US2875089A - Process for the optical brightening of - Google Patents
Process for the optical brightening of Download PDFInfo
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- US2875089A US2875089A US2875089DA US2875089A US 2875089 A US2875089 A US 2875089A US 2875089D A US2875089D A US 2875089DA US 2875089 A US2875089 A US 2875089A
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- optical brightening
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- 238000000034 method Methods 0.000 title claims description 44
- 238000005282 brightening Methods 0.000 title claims description 36
- 230000003287 optical Effects 0.000 title claims description 34
- 239000000463 material Substances 0.000 claims description 48
- 150000001875 compounds Chemical group 0.000 claims description 40
- 229920000728 polyester Polymers 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000975 dye Substances 0.000 claims description 8
- 230000003381 solubilizing Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 description 66
- 239000000835 fiber Substances 0.000 description 50
- 238000005406 washing Methods 0.000 description 36
- 239000004744 fabric Substances 0.000 description 26
- 239000000203 mixture Substances 0.000 description 26
- 239000005977 Ethylene Substances 0.000 description 22
- 230000000694 effects Effects 0.000 description 18
- 239000005020 polyethylene terephthalate Substances 0.000 description 16
- 125000004432 carbon atoms Chemical group C* 0.000 description 14
- 239000007859 condensation product Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- -1 thiazolium compounds Chemical class 0.000 description 12
- 229920004933 Terylene® Polymers 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000000344 soap Substances 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 229940100996 SODIUM BISULFATE Drugs 0.000 description 8
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M Sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 8
- 150000002191 fatty alcohols Chemical class 0.000 description 8
- 125000005842 heteroatoms Chemical group 0.000 description 8
- 125000000623 heterocyclic group Chemical group 0.000 description 8
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 8
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 6
- 229920004934 Dacron® Polymers 0.000 description 6
- FEWJPZIEWOKRBE-XIXRPRMCSA-N Mesotartaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-XIXRPRMCSA-N 0.000 description 6
- AYTGUZPQPXGYFS-UHFFFAOYSA-N Urea nitrate Chemical compound NC(N)=O.O[N+]([O-])=O AYTGUZPQPXGYFS-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 125000004433 nitrogen atoms Chemical group N* 0.000 description 6
- 229960001367 tartaric acid Drugs 0.000 description 6
- 235000002906 tartaric acid Nutrition 0.000 description 6
- 239000011975 tartaric acid Substances 0.000 description 6
- 239000004753 textile Substances 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N Chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- 125000003282 alkyl amino group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000007844 bleaching agent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000001264 neutralization Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 125000002971 oxazolyl group Chemical group 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920000151 polyglycol Polymers 0.000 description 4
- 239000010695 polyglycol Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- ZLYYJUJDFKGVKB-OWOJBTEDSA-N (E)-but-2-enedioyl dichloride Chemical compound ClC(=O)\C=C\C(Cl)=O ZLYYJUJDFKGVKB-OWOJBTEDSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- LCJRHAPPMIUHLH-UHFFFAOYSA-N 1-$l^{1}-azanylhexan-1-one Chemical compound [CH]CCCCC([N])=O LCJRHAPPMIUHLH-UHFFFAOYSA-N 0.000 description 2
- AQXYVFBSOOBBQV-UHFFFAOYSA-N 1-amino-4-hydroxyanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2N AQXYVFBSOOBBQV-UHFFFAOYSA-N 0.000 description 2
- WNKQDGLSQUASME-UHFFFAOYSA-N 4-sulfophthalic acid Chemical compound OC(=O)C1=CC=C(S(O)(=O)=O)C=C1C(O)=O WNKQDGLSQUASME-UHFFFAOYSA-N 0.000 description 2
- 239000004129 EU approved improving agent Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N Sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N Sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 210000002268 Wool Anatomy 0.000 description 2
- 125000004442 acylamino group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 125000000033 alkoxyamino group Chemical group 0.000 description 2
- 125000005577 anthracene group Chemical group 0.000 description 2
- 150000003851 azoles Chemical group 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-O hydron;1,3-oxazole Chemical compound C1=COC=[NH+]1 ZCQWOFVYLHDMMC-UHFFFAOYSA-O 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 125000005341 metaphosphate group Chemical group 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 150000002916 oxazoles Chemical class 0.000 description 2
- 125000004043 oxo group Chemical group O=* 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N oxygen atom Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atoms Chemical group O* 0.000 description 2
- 230000002085 persistent Effects 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000011528 polyamide (building material) Substances 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3437—Six-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/60—Optical bleaching or brightening
Definitions
- the material to be improved by the use of the present process can exist in any stage of processing, it being obviously advantageous to treat it in the described manner at a stage when all other treatments have been completed which would have the effect of removing again the agent used according to the invention or would have an unfavorable etfect upon it.
