US3667999A - Flame retardant cellulosic materials - Google Patents
Flame retardant cellulosic materials Download PDFInfo
- Publication number
- US3667999A US3667999A US3667999DA US3667999A US 3667999 A US3667999 A US 3667999A US 3667999D A US3667999D A US 3667999DA US 3667999 A US3667999 A US 3667999A
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- United States
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- flame retardant
- urea
- Prior art date
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 20
- 239000003063 flame retardant Substances 0.000 title abstract description 20
- 239000000463 material Substances 0.000 title abstract description 19
- 238000000034 method Methods 0.000 abstract description 25
- 239000004925 Acrylic resin Substances 0.000 abstract description 24
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 abstract description 23
- 229920000178 Acrylic resin Polymers 0.000 abstract description 20
- 150000001875 compounds Chemical class 0.000 abstract description 10
- -1 AMINO GROUP Chemical group 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 83
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 40
- 239000004202 carbamide Substances 0.000 description 18
- 239000007787 solid Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 229920000058 polyacrylate Polymers 0.000 description 5
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000003906 humectant Substances 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- YBBLOADPFWKNGS-UHFFFAOYSA-N 1,1-dimethylurea Chemical compound CN(C)C(N)=O YBBLOADPFWKNGS-UHFFFAOYSA-N 0.000 description 2
- ZWAVGZYKJNOTPX-UHFFFAOYSA-N 1,3-diethylurea Chemical compound CCNC(=O)NCC ZWAVGZYKJNOTPX-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- RYECOJGRJDOGPP-UHFFFAOYSA-N Ethylurea Chemical compound CCNC(N)=O RYECOJGRJDOGPP-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 2
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229960004198 guanidine Drugs 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- XGEGHDBEHXKFPX-NJFSPNSNSA-N methylurea Chemical compound [14CH3]NC(N)=O XGEGHDBEHXKFPX-NJFSPNSNSA-N 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 101100412856 Mus musculus Rhod gene Proteins 0.000 description 1
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- CSHVYSHWQBIBNQ-UHFFFAOYSA-N N=NC(=O)N.NC(=N)N Chemical compound N=NC(=O)N.NC(=N)N CSHVYSHWQBIBNQ-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- RQOGVELQGMBDGS-UHFFFAOYSA-N ethenyl acetate;ethyl prop-2-enoate Chemical compound CC(=O)OC=C.CCOC(=O)C=C RQOGVELQGMBDGS-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 238000005303 weighing Methods 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
- D21H21/34—Ignifugeants
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
-
- 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
- D21H5/00—Special paper or cardboard not otherwise provided for
- D21H5/0002—Flame-resistant papers; (complex) compositions rendering paper fire-resistant
-
- 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
- Y10S428/92—Fire or heat protection feature
- Y10S428/921—Fire or flameproofing
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
- Y10T428/31906—Ester, halide or nitrile of addition polymer
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
- Y10T428/31993—Of paper
Definitions
- Such products exist as single ply paper structures or as multiple ply paper structures, or as laminated products in which these structures are adhered to each other or to other sheet-like or fabric-like materials, which may be strengthened by films, strands, gauze, scrim, netting, plastic networks, or other reinforcing materials.
- Such compounds include, for example, urea, derivatives of urea such as methyl urea, ethyl urea, 1,1-dimethyl urea, 1,3-diethyl urea, thiourea, derivatives of thiourea such as l-methyl thiourea,, 1,3-diethyl thiourea, 1,3-di1nethyl thiourea, arninourea (semi-carbazide), diaminourea (carbazide), and imino urea (guanidine) and dicyandiamide- (l-cyano guanidine) It is to be appreciated that these components are preferablyemployed in a single-bath impregnating or saturating process.
- the components may be separately applied to the base cellnlosic structure in a plurality of impregnating baths. Such, however, is less economical, less convenient, and less eflicient and is resorted to only ofnecessity.
