US2528324A - Method of treating paper and the resulting products - Google Patents
Method of treating paper and the resulting products Download PDFInfo
- Publication number
- US2528324A US2528324A US661069A US66106946A US2528324A US 2528324 A US2528324 A US 2528324A US 661069 A US661069 A US 661069A US 66106946 A US66106946 A US 66106946A US 2528324 A US2528324 A US 2528324A
- Authority
- US
- United States
- Prior art keywords
- paper
- amount
- acid
- groups
- stilbene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- 239000000123 paper Substances 0.000 description 59
- 239000002253 acid Substances 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 17
- -1 NH2 radicals Chemical class 0.000 description 15
- 230000002087 whitening effect Effects 0.000 description 15
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 13
- 125000003118 aryl group Chemical group 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000007844 bleaching agent Substances 0.000 description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 7
- BIEFDNUEROKZRA-UHFFFAOYSA-N 2-(2-phenylethenyl)aniline Chemical class NC1=CC=CC=C1C=CC1=CC=CC=C1 BIEFDNUEROKZRA-UHFFFAOYSA-N 0.000 description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003435 aroyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NQDXQECIJLEBLG-UHFFFAOYSA-N 2-benzamido-6-(1,2-diamino-2-phenylethenyl)benzenesulfonic acid Chemical compound NC(=C(C=1C(=C(C=CC1)NC(C1=CC=CC=C1)=O)S(=O)(=O)O)N)C1=CC=CC=C1 NQDXQECIJLEBLG-UHFFFAOYSA-N 0.000 description 2
- HSHNITRMYYLLCV-UHFFFAOYSA-N 4-methylumbelliferone Chemical compound C1=C(O)C=CC2=C1OC(=O)C=C2C HSHNITRMYYLLCV-UHFFFAOYSA-N 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VIFBEEYZXDDZCT-UHFFFAOYSA-N 2-(2-phenylethenyl)benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1C=CC1=CC=CC=C1 VIFBEEYZXDDZCT-UHFFFAOYSA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 241001648341 Orites Species 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 125000003944 tolyl 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
- D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/916—Fraud or tamper detecting
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/916—Natural fiber dyeing
- Y10S8/918—Cellulose textile
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/916—Natural fiber dyeing
- Y10S8/919—Paper
Definitions
- Patented Oct. 31, 1950 METHOD OF TREATING PAPER AND THE RESULTING PRODUCTS Richard Thomas, Bromborough, England, asaignor to Lever Brothers Company. a corporation of Maine No Drawing. Application April 10, 1946, Serial No. 661,069. In Great Britain April 12, 1945 such as hypochlorite. It also relates to the resulting treated paper.
- an improved whitening efiect of stability and durability can be obtained by using as a treating agent a derivative of a di-aminobenzoylaminostilbene-sulfonic acid formed by the substitution of at least one of the hydrogen atoms in each of the NH2 radicals attached to the terminal rings by an organic radical which does not contain an NH: radical directly attached to an aromatic nucleus and which would not itself render the substituted compound formed unstable to light and oxygen.
- the improved whiteening effect and stability can be imparted to paper and the like in any of several ways as described hereinafter.
- the resulting treated paper does not lose its improved whiteness upon treat- 10 Claims. (Cl. 117-335) ment with a dilute solution of hypochlorite or similar ink removing agent.
- the objects achieved by the present invention include the provision of a treating process for imparting an improved whitening effect of great stability to paper; the provision of paper comprising a small proportion of an aminostilbene derivative adapted to impart an improved whiteening effect thereto; and other objects which will be apparent after the invention is developed in more detail hereinafter.
- the stilbene derivative may be applied to normally white paper by treating the said material in a dilute aqueous solution of the stilbene derivative. If desired, the stilbene derivative may be applied to the paper after the formation into an article, such as a box or the like, or any suitable intermediate stage of the formation of the paper.
- the above defined stilbene derivatives may be derived by substituting in a diaminobenzoylamino-stilbene sulfonic acid, such as 4 :4'-di-p-aminobenzoylamino-stilbene-2 2' disulfonic acid, 4:4'-di-p-aminobenzoylaminostilbene-3:3'-disulfonic acid, 4:4'-di-p-aminobenzoyiamino-stilbene- 2:2, 6:6 tetrasulfonic acid, one or both amino hydrogen atoms by an organic radical which does not itself contain a terminal NH: radical attached to an aromatic nucleus such as a benzene ring.
- the terminal primary amino groups of the above named compounds may be benzoylated or acetylated, etc. in the usual and well-known manner. It is essential that the aminostilbene derivative contain no primary-amino aryl groups in the molecule.
- aminostilbene derivatives which may be used in accordance with the invention may be illustrated by the following formula:
- X is alkyl, aryl, aroyl, acyl, or carbamyl
- Y is H, alkyl or aryl.
- the lower aliphatic or aromatic groups are preferred as the X in the above formula.