- the agents used can for example be added to the material to be improved either before or during the shaping thereof.
- they can be added to the moulding mass to be used in the manufacture of foils or shaped bodies or can be dissolved or finely distributed in a spinning mass before the spinning thereof.
- the present process has proved to be of especial advantage for the improvement of textile fibers of the specified constitution.
- fibers to be treated such of polyesters of terephthalic acid are especially concerned.
- Staple fibers or also monofilaments can be used, for example the products obtainable under the names Dacron and Terylene.
- the compounds used according to this invention for the improvement of the specified materials must satisfy the requirements set forth in their above-description. They must contain no acid salt-forming or water-solubilizing groups, that is to say no sulfonic acid or carboxylic acid groups. Moreover, they must at most be only slightly colored and must have no dyestufi character, i. e. they should not dye the material under treatment when applied in the customary concentrations.
- the compounds have as a rule basic character and can be used in'the present process either as free bases or in the form of salts which are capable of the formation of the free bases. As above specified, however, the use is excluded from the present process of the quaternary salts obtainable from these compounds (imidazolium, oxazolium' or thiazolium compounds).
- the compounds used in the improvement process of this invention contain two S-membered heterocyclic-rings and each of these rings, which as re- States Patent gards chemical constitution are comprised within the ice definition azole rings, possesses a structure which corresponds to one or other of the following formula
- the two adjacent carbon atoms are at the same time ring members of a benzene ring which may contain further substituents.
- the two rings are attached together through the carbon atom between the two hetero atoms by way of an ethylene bridge.
- the compounds to be used in the present process are known in large numbers and others can be prepared by customary methods known per se.
- the quantity of the improving agent to be used can vary within wide limits. Even with very small quantities, in some cases, for example, of 0.01 percent, a distinct and permanent effect can be attained. Although quantities of more than about 3 percent are in general not disadvantageous, they offer no advantages compared with the normal quantities.
- the polyester fibers can be simultaneously dyed and improved as regards optical properties if they are treated according to the present process, advantageously in the presence of a dispersing agent and dyed by the dispersion method, using as dyestuffs colored compounds which possess the anthracene structure and which in addition contain at least one nuclear-bound oxo group, at least one hydroxyl group or a non-water-solubilizing, sulfur-containing substituent and in which the number of any basic, nitrogen-containing groups present is at most equal to the number of the hydroxyl groups and sulfur-containing substituents.
- l-hydroxy-anthraquinone 1-amino-4z5:8-trihydroxy-anthraquinone and 1- amino-4-hydroxyanthraquino
- washing agents and brightening agents can be separately added to the washing baths to be used. It is also advantageous to use washing agents which contain brightening agents admixed therewith.
- washing agents are suitable for example, soaps, salts of sulfonate washing agents, as for example, of sulfonated benzimidazoles substituted on the Z-carbon atom by higher alkyl residues, also salts of monocarboxylic acid esters of 4-sulfophthalic acid with higher fatty alcohols or salts of fatty alcohol sulfonates, alkylaryl sulfonic acids or condensation products of higher fatty acids with aliphatic hydroxyor amino-sulfonic acids.
- Non-ionic washing agents can also be used, for example polyglycol ethers which are derived from ethylene oxide and higher fatty alcohols, alkyl phenols or fatty amines.
- the washing agents of the above specified type can also contain the customary washing agent additions, such as alkali metal carbonates, phosphates, pyrophosphates, polyphosphates, metaphosphates, silicates, perborates or percarbonates, so long as the brightening agents are compatible with such additions. It is also possible to prepare washing agents which consist solely or for the most part of inorganic compounds of cleansing effect and the brightening agents.
- the production of the mixtures of the washing agents and optical brightening agents takes place in a simple manner by mixing and/or grinding of the components together. In this case it may be of advantage to use one or the other component in the dissolved or molten condition for the purpose of facilitating distribution.
- the optical improving agents to the washing agents suffices.
- quantities of 0.1 to 5 percent calculated on the washing agent are concerned, for example, quantities of 0.1 to 5 percent calculated on the washing agent.
- smaller quantities for example, 0.01 percent or even less can be added.
- mixtures with other known brightening agents can be used.
- the washing agents are used in the customary washing processes. In this manner materials to be cleansed can be simultaneously washed and brightened.
- the combined treatment advantageously takes place with the aid of suitably constituted preparations.
- These stable preparations are characterized by a content of compounds of the type specified above, especially derivatives of oxazole, and also further textile treating agents, for example dyestuffs, chemical bleaching agents, finishing agents or especially washing agents.