- Thecross-linking polymeric acrylic resins saturate and impregnate the paper and paper products and considerably increase the tensile strength, improve the tear resistance andelongation, and enhance their drape and softness of hand.
- Particularly suitable for this purpose are ethyl acrylate polymers, methyl acrylate polymers, ethyl hexyl acrylate polymers, butyl acrylate polymers, ethyl acrylate-methyl methacrylate copolymers, ethyl hexyl acrylate-methyl methacrylate copolymers, butyl acrylate-methyl methacrylate copolymers, ethyl acrylate-polyvinyl acetate copolymers, and ethyl hexyl acrylate-polyvinyl acetate copolymers.
- the polymeric acrylic resin is normally applied to the paper or paper product in the form of an aqueous emul sion or latex and should be included in the impregnating bath in such amounts as to provide a concentration of polymeric acrylic resin solids in the range of from about 3% by weight up to about 30% by weight of the total impregnating bath. Within the preferred embodiments of the present invention, however, a range of from about 7% .by weight to about 13 by weight of the polymeric acrylic resin solids in the impregnating bath is found more desirable.
- Flame retardancy which includes the reduction of the burning-rate or the prevention of flaming combustion sewa e water-soluble, inorganic salt, namely, ammonium bromide,
- a suitable weakly basic, water-soluble organic, nitrogenous, amino-containing compound such as urea, derivatives of urea such as methyl urea, ethyl urea, 1,1- dimethyl urea, 1,3-diethyl urea, thio e a; derivativs of thiourea such as l-methyl thiourea ,3 diethyl thiourea, 1,3-dimethyl thiourea, aminourea (semi-carbazide), diaminourea (carbazide), iminourea (guanidine), and dicyandiamide (l-cyano guanidine).
- urea urea
- derivatives of urea such as methyl urea, ethyl urea, 1,1- dimethyl urea, 1,3-diethyl urea, thio e a
- derivativs of thiourea such as l-methyl thiour
- ammonium bromide-amino-contaim'ng compound combination imparts the desired flame retardancy properties and characteristics and actually and unexpectedly enhances the drape and softness of hand of the resulting paper or paper product. It is also observed that the action of the ammonium bromide and amino-containing compound do not interfere in any way with each other and that they actually complement and cooperate with each other and with the acrylate resin in many ways.
- ammonium bromide is normally added to the impregnating bath in such amounts as to provide a concentration of from about 4% by weight up to about 20% by weight, based on the total weight of the bath. Within the preferred embodiments of the present invention, however, a range of from about 5% by weight to about 9% by weight of the ammonium bromide is found more desirable in the impregnating bath.
- the amino-containing compound is normally added to the impregnating bath in such amounts as to provide a concentration of from about 1% by weight up to about 20% by weight, based on the weight of the bath. Within the preferred embodiments of the present invention, however, a range of from about 3% by weight to about 6% by weight of the amino-containing compound is found more desirable in the impregnating bath.
- the polymeric acrylic resin emulsion containing the added-ammonium bromide and amino-containing compound may be applied to the paper or paper product by substantially any known coating or impregnating method or technique.
- the paper or paper product may be withdrawn from a source of supply such as a supply roll or the like and guided into the impregnation bath, being immersed completely therein to take up the desired amount of wet treating agent.
- a source of supply such as a supply roll or the like
- the paper or paper product may be guided between the nip of an upper rotable pressure roll and a lower rotable immersion roll which is positioned partially in the impregnation bath from which it picks up the wet treating agent and transfers it to the paper or paper product at the nip with the upper pressure roll.
- the amount of wet pick-up of the aqueous treating agent by the paper or paper product may be varied within relatively wide limitations and is normally in the range of from about 75% by weight to about 250% by weight, based on the weight of the paper or paper product being treated. Within the preferred embodiments of the present invention, however, wet pick-up ranges of the aqueous treating agent of generally from about 175% by weight to about 225% by weight, based on the weight of the paper product, are found more desirable.