- stilbene derivatives may contain one or more sulfonic acid groups and these may be attached anywhere in the molecule.
- the stilbene derivative may be of the symmetrical type or non-symmetrical type.
- the benzoyl group may be replaced by a corresponding polynuclear aroyl group.
- a (non-primary amino)aroylaminostilbene sulfonic acid is used as the whitening agent.
- the non-primary amino groups which are directly attached to an aryl group may be secondary (i. e. RNH-) or tertiary (i. e. R2N-), as long as R does not contain a'primary amino (NH2) group directly attached to any aryl group.
- stilbene sulfonic acids may be used in the form of their salts (i. e. sodium salt) and it is intended that the term acid compound appearing herein include the acid itself and also derivatives such as the salts which contain the anion of the acid.
- the aminostilbene derivative must be water soluble or dispersible in the presence of a detergent and this will exclude groups which impart thereto non-dispersibility in water.
- the aminostilbene derivatives used in accordance with the invention should not contain a group or radical which imparts tinctorial properties (i. e. an actual color producing or chromophorous group) or groups which tend to discolor upon exposure to light, air, or bleaching agents such as sodium hypochlorite (i. e. potential color producing or chromophorous groups).
- a group or radical which imparts tinctorial properties i. e. an actual color producing or chromophorous group
- bleaching agents such as sodium hypochlorite (i. e. potential color producing or chromophorous groups).
- phenolic hydroxy groups would be unsuitable since such phenolic compounds are known to discolor upon exposure to air.
- Thiophenolic groups are also excluded since they would tend to discolor upon exposure to air. All such groups are
- the quantity incorporated in the paper in this way may be considerably less than 0.1% (calculated on c the weight of the paper) and as little as 0.000l% has in some cases been found effective.
- the proportions (calculated on the weight of the paper) will vary between 0.01% to 0.025% and 0.0001% but, smaller amounts can be used.
- the optimum proportions for any given case within the ranges mentioned will be readily apparent to one skilled in the art. There is no advantage in using more than necessary to obtain the desired whitening effect and, of course, the amounts used should be less than sumcient to impart a colored effect to the paper.
- Example 1 An 0.1% by weight solution of sodium salt of 4:4 -di p acetylaminobenzoylamino stilbene- 2:2 -disulfonic acid is applied to the surface of the paper at a convenient stage in its manufacture, by spraying. Alternatively, a waterdoctor or any other device well known in the art for surface treatment of the paper may be used. The amount of solution applied to the paper in this way may be adjusted to leave in the paper after drying any desired percentage of the stilbene derivative in the proportions (calculated on the weight of the paper) recommended above. The resulting treated paper shows a brilliant white appearance which is not noticeably effected upon long exposure to light. The whiteness is not effected by treatment with ink eradicating agents, such as hypochl'orite solutions.
- ink eradicating agents such as hypochl'orite solutions.
- the stilbene derivative may be incorporated with the cleaned and bleached pulp before its formation into paper sheet, or it may be applied to the finished paper by immersing or dipping the paper into a solution of the stilbene derivative at any stage during the manufacture -of the paper or after it is manufactured.
- Example 2 As an example of treating a. paper by dipping it in a solution of a blue-fluorescent compound may be cited the following.
- the paper to be treated was dipped in a 0.0005% aqueous solution of 4:4 -di-p-acetylaminobenzoylamino stilbene- 2z2 -disulfonic acid. 10 parts by weight of paper were dipped in 100 parts by weight of solution for 15 minutes at 40 C., during which time the liquid was agitated continuously.
- the paper absorbed SOaH an amount of the compound corresponding to 0.0036% of the weight of the paper.
- the paper 11 CH CHONHO CO I -o C-CH;
- the invention is applicable to all types of normally white paper and by the word paper is meant the usual broad generic definition, namely cellulosic fibrous material felted or otherwise molded into sheet or other form of varying thicknesses, including cardboard and composite sheets. In general, the paper is more or less nontransparent in visible light.
- a process which comprises applying to paper. an amount in the range from 0.0001% to about 0.025%, based on the dry weight of the paper, of an aminoaroylaminostilbene sulfonic acid which is free from color producing groups and which has the following general formula:
- SOQH SOaH Y at in which X is a radical selected from the group consisting of aroyl and acyl radicals, and Y is a radical selected from the group consisting of hydrogen, alkyl and aryl radicals, by treatment with an aqueous solution of said acid, said amount of said compound being sumcient to impart a whitening effect to the paper which does not discolor upon exposure to light, air and bleaching agents.
- a process which comprises applying to paper an amount in the range from 0.0001% to about 0.025%, based on the dry weight of the paper, of a benzoylaminobenzoylaminostilbene sulfonic acid which is free from color producing groups and primary amino groups directly attached to an aryl nucleus by treatment with an aqueous solution of said acid, said amount of said compound being suificient to impart a whitening effect to the paper which does not discolor upon exposure to light, air and bleaching agents.