- Example 1 Polyester fabrics are treated for 20 minutes at C. in a bath ratio 1:40 with 0.02 percent of ucfldi-[benzoxazyl-(2) J-ethylene of the formula S thenrinsed and dried. The resulting fabric has a higher white content than the untreated material. If instead of 1 gram of disodium sulfate, 1 gram of 85' percent formic acid is used, a similar efiect is attained.
- the fabric appears brighter than the untreated material.
- Example'j 30 parts of 7 ct :fl-di-[N-methyhbenzimidagyh(Z) ]-eth'y1- are are ground to a fine, homogeneous powder in a suitable mixing and gr'inding apparatus with 60 parts of sodium bisulfate and 910 parts of a condensation product from naphthalene sulfonic acid and formaldehyde.
- Polyester fibers for example Terylene, which have been treated in a bath ratio of 1:30 for 30 minutes at 80100 C. with 2 percent of this powder in a bath which contains per liter l-2 cc. of ammonia, then rinsed and dried, possess a brighter appearance than the untreated material.v v r If the 60 grams of sodium bisulfate are replaced by 60 grams of a condensation product from naphthalene sulfonic acid and formaldehyde or 60 grams of urea nitrate or 60 grams 'of tartaric acid, a product with similar properties is obtained.
- Example 4 so parts of aiB-di-[N-methyl benzirnidazyl- (2)]:ethy1- en'eare ground to a fine, homogeneous powder with 950 parts oftartaric acid.
- Polyester fibers, 'for example Dacron which are treated in a-bath ratio. of 1:40 for 30 minutes at -95 C. with 1- percent of the powder in a bath which contains per liter 1-2.cc. of ammonia and 1 gram ofthe sodium salt of 2-heptadecyl-N-benzylbenzimidazyl disulfonic acid, then rinsed 'and dried, possess a brighter appearance than the untreated material.
- a soap is produced which contains 0.3 percent of 2:5 di-[5-methylbenzoxazolyl t2)]-ethylene.
- Polyester fibers for example Tery lenef which have been Washed in the usual way with-thissoap,"have a brighter appearance than ⁇ material which isi only washed with soap. 1
- Example 6 12 parts of a:B-di-[5-methylbenzoxazolyl-(2)]-ethylene are worked up to a .finely dispersed paste with l2'parts of an addition-product from, about 30 mols of ethylene oxide to a mixture of saturated fatty alcohols most of which have 18 carbon: atoms and 76 parts of water.
- Polyester fibers for example Dacron, which are treated in a bath ratio'of 1:30 for 30 minutes: at 60- C. with 0.2-percent of this paste in a bath which contains per liter 1 cc. of ammonia, then rinsed and dried, possess a brighter appearance than the untreated material.
- other dispersion agents can also. be used, for example a condensation product from naphthalene sulfonic acid and formaldehyde.
- the a: S-di-[S-methyl-berixoxazolyL(2)I-ethylene may be prepared as follows: I
- Example 7 A mixed fabric frompolyester fibers, for example Terylene and wool is treated in a bath ratio-1:50 for 30 minutes at 60-90 C. with 2 percent of the preparation obtained according to Example 3, in a bath containing 1 gram of ammonia per liter. a
- the resulting fabric has a higher white content than the untreated material.
- Example -Terylene, C. in a bath of the Example 9 T erylene fabric is dyed for one hour at 90-95 C. in a bath which (calculated on the fabric) contains:
- a fabric dyed in the same manner but without the addition of the di-imidazole compound is less pure in shade and does not fluoresce.
- Example 10 "Ierylene fabric is treated at 80-90 C. in a finishing bath of the following composition: I
- a process for the optical brightening of materials of polyesters which comprises treating the material with a non-quaternary compound which is free from acid saltforming, water solubilizing groups and groups imparting dyestuif character, which in solution fluoresces green-blue to violet and which corresponds to the formula crystallized from dioxane.
- A is a monocyclic aromatic radical condensed in the manner indicated by the valence bonds with the oxazole ring.
- a process for the optical brightening of polyester fibers which comprises applying to said fibers in a finely dispersed state the optical brightening agent of the formula 3.
- a process for the optical brightening of polyester fibers which comprises applying to said fibers in the presence of a dispersing agent the optical brightening agent of the formula 4.
- a process for the optical brightening of polyester fibers which comprises applying to said fibers in the presence of a washing agent the optical brightening agent of the formula 5.