- Paper or paper products do exist, however, particularly in the heavier basis weight types, wherein it is desirable not to pick up large quantities of the aqueous treating agent inasmuch as such creates problems subsequently in the removal of the large quantities of water during drying. In such cases, it is more desirable to employ impregnating baths containing a higher concentration of components and to have a lower wet pick-up on the order of only about 75 by weight to about by weight of the paper or paper product.
- Such other materials may be included in the impregnating bath in order to impart to the paper or paper product specified properties and characteristics and special effects.
- Such other materials include opacifiers, absorbency control agents such as water repellents, fillers, humectants, dyes or pigments, cellulosic plasticizers, or emollients, perfumes, etc.
- the treated paper or paper product may be dried in any desired apparatus such as a conventional air-heated oven or drying cans capable of being heated to sufficiently elevated temperatures to dry the paper or paper product. Normally, temperatures in the range of from about 240 F. to about 330 F. are used, depending upon the speed of the paper or paper product through the drying zone or over the drying cans.
- a conventional air-heated oven or drying cans capable of being heated to sufficiently elevated temperatures to dry the paper or paper product. Normally, temperatures in the range of from about 240 F. to about 330 F. are used, depending upon the speed of the paper or paper product through the drying zone or over the drying cans.
- the finished treated paper on paper product contains from about 35% by weight to about 75 by weight of the base cellulosic material; from about 2% by weight to about 25% of the polymeric acrylic resin, from about 7% by weight to about 15% by weight of ammonium bromide, and from about 1% by weight to about 25% by weight of the amine. If desired, up to about 20% by weight of additives, as defined herein, may also be included.
- the paper or paper products being treated in accordance with the principles of the present invention may include basically any type of paper or paper product intended for packaging and shipping, printing and writing, building and construction, or of use in the medical and surgical fields, the food handling and processing industry, the clothing or home furnishings industries, or any other application wherein the preparation, processing, handling, storage, use or disposal of such products involves a flame retardancy problem.
- Such products exist as single ply paper structures or as multiple ply paper structures, or as laminated products in which these structures are adhered to each other or to other sheet-like or fabriclike materials, which may be strengthened by films, strands, gauze, scrim, netting, plastic networks, or other reinforcing materials.
- creped tissue paper either single ply or multiple plies, in the basis weight of from about 7 pounds to about 75 pounds per 3000 square feet and having stretch levels in the range of from about 5% to about 50%.
- the invention also finds excellent applicability to laminated tissue structures comprising one or a plurality of layers of creped cellulosic tissue, each layer having a basis weight of from about 7 pounds to about 35 pounds per 3000 square feet and which may be strengthened or reinforced by films, strands, gauze, scrim, netting, plastic networks, and the like, having an equivalent basis weight of from about 2 pounds to about 20 pounds per 3000 square feet.
- the total basis weights of such laminated structures, after adherence by adhesive, is normally in the range of from about pounds per 3000 square feet up to about 150 pounds or more per 3000 square feet. It is to be noted that such creped tissue paper and such laminated structures are used to illustrate the application of the principles of the present invention and that such is not to be construed as limitative of the broader aspects of the present invention.
- EXAMPLE I Single ply creped cellulose tissue having a basis weight of about 18 pounds per 3000 square feet is immersed at room temperature in an aqueous impregnating bath containing ammonium bromide, urea, and a self-cross linking vinyl acetate-ethyl acrylate-N-methylol acrylamid terpolymer latex (X-Link Resyn 2873, National Starch & Chemical Corp.). Suflicient amounts of these materials and suflicient water is included in the bath so that.
- the polymeric acrylic resin solids are present in an amount equal to about by weight of the impregnating bath,
- ammonium bromide is present in an amount equal to about 12% by weight of the impregnating bath
- the urea is present in an amount equal to about 10% by Weight of the impregnating bath.
