US2363330A - Safety paper and preparation thereof - Google Patents
Safety paper and preparation thereof Download PDFInfo
- Publication number
- US2363330A US2363330A US346870A US34687040A US2363330A US 2363330 A US2363330 A US 2363330A US 346870 A US346870 A US 346870A US 34687040 A US34687040 A US 34687040A US 2363330 A US2363330 A US 2363330A
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- Prior art keywords
- paper
- agent
- stain
- nitrogen
- compounds
- Prior art date
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- 238000002360 preparation method Methods 0.000 title description 2
- 239000003795 chemical substances by application Substances 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000000126 substance Substances 0.000 description 23
- 125000005842 heteroatom Chemical group 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 230000001235 sensitizing effect Effects 0.000 description 15
- 230000001590 oxidative effect Effects 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 125000001424 substituent group Chemical group 0.000 description 7
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 150000004897 thiazines Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- -1 allroxy Chemical group 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 125000002837 carbocyclic group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical group [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004891 diazines Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000003375 sulfoxide group Chemical group 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
- D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
- D21H21/46—Elements suited for chemical verification or impeding chemical tampering, e.g. by use of eradicators
Definitions
- This invention relates to paper that is prepared or treated with a chemical or chemicals designed to form an easily discernible stain on the paper in the event of an attempt to use ink eradicating chemicals to remove writing or ink from the paper.
- sensitizing chemicals heretofore proposed, however, have had the objection of being rather easily removed from the paper. This enables a person who wishesto alter the writing on the paper to remove the sensitizlng chemical or chemicals before applying. an eradicator to the ink. Water soluble sensitizing chemicals are especially open to this objection since they may be removed before altering the writing on a check or other paper, and thus they do not furnish a telltale stain or other indication of the alteration.
- sensitizing chemicals used for thispurpose should be such that they produce a permanent stain that carmot be removed after the stain is formed.
- sensitizing safety paper should be stable to sunlight, ageing and other-exposures to which the paper may be subjected, because if the chemicals lose their staining properties after the paper has been cyclic rings, each such ring containing two hetero atoms, at least one of which is a nitrogen atom, can be incorporated in or on paper to yield a permanent telltale stain of dark character upon the application of an oxidizing agent such as a hypochlorite commonly used in ink eradicators.
- the other hetero atom may be a sulfur atom, in which case the compound would be classed as a thiazine; or another nitrogen atom in which case it would belong to the class of diazines; or an oxygen atom when it would be classed as an oxazine.
- the second hetero atom of the ring isfisulfur, it may exist as the sulfide or be associated with oxygen in the form cfa sulfoxide or sulfone.
- an object of this invention is to provide safety v paper carrying a stable staining chemical that produces a conspicuous and relatively permanent stain upon the application of common ink eradicators to the paper.
- Another object is the provision of paperv carr ing'a sensitizing chemical that cannot be readily removed from the paper prior to the application of an ink eradicator thereto without leaving-some indication of the removal.
- Another object is to Provide such a safety paper that does not become objectionably discolored upon ageing or exposure to sunlight and that retains this staining property for relatively long periods of time;
- B. may be hydrogen or any suitable substituent therefor.
- These compounds may be incorporated in or on paper to yield a permanent telltale stain of dark charact dizing agent such as hypochlorite commonly used in ink 'eradicators.
- the stains produced by these compounds are usually dark blue or blue-black, and it is virtually impossible to remove the stain after it is formed without leaving some other mark on the paper that will call attention to the alteration.
- the stain producing compounds of this invention are relatively insoluble in water and, therefore, cannot easily be removed from the paper prior to the application oi ink eradicator simply by soaking the paper in water.
- the compounds also have the advantage of not, being substantially affected by a relatively weak acid -solution.which is applied sometimes as a preliminary treatment in the application 01 ink .eradicator.
- the preferred compounds used according to this invention are the substantially colorless, or only slightly colored, light stable thiazines hav the formula ,stituted or unsubstituted arylene or other carbocyclic radicals joined ortho to the nitrogen and sulfur atoms, and It is hydrogen or any suitablevsubstituent such as an acyl, allroxy, alkyl,
- the sulfur may be present as sulfide, or-in combination with oxygen as a sulione or a sulfoxide group.