- a composition of matter substantially consisting of a polyester and having incorporated in it a small quantity of a non-quaternary compound which is free from acid salt-forming, water solubilizing groups and groups imparting dyestuff character, which in solution fluoresces green-blue to violet and which corresponds to the formula in which A is monocyclic aromatic radical condensed in the manner indicated by the valence bonds with the oxazole ring.
- composition of matter substantially consisting of polyester fibers having incorporated a small quantity of the optical brightening agent of the formula References Cited in the file of this patent UNITED STATES PATENTS H1O CHI 2,463,264 Graenacher Mar. 1, 1949 2,483,392 Meyer Oct. 4, 1949 2,488,094 Graenacher Nov. 15, 1949 2,515,173 Ackermann July 18, 1950 2,604,454 Ackermann July 22, 1952 2,785,133 Craig Mar. 12, 1957 FOREIGN PATENTS 611,510 Great Britain Nov. 1, 1948
Description
PROCESS FOR THE OPTICAL BRIGHTENING OF MATERIALS OF POLYESTERS Franz Ackermann, Binningeu, and Adolf Emil Siegrist, Basel, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swiss firm w No Drawing. Application February 6, 1956 Serial No. 563,446
Claims priority, application Switzerland February 15, 1955 6 Claims. or. 117- 435 This invention is based onthe observation that materials of polyesters, especially polyester fibers, can be optically brightened when such a material is treated with a non-quaternary compound having no dyestuff character, which is colorless or only slightly colored, contains no acid salt-forming or water-solubilizing group, which in solution or on a substratum fluoresces green-blue to violet in daylight or ultra-violet light and which contains two five-membered heterocyclic rings, each of which consists of two adjacent carbon atoms which are at the same time ring members of a benzene ring, a nitrogen atom attached to one of the two mentioned carbon atoms, a hetero atom having an atomic number of at least 7 and at most 8, viz. an oxygen, or nitrogen atom attached to the other of the two mentioned carbon atoms and a carbon atom attached to both hetero atoms, the two latter carbon atoms of the two heterocyclic rings being attached together by way of an ethylene bridge.
The material to be improved by the use of the present process can exist in any stage of processing, it being obviously advantageous to treat it in the described manner at a stage when all other treatments have been completed which would have the effect of removing again the agent used according to the invention or would have an unfavorable etfect upon it. The agents used can for example be added to the material to be improved either before or during the shaping thereof. Thus they can be added to the moulding mass to be used in the manufacture of foils or shaped bodies or can be dissolved or finely distributed in a spinning mass before the spinning thereof.
The present process has proved to be of especial advantage for the improvement of textile fibers of the specified constitution. As fibers to be treated, such of polyesters of terephthalic acid are especially concerned. Staple fibers or also monofilaments can be used, for example the products obtainable under the names Dacron and Terylene.
The compounds used according to this invention for the improvement of the specified materials must satisfy the requirements set forth in their above-description. They must contain no acid salt-forming or water-solubilizing groups, that is to say no sulfonic acid or carboxylic acid groups. Moreover, they must at most be only slightly colored and must have no dyestufi character, i. e. they should not dye the material under treatment when applied in the customary concentrations. The compounds have as a rule basic character and can be used in'the present process either as free bases or in the form of salts which are capable of the formation of the free bases. As above specified, however, the use is excluded from the present process of the quaternary salts obtainable from these compounds (imidazolium, oxazolium' or thiazolium compounds).
As stated above the compounds used in the improvement process of this invention contain two S-membered heterocyclic-rings and each of these rings, which as re- States Patent gards chemical constitution are comprised within the ice definition azole rings, possesses a structure which corresponds to one or other of the following formula In both rings the two adjacent carbon atoms are at the same time ring members of a benzene ring which may contain further substituents. Moreover, the two rings are attached together through the carbon atom between the two hetero atoms by way of an ethylene bridge.
Accordingly, in the present process compounds are'used of the formula (a) B\ Y A A o-oH=oH-o V A I in which A indicates abenzene radical condensed with the hetero ring as shown by the valence bonds, B is an oxygen atom or the group and D are nitrogen atoms of which each is also further attached to-a low molecular alkyl radical, for example such a radical containing at most six-carbon atoms, but preferably an ethyl or methyl group.
Since the double bonds of the radical Act the abovementioned general formulae are in conjugation with the double bond of the heterocyclic ring, by suitable substitution of this radical an increase of the fluorescence can also be attained. As substituents in the radical A there are concerned alkyl, alkoxy, alkylamino or acylamino groups or halogen atoms. I
Thus, for example, valuable results can also be achieved with the compounds of the formula Illa it A1. bQ/oqzrhon-ofi in 3 azfl-di-[benzoxazolyl-(Z)J-ethylenes of the Formula 3 whose benzene radicals A are substituted by low molecular alkyl groups, particularly methyl groups which are preferably in the S-positions of the benzoxazole radicals.