- the creped tissue picks up approximately 100% by weight of the wet treating agent. Drying and curing takes place in a heated oven at temperatures in the range of from about 260 F. to about 325 F.
- the dried paper product contains 70.4% by Weight of the base cellulosic creped tissue, 14.0% by weight of the polymeric acrylic resin, 8.6% by weight of the ammonium bromide, and 7.0% by weight of the urea. All materials in this and subsequent examples are dried and then ovenaged at 240 F. for 10 minutes prior to testing.
- the material is tested in a flame retardancy vertical char test (TAPPI T-46l os-68) and the char length is determined to be only 2.5 inches which is below the necessary passing value of 5.5 inches and well below the desired value of 4.5 inches. There is no appreciable after glow.
- the test comprises suspending a 2% x 8%" sample of the material with the long dimension hanging vertically. A Bunsen or Tirrill gas burner having a 1%" flame with the air supply closed is placed immediately below the sample with the top of the burner tube from the bottom edge of the sample. The test flame is applied for 12 and withdrawn. The char length is measured. The after flame is the time in seconds required for the sample to stop flaming. The after glow is the time in seconds required for the sample to stop glowing.
- the material also passes the flame retardancy tests as described in ASTM D-777 and AATCC Spec. No. 34-1952 which are generally similar.
- the treated paper has outstanding textile-like drape and softness as determined subjectively by a panel of 6 laboratory technicians.
- the tensile strength in the machine direction (M.D.) is increased from 1.07 pounds to 3.54 pounds per inch width.
- the wet tensile strength in the machine direction is increased from 0.26 pound to 2.46 pounds per inch width.
- the wet tensile strength is increased from 0.082 pound to 0.795 pound per inch width in the cross direction.
- the elongation in the machine direction is increased from 21.8% to 30.3%.
- the elongation in the cross direction is increased from 4.3% to 9.8%.
- the permeability of the creped cellulose tissue has not been reduced materially by the flame retardant treatment; the voids in the tissue remain unfilled.
- the creped cellulose tissue handles very easily on converting equipment and it can be readily subjected to cutting, folding, printing and like operations. It is well suited for conversion into hospital pillow cases and is found to be flame retardant, soft and strong, and is tough in the sense that it possesses excellent energy-absorbing ability, that is, it is capable of absorbing applied loads Without rupturing.
- Example II The procedures of Example I are followed substantially as set forth therein except that the aqueous impregnating bath contains 20% by weight of polymeric acrylic resin solids, 16% by weight of ammonium bromide, and 1% by weight of urea.
- the finished, dried product contains 73% by weight of the base creped cellulose tissue, 15% by 'weight of the polymeric acrylic resin, 11% by weight of ammonium bromide and 1% by weight of urea.
- the flame retardancy vertical char length is 3.5 inches.
- the treated product has excellent textile-like draft and softness as determined subjectively by a panel of 6 laboratory technicians.
- the dry tensile strength in the machine direction is increased from 1.07 pounds to 3.57 pounds per inch width.
- the cross direction the dry tensile strength is increased from 0.38 pound to 1.12 pounds per inch width.
- the wet tensile strength in the machine direction is increased from 0.26 pound to 2.68 pounds per inch width. It is increased from 0.082 pound to 0.825 pound per inch width in the cross direction.
- the elongation in the machine direction is increased from 21.8% to 26.5%.
- the elongation in the cross direction is increased from 4.3% to 8.3%.
- the other properties and characteristics are improved, comparably to those noted in Example I.
- Example III The procedures of Example I are followed substantially as set forth therein except that the aqueous impregnating bath contains 20% by weight of polymeric acrylic resin solids, 16% by weight of ammonium bromide, and 5% by weight of urea.
- the finished, dried product contains 71.0% by weight of cellulosic fiber, 14.2% by weight of the polymeric acrylic resin, 11.3% by weight of ammonium bromide, and 3.5 percent by weight of urea.
- the flame retardancy vertical char length is 3.4 inches.