- dibenzo-, or conjugated cyclic, thiazines is the well known compound phenothiazine, also known as thiodiphenylamine. This compound, although it produces a good stain when oxidized, is slightly sensitive to light, and therefore we prefer to employ the dibenzo-, or conjugated cyclic, thiazines that are substituted in one or more positions by one or more.
- substltuents either on one or both of the carer upon the application of an oxibocyclic rings, or Joined dire atom, or both.
- Suitable thiazines for purposes of this invention include the substituted thiodiphenylamines,
- Mtoamino-N-mothylthiodiphenylamin 40 substituted thiaz i nescontaining one or more monocarbocyclic or polycarbocyclic rings or their substituents or derivatives in place of one or both of the carbocyclic rings or the foregoing compounds may be employed.
- the thiazines that are used in accor this invention are relatively insoluble in water and generally unaffected by oxalic acid or other acid solutions which might be used in ink eradicators. For this reason, it is very difiicult, if not virtually impossible, to remove these compounds from the paper without making the tampering attempt clearly apparent to the naked eye.
- thlazines also'produce very rapidly a deep stain on the paper fibres when subjected to the 55 action 0! an oxidizing agent, and these stains are permanent to such an extent that they cannot be removed without leaving on the paper some mark that calls attention to the altered surface of the paper.
- the sensitizing compounds of this invention can be incorporated into the paper or applied as a coating or as an ingredient of a coating thereon, or they may be dissolved in an appropriate solvent and the paper immersed therein.
- the 76 thiazine type or sensitizing agent may be mixed dance with Q with the sizing material beforeit is mixed with the pulp, thus obtaining a more uniform distribu-' tion of the chemical throughout the pulp.
- the sensitizing chemical may be mixed withor dispersed in starch or-other commonly used surface or tub sizing materials and applied with these materials in the usual tub sizing operation.
- water soluble salts or other derivain which R is a substituted or unsubstituted arylene radical attached by two adjacent carbon Y atoms respectively to the nitrogen and X atoms,
- R. is hydrogen or a substituent therefor forming a stable material with the balance of the compound
- -x is a substance selected from the group consisting of 8, S0 and S0: with only the tive; .of these sensitizing compounds that react as byhydrolysis or the like to leave the relatively the paper may be insoluble compound in or on employed.
- sensitizing chemical may be varied within fairly wide limits, although usually I
- thiazine is used in the specification and claims in its broad sense to include compounds in which the sulfur atom in the heterocyclic ring may exist as a' sulfide or in an oxidized condition as a sulione or sulfoxide.
- Paper having an agent associated therewith in such a manner as to produce a stain upon the application of an oxidizing reagent to the p per, said agent comprising a light stable substantially colorless organic compound having at least one six membered unsaturated heterocyclic ring containing two hetero atoms disposed para to each other, at least one of said hetero atoms being nitrogen.
- Paper having an agent associated therewith in such a manner as to produce a stain upon the application of an oxidizing reagent to the paper, said agent comprising a substantially colorless, light stable organic compound having at least one six membered unsaturated heterocyclic rin containing twohetero atoms disposed in the para positions, one of said hetero atoms being nitrogen and the other of said hetero atoms being selected from the class consisting of nitrogen, oxygen and sulfur.
- Paper having an agent associated therewith in such a manner as to produce a stain upon the application of an oxidizing reagent to the paper said agent comprising a diarylene heterocyclic compound that is no more than slightly colored having a six membered unsaturated heterocyclic ring containing four carbon atoms, a nitrogen sulfur atom in the ring.
- Paper having an agent associated in such a manner as to produce a stain upon the application of an oxidizing reagent to the paper, said agent comprising a substantially colorless compound having the formula in which R is a substituted or unsubstituted arylene radical attached by two adjacent carbon atoms respectively to the two nitrogen atoms.