The compounds to be used in the present process are known in large numbers and others can be prepared by customary methods known per se.
If it is a question of improving textile fibers by the present process which can exist as staple fibers or monofilaments, in the crude state or in the form of yarns or fabrics, this operation is conducted with advantage in an aqueous medium in which the compounds to be used are dissolved or suspended. If desired dispersing agents can be added in the treatment, for example, soaps, polyglycol ethers of fatty alcohols or fatty amines, cellulose sulfite waste liquor. or condensation products with formaldehyde of naphthalene sulfonic acids which may be alkylated.
It'is of particular advantage, especially when the treatment of the fibers is exclusively for the purpose of improving the optical properties, to work in neutral, weakly alkaline or acid baths. It is likewise of advantage if the treatment takes place at elevated temperature, for example at the boiling temperature of the bath or in the neighborhood thereof (about 90 C.). It is surprising that the compounds of the composition set forth above possess a good atfinity for the fibers and can be fixed thereon in a similar manner to dyestufis. In this connection it may be remarked that in the case of these synthetic fibers many optical improving and brightening agents which are of good applicability for other fiber materials, cannot be used for the reason that in this case they cannot be fixed on the fiber or do not give rise to the desired effect. The fastness to light of the materials treated according to the present process is also good, the effect persisting even after long exposure to light.
The quantity of the improving agent to be used, calculated on the material to be treated, can vary within wide limits. Even with very small quantities, in some cases, for example, of 0.01 percent, a distinct and permanent effect can be attained. Although quantities of more than about 3 percent are in general not disadvantageous, they offer no advantages compared with the normal quantities.
As indicated above, the present process can advantageously be combined with other processing methods. Thus the compounds to be used according to the present invention can' also be applied as follows:
(a) In admixture with dyestuffs or as additions to dyebaths or printing, discharge or reserve pastes. Further also for the after-treatment of dyeings, prints or discharge prints, especially in the soaping process. Thus, for example, the polyester fibers can be simultaneously dyed and improved as regards optical properties if they are treated according to the present process, advantageously in the presence of a dispersing agent and dyed by the dispersion method, using as dyestuffs colored compounds which possess the anthracene structure and which in addition contain at least one nuclear-bound oxo group, at least one hydroxyl group or a non-water-solubilizing, sulfur-containing substituent and in which the number of any basic, nitrogen-containing groups present is at most equal to the number of the hydroxyl groups and sulfur-containing substituents. As examples of such compounds may be mentioned l-hydroxy-anthraquinone, 1-amino-4z5:8-trihydroxy-anthraquinone and 1- amino-4-hydroxyanthraquinone.
(b) In admixture with chemical bleaching agents 0 as additions to bleaching baths.
. (c) In admixture with finishing agents such as starch or synthetic finishes. The compounds to be used according to the invention can for example also be added to the baths used for the production of a crease-proof finish. r
(d) In combination with washing agents: The washing agents and brightening agents can be separately added to the washing baths to be used. It is also advantageous to use washing agents which contain brightening agents admixed therewith. As washing agents are suitable for example, soaps, salts of sulfonate washing agents, as for example, of sulfonated benzimidazoles substituted on the Z-carbon atom by higher alkyl residues, also salts of monocarboxylic acid esters of 4-sulfophthalic acid with higher fatty alcohols or salts of fatty alcohol sulfonates, alkylaryl sulfonic acids or condensation products of higher fatty acids with aliphatic hydroxyor amino-sulfonic acids. Non-ionic washing agents can also be used, for example polyglycol ethers which are derived from ethylene oxide and higher fatty alcohols, alkyl phenols or fatty amines.
The washing agents of the above specified type can also contain the customary washing agent additions, such as alkali metal carbonates, phosphates, pyrophosphates, polyphosphates, metaphosphates, silicates, perborates or percarbonates, so long as the brightening agents are compatible with such additions. It is also possible to prepare washing agents which consist solely or for the most part of inorganic compounds of cleansing effect and the brightening agents. The production of the mixtures of the washing agents and optical brightening agents takes place in a simple manner by mixing and/or grinding of the components together. In this case it may be of advantage to use one or the other component in the dissolved or molten condition for the purpose of facilitating distribution.
In general a small addition of the optical improving agents to the washing agents suffices. There are concerned, for example, quantities of 0.1 to 5 percent calculated on the washing agent. Also smaller quantities, for example, 0.01 percent or even less can be added. Also mixtures with other known brightening agents can be used. The washing agents are used in the customary washing processes. In this manner materials to be cleansed can be simultaneously washed and brightened.
