers (Comparative Examples 2 6). Of the conventional desensitizers, the compound shown in Comparative Example 3 provides better results than the other conventional compounds. However, the desensitizing effect thereof varies depending upon the kind of color former. In contrast, the desensitizers of the invention all exhibit great desensitizing effect regardless of the kind of color formers, and hence they are extremely desirable.
• a developer sheet comprising a color developer layer and a desensitizer composition for desensitizing a color developer capable of reaction with a substantially colorless color former to form a color containing as a desensitizer at least one of a. a spiroacetal diamine compound represented by the following general formula:
• said desensitizer composition is present in an amount offrom about 0.5 to about 10 g/m on said color developer layer in the areas of said color developer layer containing said desensi tizer composition.
• said spiroacetal diamine compound is 3,9- bis(aminomethyl )-2,4,8 l O-tetraoxaspiro 5 ,5 ]undecane, 3,9-bis(2-aminoethyl)-2,4,8,l0-tetraoxaspiro[5,- 5]undecane, 3,9-diethyl-3,9-bis(2-aminoethyl)-2, 4,8,- 10-tetraoxaspiro[5 ,5 ]undecane, 3 ,9bis( 3- aminopropyl)-2,4,8,l-tetraoxaspiro[5,SIundecane,
• said compound having at least one oxirane ring is an alkyl glycidyl ether, an allyl glycidyl ether, an alkylene oxide, an alicyclic epoxide, an epoxidized vegetable oil fatty acid, or an epoxidized glyceride.
• a developer sheet as claimed in claim 1 comprising a support having thereon a color developer layer and a layer, at least in selected areas of said developer sheet, of said desensitizer composition.
• said color developer is a clay, an organic acid, an acidic polymer, a metal salt of an aromatic carboxylic acid, or mixtures thereof.
• a process for desensitizing the coloration generated by a color former'contacting a color developer V which comprises applying to a layer of said color devel- CH O R 1mm, o cn (CH2O wherein R represents a hydrogen atom or an alkyl group, and R and R each represents a straight or branched chain alkylene residue, or
• said desensitizer composition is present in an amount of from about 05 to about 10 g/m on said color developer layer in the areas of said color developer layer containing said layer of said desensitizer composition.
• saidi spiroacetal diamine compound is 3,9-bis(aminomethyl)-2,4,8,10- tetraoxazpiro[5 ,5]undecane, 3 ,9-bis( 2aminoethyl 2,4,8, 1 0-tetrao;.aspiro[5,5 ]undecane, 3,9-diethyl-3 ,9- bis(2-aminoethyl)-2,4,8,lO-tetraoxaspir0[5,5]undecane, 3 ,9-bis( 3 aminopropyl)2.,4,8, l 0-tetraoxaspiro[ 5 5]undecane, 3 ,9-bis (4-aminobutyl)-2,4,8 ,10- tetraoxaspiro[5,5]undecane, 3,9bis(5-aminobenzyl)- 2,4,8, lO-tetraoxas
• said desensitizer is said reaction product of said spiroacetal diamine compound with a compound having at least one oxirange ring.
• said compound having at least one oxirane ring is an alkyl glycidyl ether, an allyl glycidyl ether, an alkylene oxide, an alicyclic epoxide, an epoxidized vegetable oil fatty acid, or an epoxidized glyceride.

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Citations (9)

• 1973
  • 1973-08-27 FR FR7330932A patent/FR2198416A5/fr not_active Expired
  • 1973-08-29 ES ES418319A patent/ES418319A1/es not_active Expired
  • 1973-08-30 GB GB4097773A patent/GB1407645A/en not_active Expired
  • 1973-08-30 US US393089A patent/US3900218A/en not_active Expired - Lifetime
  • 1973-08-30 DE DE19732343800 patent/DE2343800A1/de active Pending

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