- the treated product has excellent textile-like drape and softness as determined subjectively by a panel of 6 laboratory technicians.
- the dry tensile strength in the machine direction is increased from 1.07 pounds to 3.52 pounds per inch width.
- the dry tensile strength is increased from 0.38 pound to 1.15 pounds per inch width.
- the wet tensile strength in the machine direction is increased from 0.26 pound to 2.59 pounds per inch width. It is increased from 0.082 pound to 0.760 pound per inch width in the cross direction.
- the elongation in the machine direction is increased from 21.8% to 26.2%.
- the elongation in the cross direction is increased from 4.3% to 9.2%.
- the other properties and characteristics of the finished product are comparable to those obtained for the product of Example 1.
- Example IV The procedures of Example I are followed substantially as set forth therein except that the aqueous impregnating bath contains 20% by weight of polymeric acrylic resin solids, 16% by weight of ammonium bromide, and 10% by weight of urea.
- the finished, dried product contains 68.5% by weight of cellulose fiber, 13.7% by weight of the polymeric acrylic resin, 10.9% by weight of the ammonium bromide, and 6.9% by weight of urea.
- the flame retardancy vertical char length is 2.9 inches.
- the treated product has excellent textile-like drape and softness as determined subjectively by a panel of 6 laboratory technicians.
- the dry tensile strength in the machine direction is increased from 1.07 pounds to 3.95 pounds per inch width.
- the dry tensile strength is increased from 0.38 pound to 0.93 pound per inch width.
- the wet tensile strength in the machine direction is increased from 0.26 pound to 2.72 pounds per inch width. It is increased from 0.082 pound to 0.643 pound per inch width in the cross direction.
- the elongation in the machine direction is increased from 21.8% to 27.5%.
- the elongation in the cross direction is increased from 4.3% to 9.7%.
- the other properties and characteristics of the finished product are comparable to those obtained for the product of Example I.
- composition of the treating bath is as follows:
- Example II solids
- the procedures of Example I are followed substantially Pwnds Pounds Percent s w t 1,135 as set forth therein except that the aqueous impregnating ggi bromide m 174 M bath has the following initial composition: Urea 100 100 Humectant (96%) 57 55 2. 8 S 11d X-Link Resyn 2833 (45%), National weight 0 S Starch & Chemical Corp 484 21s 11. 2 pounds Pounds Percent Total 1,950
- the first two samples have a Wet pick-up Humectant 4.1 of approximately y Weight of the p e
- the X-Link Resyn 2833, National Starch and Chemical solids content of the bath is then reduced approxlm ly Corp. 16.5 by the addition of 720 pounds of water to a bath 25 weighing 1380 pounds.
- the subsequent wet pick-up is 1001) maintained at approximately 250% by weight of the sample. After drying, the compositions of these samples are determined and are set forth in the following table:
- the sample is oven-aged at 240 F. for ten minutes and is then tested for its flame retardancy according to The five samples are accelerated-aged in an oven at 240 F. for ten minutes and are then tested for their flame retardancy according to the TAPPI T-461 os-68 Flame Resistance Test and all passed. There was no ignition. Other properties of the five samples are determined and are set forth in the following table:
- the wet tensile Treated Drytensll" Wet tensile ggg gfs strength in the machine direction is increased from 0.26 samples M.D. C.D. M.D. C.D. O.D. MD. pound to 175 pounds per mch width.
- the wet tensile 080 257 059 16,5 41 strength in the cross direction is increased from 0.082
- EXAMPLE VII Internal D1 tensile Wet tensile Elongatear, Untreated non, MD. The procedures of Example VI are followed substancontrol M.D. 0.1). MB. CD. CD. (grams) tially as set forth except that 2 samples of a 2-ply t1ssue A 117 0.38 0.29 0.096 M 24 are used. Each sample has a total basis weight of 23.3 B- 1.02 0.42 0. 24 0.081 4.6 30 pounds per 3000 square feet. 0 1. 03 0. 35 0. 25 0. 079 4. 0 20 These three untreated samples did not pass the ASTM- D-1230 Flame Resistance Test.