- Paper having an agent associated therewith in such a manner as'to produce a stain upon the application of an oxidizing reagent to the paper said agent comprising a substantially colorless compound having the formula in which 1R is a substituted or unsubstituted arylene radical attached by two adjacent carbon atoms respectively to the nitrogen and oxygen, and R is hydrogen or a substituent therefor forming a stable material with the balance of the compound.
- sa d agent comprising a substantially colorless compound having the formula I k i in which R. is a substituted or unsubstituted atom and a1 second hetero atom para to the nitrogen and selected from. the class consistih of nitrogen, oxygen and sulfur.
- said'agent comprising a substantially colorless compound having the formula arylene radical attached by two adjacent carbon atoms respectively to the nitrogen and sulfur, and R. is hydrogen or a substituent therefor forming a. stable material with the balance of the compound.
- said agent comprising a light stable N-substituted thiodiphenylamine.
- a method of preparing safety paper comprising treating paper with a solution of a light stable substantially colorless organic compound having at least one six membered unsaturated heterocyclic ring containing two hetero atoms para to each other, at least one of said hetero atoms being nitrogen.
- a method of preparing safety paper comprising incorporating therein a small amount 01 rated heterocyclicwring containing two hetero atoms para to each other, at least one of said hetero atoms being nitrogen.
- a method 01 preparing safety p p r comprising preparing paper with a small amount of a sensitizing agent incorporated in the surface thereof, said agent comprising a light stable substantially colorless organic compound having at least one six member unsaturated heterocyclic ring containing two hetero atoms para to each other, at least one oi! said hetero atoms being nitrogen.
- said agent being present in an amount of from 0.25 to 2% 01 the paper by weight and comprisin a light stable substituted thiodiphenylamine that is no more than slightly colored.
- Paper having an agent associated therewith in such a manner as to produce a stain upon the application of an oxidizing reagent to the paper, said agent being present in an amount of from 0.25 to 2% of the paper by weight and comprising a light stable N-substituted thiodiphenylamine.
Landscapes
- Paper (AREA)
Description
Patented Nov- 21, 1944 L *SAFETY PAPER AND PREPARATION THEREOF Donald T. Jacksonand John L. Parsons, Erie, Pa., assignors to Hammermill Paper Company, Erie, Pa., a corporation of Pennsylvania No Drawing. Application July 22, 1940, Serial No. 346,870
at Claims. (Ci. 117-1) This invention relates to paper that is prepared or treated with a chemical or chemicals designed to form an easily discernible stain on the paper in the event of an attempt to use ink eradicating chemicals to remove writing or ink from the paper. I
Various chemical treatments have been -pro posed for paper to renderit sensitive to ink eradicating chemicals and thus attempt to expose the alteration of matter written in ink on, the paper when it is used for such things as bank checks, drafts, wills or the like.
The majority of the sensitizing chemicals heretofore proposed, however, have had the objection of being rather easily removed from the paper. This enables a person who wishesto alter the writing on the paper to remove the sensitizlng chemical or chemicals before applying. an eradicator to the ink. Water soluble sensitizing chemicals are especially open to this objection since they may be removed before altering the writing on a check or other paper, and thus they do not furnish a telltale stain or other indication of the alteration.
, It is also important in safety paper to have a readily nOticeabIestalndeVeIOp immediately upon the application of ink eradicating chemicals to the paper. Furthermore, the sensitizing chemicals used for thispurpose should be such that they produce a permanent stain that carmot be removed after the stain is formed.- Still other requirement of chemicals used in sensitizing safety paper is that the chemicals be stable to sunlight, ageing and other-exposures to which the paper may be subjected, because if the chemicals lose their staining properties after the paper has been cyclic rings, each such ring containing two hetero atoms, at least one of which is a nitrogen atom, can be incorporated in or on paper to yield a permanent telltale stain of dark character upon the application of an oxidizing agent such as a hypochlorite commonly used in ink eradicators.