When the present process is combined with other treatment or improvement methods, for example those set forth above under (a) to (d), the combined treatment advantageously takes place with the aid of suitably constituted preparations. These stable preparations are characterized by a content of compounds of the type specified above, especially derivatives of oxazole, and also further textile treating agents, for example dyestuffs, chemical bleaching agents, finishing agents or especially washing agents.
Further valuable preparations which are primarily suited for the improvement of polyester fiber as regards optical properties alone, that is to say without additional treatment according to (a) to (d), are distinguished by the fact that they contain in addition to the compounds of the composition initially described above also acidreacting, preferably solid substances. As examples of such substances may be mentioned sodium bisulfate, tartaric acid and urea nitrate.
The following examples illustrate the invention, the parts and percentages being by weight unless otherwise stated:
Example 1 Polyester fabrics are treated for 20 minutes at C. in a bath ratio 1:40 with 0.02 percent of ucfldi-[benzoxazyl-(2) J-ethylene of the formula S thenrinsed and dried. The resulting fabric has a higher white content than the untreated material. If instead of 1 gram of disodium sulfate, 1 gram of 85' percent formic acid is used, a similar efiect is attained.
I Example 2 V The process is conducted as described in Example 1 but there is used instead of 0.02 percent of azp-di-[benzoxazyl-(2)]-ethylene 0.2 percent of a-[N-hydroxyethylbenzimidazyl (2)] 13 [N methylbenzimidazyl (2)]-ethylene of the formula N /N CCH=CHO omomorr H3 The fabric appears brighter than the untreated material. Similar effects are obtained with the compounds of the following formulae l& CHPCHQNQCHM I Example'j 30 parts of 7 ct :fl-di-[N-methyhbenzimidagyh(Z) ]-eth'y1- are are ground to a fine, homogeneous powder in a suitable mixing and gr'inding apparatus with 60 parts of sodium bisulfate and 910 parts of a condensation product from naphthalene sulfonic acid and formaldehyde.
Polyester fibers, for example Terylene, which have been treated in a bath ratio of 1:30 for 30 minutes at 80100 C. with 2 percent of this powder in a bath which contains per liter l-2 cc. of ammonia, then rinsed and dried, possess a brighter appearance than the untreated material.v v r If the 60 grams of sodium bisulfate are replaced by 60 grams of a condensation product from naphthalene sulfonic acid and formaldehyde or 60 grams of urea nitrate or 60 grams 'of tartaric acid, a product with similar properties is obtained.
:imilar effects are obtained with azfi-di-[N-ethylbenzimidazyl-(Zfl-ethylene.
Example 4 so parts of aiB-di-[N-methyl benzirnidazyl- (2)]:ethy1- en'eare ground to a fine, homogeneous powder with 950 parts oftartaric acid. Polyester fibers,= 'for example Dacron which are treated in a-bath ratio. of 1:40 for 30 minutes at -95 C. with 1- percent of the powder in a bath which contains per liter 1-2.cc. of ammonia and 1 gram ofthe sodium salt of 2-heptadecyl-N-benzylbenzimidazyl disulfonic acid, then rinsed 'and dried, possess a brighter appearance than the untreated material. v
- Byusing instead of 1 gram of the above preparation, 1 gram of a powder whichcontains instead of the tartaric acid, sodium bisulfate or urea nitrate or another suitable solid substancesoluble in water with an acid reaction, the resulting fabriehas a similar efiect.
Example, 5
A soap is produced which contains 0.3 percent of 2:5 di-[5-methylbenzoxazolyl t2)]-ethylene. I
Polyester fibers, for example Tery lenef which have been Washed in the usual way with-thissoap,"have a brighter appearance than}material which isi only washed with soap. 1
A similar effect is obtained when there is added per liter of wash liquor 0.5 grampf active chlorine in the formof sodium hypochlorite'f 7 Instead of the soap a washing material ca n be used of the following composition or also synthetic washingagents. Example 6 12 parts of a:B-di-[5-methylbenzoxazolyl-(2)]-ethylene are worked up to a .finely dispersed paste with l2'parts of an addition-product from, about 30 mols of ethylene oxide to a mixture of saturated fatty alcohols most of which have 18 carbon: atoms and 76 parts of water. I
Polyester fibers, for example Dacron, which are treated in a bath ratio'of 1:30 for 30 minutes: at 60- C. with 0.2-percent of this paste in a bath which contains per liter 1 cc. of ammonia, then rinsed and dried, possess a brighter appearance than the untreated material. 4 4 i Instead of the above described addition product, other dispersion agents can also. be used, for example a condensation product from naphthalene sulfonic acid and formaldehyde. The a: S-di-[S-methyl-berixoxazolyL(2)I-ethylene may be prepared as follows: I
76 parts of fumaric acid dichloride are added dropwise to a solution of 123 parts of 1-amino-Z-hydroxy-S-methylbenzene in l200'parts of 'chlorobenzene with stirring and exclusion of air at 125-130 C. in the course of one hour, and the mixture is then maintained at a gentle boil for 6 hours; The'resulting yellowish condensation product of the formula 7 then added dropwise, the temperature being allowedv to drop. Concentrated hydrochloric acid is then added until the reaction is acid. The mixture is stirred for another hour at abouta60 C., the'separated product is filtered off, washed with water until the. filtrate shows a neutral reaction and, if necessary, is There is obtained a:B-di-[S-methyl-benzoxazolyl-(2)]- ethylene in the form of pale crystals which melt at 292 C. The solution in dioxaneexhibits a bluish fluorescence.