- a process which comprises applying to paper an amount in the range from 0.0001% to 0.01%, based on the dry weight of the paper, of a 4,4- di-p benzoylaminobenzoylaminostilbene-2,2'-disulfonic acid which is free from color producing groups, by treatment with an aqueous solution of said acid, said amount of said compound being sufficient to impart a whitening effect to the paper which does not discolor upon exposure to light, air and bleaching agents.
- a process which comprises applying to paper an amount in the range from 0.0001% to 0.01%, based on the dry weight of the paper, of a 4,4- di-p acetylaminobenzoylaminostilbene-2,2'-disulfonlc acid which is free from color producing groups by treatment with an aqueous solution of said acid, said amount of said compound being sufficient to impart a whitening effect to the paper which does not discolor upon exposure to light, air and bleaching agents.
- a paper comprising an amount in the range from about 0.0001% to about 0.025% by weight of an aminoaroylaminostilbene sulfonic acid which is free from color producing groups and which has the following general formula:
- a paper comprising an amount in the range from about 0.0001% to about 0.025% by weight of a benzoylaminobenzoylaminostilbene sulfonic acid which is free from color producing groups and primary amino groups directly attached to an aryl nucleus by treatment with an aqueous solution of said acid, said amount of said compound being suflicient to impart a whitening eii'ect to the paper which does not discolor upon exposure to light, air and bleaching agents.
- a paper comprising an amount in the range from about 0.0001% to about 0.025% by weight of an acetylaminobenzoylaminostilbene sulfonic acid which is free from color producing groups and primary amino groups directly attached to an aryl nucleus by treatment with an aqueous solution of said acid, said amount of said compound being suflicient to impart a whitening effect to the paper which does not discolor upon exposure to light, air and bleaching agents.
- a paper comprising an amount in the range from about 0.0001% to about 0.01% by weight of a 4,4'-di p-benzoylaminobenzoylaminostilbene- 2,2'-disu1fonic acid. said amount of said compound being sufilcient to impart a whitening effect to thepaper which does not discolor upon exposure to light. air and bleaching agents.
- a paper comprising an amount in the range from about 0.0001% to about 0.01% by weight of a 4,4 di p-acetylaminobenzoylaminostilbene- 2,2'-disulfonic acid, said amount of said compound being sufficient to impart a whitening eflect to the paper which does not discolor upon exposure to light, air and bleaching agents.
Landscapes
- Paper (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB913545A GB595281A (en) | 1945-04-12 | Improvements in the treatment of paper |
Publications (1)
Publication Number | Publication Date |
---|---|
US2528324A true US2528324A (en) | 1950-10-31 |
Family
ID=9866042
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US661069A Expired - Lifetime US2528324A (en) | 1945-04-12 | 1946-04-10 | Method of treating paper and the resulting products |
Country Status (4)
Country | Link |
---|---|
US (1) | US2528324A (is") |
BE (1) | BE464496A (is") |
CH (1) | CH252536A (is") |
FR (1) | FR925642A (is") |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2710285A (en) * | 1951-08-11 | 1955-06-07 | Davics Young Soap Company | Paper coating composition containing an optical brightener |
US2723288A (en) * | 1955-11-08 | Fluorescent agents | ||
US2876130A (en) * | 1955-12-21 | 1959-03-03 | Palco Chemical Company | Process for brightening suede |
US3041200A (en) * | 1958-08-28 | 1962-06-26 | Champion Papers Inc | Paper and process for manufacture |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2089413A (en) * | 1937-08-10 | Production of novel effects on | ||
US2089293A (en) * | 1934-08-08 | 1937-08-10 | Ici Ltd | Safety paper |
-
0
- BE BE464496D patent/BE464496A/xx unknown
-
1946
- 1946-04-03 CH CH252536D patent/CH252536A/de unknown
- 1946-04-10 US US661069A patent/US2528324A/en not_active Expired - Lifetime
- 1946-04-15 FR FR925642D patent/FR925642A/fr not_active Expired
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2089413A (en) * | 1937-08-10 | Production of novel effects on | ||
US2089293A (en) * | 1934-08-08 | 1937-08-10 | Ici Ltd | Safety paper |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2723288A (en) * | 1955-11-08 | Fluorescent agents | ||
US2710285A (en) * | 1951-08-11 | 1955-06-07 | Davics Young Soap Company | Paper coating composition containing an optical brightener |
US2876130A (en) * | 1955-12-21 | 1959-03-03 | Palco Chemical Company | Process for brightening suede |
US3041200A (en) * | 1958-08-28 | 1962-06-26 | Champion Papers Inc | Paper and process for manufacture |
Also Published As
Publication number | Publication date |
---|---|
BE464496A (is") | |
CH252536A (de) | 1948-01-15 |
FR925642A (fr) | 1947-09-09 |
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