While it appears necessary that one of the hetero atoms of the ring be a nitrogen atom, the other hetero atom may be a sulfur atom, in which case the compound would be classed as a thiazine; or another nitrogen atom in which case it would belong to the class of diazines; or an oxygen atom when it would be classed as an oxazine. If the second hetero atom of the ring isfisulfur, it may exist as the sulfide or be associated with oxygen in the form cfa sulfoxide or sulfone. Compounds in which the two hetero atoms occur para to each exposed tcsunlight', or if they produce discoloration of the paper u'pon ageing or exposure to the sunlight, they have little'practical valuefor pur-' P ses of this invention.
'An object of this invention is to provide safety v paper carrying a stable staining chemical that produces a conspicuous and relatively permanent stain upon the application of common ink eradicators to the paper.
Another object is the provision of paperv carr ing'a sensitizing chemical that cannot be readily removed from the paper prior to the application of an ink eradicator thereto without leaving-some indication of the removal.
Another object is to Provide such a safety paper that does not become objectionably discolored upon ageing or exposure to sunlight and that retains this staining property for relatively long periods of time;
Further objects of the invention will be specifically described and will be apparent from the following description of the invention.
We have discovered that certain compounds which contain one or more 6 membered heteroother appear tobe particularly suited for purposes of this invention and such compounds may be represented by the following type formulae:
group or condensed ring structure, and B. may be hydrogen or any suitable substituent therefor.
" We prefer to use compounds in which the same or difierent arylene'o r other suitable carbocyclic ring structures occupy positions 2 and 3, and the Derivatives of thesecompoun'ds positions and 6; respectively. The following are examples of such compounds.
Phenazine Phenoxa'ginc in which one or more additional substituents are substituted in any of the positions susceptible to substitution appear to possess the desirable properties to thegreatest degree for use as a sensitizing agent in or on paper. Also, the salts of any of these compounds capable of forming salts may be used.
These compounds may be incorporated in or on paper to yield a permanent telltale stain of dark charact dizing agent such as hypochlorite commonly used in ink 'eradicators. The stains produced by these compounds are usually dark blue or blue-black, and it is virtually impossible to remove the stain after it is formed without leaving some other mark on the paper that will call attention to the alteration. The stain producing compounds of this invention are relatively insoluble in water and, therefore, cannot easily be removed from the paper prior to the application oi ink eradicator simply by soaking the paper in water. The compounds also have the advantage of not, being substantially affected by a relatively weak acid -solution.which is applied sometimes as a preliminary treatment in the application 01 ink .eradicator.
Ingeneral, the preferred compounds used according to this invention are the substantially colorless, or only slightly colored, light stable thiazines hav the formula ,stituted or unsubstituted arylene or other carbocyclic radicals joined ortho to the nitrogen and sulfur atoms, and It is hydrogen or any suitablevsubstituent such as an acyl, allroxy, alkyl,
m1, alkaryl, aralkyl group. The sulfur may be present as sulfide, or-in combination with oxygen as a sulione or a sulfoxide group. i
One or the simplest dibenzo-, or conjugated cyclic, thiazines is the well known compound phenothiazine, also known as thiodiphenylamine. This compound, although it produces a good stain when oxidized, is slightly sensitive to light, and therefore we prefer to employ the dibenzo-, or conjugated cyclic, thiazines that are substituted in one or more positions by one or more.
substltuents either on one or both of the carer upon the application of an oxibocyclic rings, or Joined dire atom, or both.
Suitable thiazines for purposes of this invention include the substituted thiodiphenylamines,
ctly to the nitrogen thiophenylnaphthylamines, and thiodinaphthylamines or their salts. The following are examples of suitable substituted thiophenylamines, it being understood that other similar substituents m may be used with theother thiodi'arylamines.
s v 01 mol 01 no! N Tetrachlorothiodiphenyiamine 1 NH N 2 4,8-diaminothiodiphenylamine s E1 N-phenylthiodiphenylarnine NHcoom 85 (1 N AH: I
Mtoamino-N-mothylthiodiphenylamin 40 Similarly substituted thiaz i nescontaining one or more monocarbocyclic or polycarbocyclic rings or their substituents or derivatives in place of one or both of the carbocyclic rings or the foregoing compounds may be employed. The thiazines that are used in accor this invention are relatively insoluble in water and generally unaffected by oxalic acid or other acid solutions which might be used in ink eradicators. For this reason, it is very difiicult, if not virtually impossible, to remove these compounds from the paper without making the tampering attempt clearly apparent to the naked eye. These thlazines also'produce very rapidly a deep stain on the paper fibres when subjected to the 55 action 0! an oxidizing agent, and these stains are permanent to such an extent that they cannot be removed without leaving on the paper some mark that calls attention to the altered surface of the paper.