- Example 7 A mixed fabric frompolyester fibers, for example Terylene and wool is treated in a bath ratio-1:50 for 30 minutes at 60-90 C. with 2 percent of the preparation obtained according to Example 3, in a bath containing 1 gram of ammonia per liter. a
The resulting fabric has a higher white content than the untreated material. j
A similar effect visobtained in the case of a fabric consisting of polyester fibers, for example Terylene, and polyamide fibers, for example Perlon.
- Example 8 IOO pa rts of polyester fabric, for are treated for one hour at 60-90 following composition:
example -Terylene, C. in a bath of the Example 9 T erylene fabric is dyed for one hour at 90-95 C. in a bath which (calculated on the fabric) contains:
2% l:4-dimethylamino-anthraquinone and 4% a fi-di-[N-methyl-benzimidazolyl-(2) ]-ethylene The goods to liquor ratio is 1:40. After being rinsed and dried the fabric so treated has a pure greenish blue and bluish fluorescent shade.
A fabric dyed in the same manner but without the addition of the di-imidazole compound is less pure in shade and does not fluoresce.
Example 10 "Ierylene fabric is treated at 80-90 C. in a finishing bath of the following composition: I
1 liter water 20 grams potato starch 1 cc. ammonia 24% 0.5 gram of the product described in the first paragraph of Example 6 After squeezing and drying the material thus finished has a brighter appearance than material which has been finished only with starch.
What is claimed is:
l. A process for the optical brightening of materials of polyesters which comprises treating the material with a non-quaternary compound which is free from acid saltforming, water solubilizing groups and groups imparting dyestuif character, which in solution fluoresces green-blue to violet and which corresponds to the formula crystallized from dioxane.
in which A is a monocyclic aromatic radical condensed in the manner indicated by the valence bonds with the oxazole ring.
2. A process for the optical brightening of polyester fibers which comprises applying to said fibers in a finely dispersed state the optical brightening agent of the formula 3. A process for the optical brightening of polyester fibers which comprises applying to said fibers in the presence of a dispersing agent the optical brightening agent of the formula 4. A process for the optical brightening of polyester fibers which comprises applying to said fibers in the presence of a washing agent the optical brightening agent of the formula 5. A composition of matter substantially consisting of a polyester and having incorporated in it a small quantity of a non-quaternary compound which is free from acid salt-forming, water solubilizing groups and groups imparting dyestuff character, which in solution fluoresces green-blue to violet and which corresponds to the formula in which A is monocyclic aromatic radical condensed in the manner indicated by the valence bonds with the oxazole ring.