The sensitizing compounds of this invention can be incorporated into the paper or applied as a coating or as an ingredient of a coating thereon, or they may be dissolved in an appropriate solvent and the paper immersed therein. We prefer, however, to add the sensitizing agent, or a so that the chemical will be uniformly embedded in and mixed with the paper fibres making it as difficult as possible to remove the chemical from the paper. It is very convenient to add the sensitizing chemical to the pulp either at the same time or adding the size or at some subsequent stage in the paper making process. In fact, the 76 thiazine type or sensitizing agent may be mixed dance with Q with the sizing material beforeit is mixed with the pulp, thus obtaining a more uniform distribu-' tion of the chemical throughout the pulp. Furthermore, the sensitizing chemical may be mixed withor dispersed in starch or-other commonly used surface or tub sizing materials and applied with these materials in the usual tub sizing operation. Also, water soluble salts or other derivain which R is a substituted or unsubstituted arylene radical attached by two adjacent carbon Y atoms respectively to the nitrogen and X atoms,
R. is hydrogen or a substituent therefor forming a stable material with the balance of the compound, and -x is a substance selected from the group consisting of 8, S0 and S0: with only the tive; .of these sensitizing compounds that react as byhydrolysis or the like to leave the relatively the paper may be insoluble compound in or on employed.
' The proportion of sensitizing chemical may be varied within fairly wide limits, although usually I The term thiazine, is used in the specification and claims in its broad sense to include compounds in which the sulfur atom in the heterocyclic ring may exist as a' sulfide or in an oxidized condition as a sulione or sulfoxide.
The terms and expressions which we have employed are used as terms of description and not oi limitation, and we have no intention. in the use of such terms and expressions, of excluding any equivalentsof the features shown and described or portions thereof, but recognize that various modifications arepossible within the We claim:
scope of the invention claimed.
1. Paper having an agent associated therewith in such a manner as to produce a stain upon the application of an oxidizing reagent to the p per, said agent comprising a light stable substantially colorless organic compound having at least one six membered unsaturated heterocyclic ring containing two hetero atoms disposed para to each other, at least one of said hetero atoms being nitrogen.
2. Paper having an agent associated therewith in such a manner as to produce a stain upon the application of an oxidizing reagent to the paper, said agent comprising a substantially colorless, light stable organic compound having at least one six membered unsaturated heterocyclic rin containing twohetero atoms disposed in the para positions, one of said hetero atoms being nitrogen and the other of said hetero atoms being selected from the class consisting of nitrogen, oxygen and sulfur.
3. Paper having an agent associated therewith in such a manner as to produce a stain upon the application of an oxidizing reagent to the paper, said agent comprising a diarylene heterocyclic compound that is no more than slightly colored having a six membered unsaturated heterocyclic ring containing four carbon atoms, a nitrogen sulfur atom in the ring.
5. Paper having an agent associated in such a manner as to produce a stain upon the application of an oxidizing reagent to the paper, said agent comprising a substantially colorless compound having the formula in which R is a substituted or unsubstituted arylene radical attached by two adjacent carbon atoms respectively to the two nitrogen atoms.
6. Paper having an agent associated therewith in such a manner as'to produce a stain upon the application of an oxidizing reagent to the paper, said agent comprising a substantially colorless compound having the formula in which 1R is a substituted or unsubstituted arylene radical attached by two adjacent carbon atoms respectively to the nitrogen and oxygen, and R is hydrogen or a substituent therefor forming a stable material with the balance of the compound. I
7. Paper having an agent associated therewith in such a manner as to produce astain upon the ap lication of an oxidizing reagent-to the paper,
sa d agent comprising a substantially colorless compound having the formula I k i in which R. is a substituted or unsubstituted atom and a1 second hetero atom para to the nitrogen and selected from. the class consistih of nitrogen, oxygen and sulfur.