,6. A composition of matter substantially consisting of polyester fibers having incorporated a small quantity of the optical brightening agent of the formula References Cited in the file of this patent UNITED STATES PATENTS H1O CHI 2,463,264 Graenacher Mar. 1, 1949 2,483,392 Meyer Oct. 4, 1949 2,488,094 Graenacher Nov. 15, 1949 2,515,173 Ackermann July 18, 1950 2,604,454 Ackermann July 22, 1952 2,785,133 Craig Mar. 12, 1957 FOREIGN PATENTS 611,510 Great Britain Nov. 1, 1948
Claims (1)
1. A PROCESS FOR THE OPTICAL BRIGHTENING OF MATERIALS OF POLYESTERS WHICH COMPRISES TREATING THE MATERIAL WITH A NON-QUATERNARY COMPOUND WHICH IS FREE FROM ACID SALTFORMING, WATER SOLUBILIZING GROUPS AND GROUPS IMPARTING DYESTUFF CHARACTER, WHICH IN SOLUTION FLUORESCES GREEN-BLUE TO VIOLET AND WHICH CORRESPONDS TO THE FORMULA
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| US2875089A true US2875089A (en) | 1959-02-24 |
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| US2875089D Expired - Lifetime US2875089A (en) | Process for the optical brightening of |
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| US (1) | US2875089A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3005779A (en) * | 1955-02-15 | 1961-10-24 | Ciba Ltd | Process for the optical brightening of polyacrylonitrile fibers |
| US3169960A (en) * | 1965-02-16 | Asylgxazolyl optical brightening | ||
| US3242807A (en) * | 1961-12-26 | 1966-03-29 | Union Oil Co | Ultraviolet absorbing composition |
| US3262929A (en) * | 1961-09-12 | 1966-07-26 | Mitsui Kagaku Kogyo Kabushiki | 2-styrylbenzoxazole compounds |
| US3380955A (en) * | 1964-08-03 | 1968-04-30 | Mobay Chemical Corp | Polyester polyols containing a coumarin brightener and a blue dye |
| EP0982149A1 (en) * | 1998-08-28 | 2000-03-01 | Dai Nippon Printing Co., Ltd. | Fluorescent latent image transfer film, transfer method using the same, and security pattern formed matter |
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|---|---|---|---|---|
| GB611510A (en) * | 1944-09-29 | 1948-11-01 | Ciba Ltd | Process for improving the whiteness or colour of materials |
| US2463264A (en) * | 1942-12-23 | 1949-03-01 | Ciba Ltd | Derivatives of cyclic amidines and process of making same |
| US2483392A (en) * | 1949-10-04 | Substituted ethylenes and process | ||
| US2488094A (en) * | 1942-12-23 | 1949-11-15 | Ciba Ltd | Diimidazoles and process of making same |
| US2515173A (en) * | 1950-07-18 | Diimidazoles and process of making | ||
| US2604454A (en) * | 1947-03-19 | 1952-07-22 | Ciba Ltd | Detergent composition containing diimidazoles |
| US2785133A (en) * | 1954-03-26 | 1957-03-12 | Gen Aniline & Film Corp | Compositions for a method of whitening fine fabrics |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2483392A (en) * | 1949-10-04 | Substituted ethylenes and process | ||
| US2515173A (en) * | 1950-07-18 | Diimidazoles and process of making | ||
| US2463264A (en) * | 1942-12-23 | 1949-03-01 | Ciba Ltd | Derivatives of cyclic amidines and process of making same |
| US2488094A (en) * | 1942-12-23 | 1949-11-15 | Ciba Ltd | Diimidazoles and process of making same |
| GB611510A (en) * | 1944-09-29 | 1948-11-01 | Ciba Ltd | Process for improving the whiteness or colour of materials |
| US2604454A (en) * | 1947-03-19 | 1952-07-22 | Ciba Ltd | Detergent composition containing diimidazoles |
| US2785133A (en) * | 1954-03-26 | 1957-03-12 | Gen Aniline & Film Corp | Compositions for a method of whitening fine fabrics |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3169960A (en) * | 1965-02-16 | Asylgxazolyl optical brightening | ||
| US3005779A (en) * | 1955-02-15 | 1961-10-24 | Ciba Ltd | Process for the optical brightening of polyacrylonitrile fibers |
| US3262929A (en) * | 1961-09-12 | 1966-07-26 | Mitsui Kagaku Kogyo Kabushiki | 2-styrylbenzoxazole compounds |
| US3242807A (en) * | 1961-12-26 | 1966-03-29 | Union Oil Co | Ultraviolet absorbing composition |
| US3380955A (en) * | 1964-08-03 | 1968-04-30 | Mobay Chemical Corp | Polyester polyols containing a coumarin brightener and a blue dye |
| EP0982149A1 (en) * | 1998-08-28 | 2000-03-01 | Dai Nippon Printing Co., Ltd. | Fluorescent latent image transfer film, transfer method using the same, and security pattern formed matter |
| US6368684B1 (en) | 1998-08-28 | 2002-04-09 | Dai Nippon Printing Co., Ltd. | Fluorescent latent image transfer film, fluorescent latent image transfer method using the same, and security pattern formed matter |
| EP1371498A1 (en) * | 1998-08-28 | 2003-12-17 | Dai Nippon Printing Co., Ltd. | Fluorescent latent image transfer film, fluorescent latent image, transfer method using the same, and security pattern formed matter |
| EP1619039A3 (en) * | 1998-08-28 | 2010-06-16 | Dai Nippon Printing Co., Ltd. | Fluorescent latent image transfer film, fluorescent latent image transfer method using the same, and security pattern formed matter |
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