4. Paper having an'agent associated therewith insuch a manner as to produce a stain upon the application of an oxidizing reagent to the paper;
said'agent comprising a substantially colorless compound having the formula arylene radical attached by two adjacent carbon atoms respectively to the nitrogen and sulfur, and R. is hydrogen or a substituent therefor forming a. stable material with the balance of the compound. V
8. Paper having an agent associated therewith in such a manner as to produce a stain upon the thiodiphenylamine that is no more than slightly colored.
9. Paper having an agent associatedtherewith insuch a manner as to produce a stain upon the application of an oxidizing reagent to the paper,
said agent comprising a light stable N-substituted thiodiphenylamine.
10. Paper having an agent associated therewith in such a manner as to produce a stain upon the application of an oxidizing reagent to the paper,
therewith stain producing agent.
16. A method of preparing safety paper comprising treating paper with a solution of a light stable substantially colorless organic compound having at least one six membered unsaturated heterocyclic ring containing two hetero atoms para to each other, at least one of said hetero atoms being nitrogen.
17. A method of preparing safety paper comprising incorporating therein a small amount 01 rated heterocyclicwring containing two hetero atoms para to each other, at least one of said hetero atoms being nitrogen.
18. A method 01 preparing safety p p r comprising preparing paper with a small amount of a sensitizing agent incorporated in the surface thereof, said agent comprising a light stable substantially colorless organic compound having at least one six member unsaturated heterocyclic ring containing two hetero atoms para to each other, at least one oi! said hetero atoms being nitrogen.
a sensitizing agent'comprisinga light stable substantially colorless organic compound that forms a more or less permanent stain upon contact with a solution of an oxidising agent, said compound having at least one six membered unsatu- 19. Paper having an agent associated therewith in such a manner as to produce a. stain upon the application of an oxidizing reagent to the paper,
said agent. being present in an amount of from 0.25 to 2% 01 the paper by weight and comprisin a light stable substituted thiodiphenylamine that is no more than slightly colored.
20. Paper having an agent associated therewith in such a manner as to produce a stain upon the application of an oxidizing reagent to the paper, said agent being present in an amount of from 0.25 to 2% of the paper by weight and comprising a light stable N-substituted thiodiphenylamine.
DONALD T. JACKSON. JOHN L. PARSONS.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US346870A US2363330A (en) | 1940-07-22 | 1940-07-22 | Safety paper and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US346870A US2363330A (en) | 1940-07-22 | 1940-07-22 | Safety paper and preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2363330A true US2363330A (en) | 1944-11-21 |
Family
ID=23361372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US346870A Expired - Lifetime US2363330A (en) | 1940-07-22 | 1940-07-22 | Safety paper and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2363330A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3345251A (en) * | 1965-03-24 | 1967-10-03 | Monsanto Co | Method of sizing paper with chloroethyl sulfide or sulfone and paper thereof |
| US3725401A (en) * | 1968-09-16 | 1973-04-03 | Dow Chemical Co | Novel 3-amino-5-bromo-2h-1,4-thiazines |
| US4427676A (en) | 1980-12-19 | 1984-01-24 | John Wyeth & Brother Ltd. | Thiomorpholine derivatives |
-
1940
- 1940-07-22 US US346870A patent/US2363330A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3345251A (en) * | 1965-03-24 | 1967-10-03 | Monsanto Co | Method of sizing paper with chloroethyl sulfide or sulfone and paper thereof |
| US3725401A (en) * | 1968-09-16 | 1973-04-03 | Dow Chemical Co | Novel 3-amino-5-bromo-2h-1,4-thiazines |
| US4427676A (en) | 1980-12-19 | 1984-01-24 | John Wyeth & Brother Ltd. | Thiomorpholine derivatives |
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