- the self cross-linking vinyl acetate-ethyl acrylate terpolymer latex is X-Link Resyn 2833 (National Stanch and Chemical Corp.) containing a higher proportion of the The samples are oven-aged at 240 F. for ten minutes and tested for flame retardancy according to the TAPPI T-461 os-68 Flame Resistance Test. There is no ignition.
- the finished product has excellent textile-drape and soft ness as determined subjectively by a panel of 6 laboratory technicians.
- the dry tensile strength in the machine direction is increased from 1.12 and 1.28 pounds per ply per inch width to 5.01 and 4.95 pounds per inch width.
- the dry tensile strength in the cross direction is increased from 0.61 and 0.58 pound per ply per inch width to 1.59 and 1.65 pounds per inch Width.
- the wet tensile strength in the machine direction is increased from 0.21 pound per ply per inch width to 3.00 and 2.50 pounds per inch width.
- the wet tensile strength in the cross direction is increased from 0.077 and 0.081 pound per ply per inch width to 0.85 and 0.73 pound per inch width.
- the elongation in the cross direction is increased from 3.9% and 4.3% to 16.0% and 15.5%.
- the internal resistance in the machine direction is improved from 24 and 23 grams to 54 and 43 grams. Other properties and characteristics are similarly improved.
- Example VIII The procedures of Example I are followed substantially as set forth therein except that the cellulosic material comprises a three-layer reinforced laminated structure comprising: outer layers of creped cellulose tissue (each having a basis weight of 18 pounds per 3000 square); a central layer of 8 x 8 gauze (having an equivalent basis weight of 7 pounds per 3000 square feet); and an adhesive bonding the layers into a strengthened three-layer laminated structure having a basis weight of 50 pounds per 3000 square feet.
- the cellulosic material comprises a three-layer reinforced laminated structure comprising: outer layers of creped cellulose tissue (each having a basis weight of 18 pounds per 3000 square); a central layer of 8 x 8 gauze (having an equivalent basis weight of 7 pounds per 3000 square feet); and an adhesive bonding the layers into a strengthened three-layer laminated structure having a basis weight of 50 pounds per 3000 square feet.
- a different composition for the impregnating bath is used for the laminated structure and comprises:
- Percent in bath Rhoplex RC-S 18 is a self crosslinking copolymer of ethyl acrylate and methyl methacrylate.
- the wet pick up from the impregnating bath is approximately 140% by weight, based on the weight of the cellulosic product.
- the dry-add on of solids is approximately 20% by weight, based on the Weight of the cellulosic product. This is equal to a dry-add on of 12.5% by weight of ammonium bromide, 4.2% by weight of urea, and 2.5% by weight of acrylic resin.
- the resulting product passes TAPPI and ASTM Flame Retardancy Tests. All other physical properties and characteristics are improved comparably.
- Example IX The procedures of Example I are followed substantially as set forth therein except that the urea is replaced by decreased amounts of approximately of dicyandiamide in the impregnating bath.
- the resultant products are flame retardant and have textile-like drape and softness of hand as determined subjectively by a panel of six laboratory technicians.
- the products have physical properties and characteristics comparable to those obtained for the products of Example I.
- Example I The procedures of Example I are followed substantially as set forth therein except that the urea is replaced by decreased amounts of approximately 5% of aminourea (semi-carbazide) in the impregnating bath.
- the resultant products are flame retardant and have textile-like drape and softness of hand as determined subjectively by a panel of six laboratory technicians.
- the products have physical properties and characteristics comparable to those obtained for the products of Example I.
- the resultant products are flame retardant and have textile-like drape and softness of hand as determined subjectively by a panel of six laboratory technicians.
- the products have physical properties and characteristics comparable to those obtained for the products of Example I.
- Example XII The procedures of Example I are followed substantially set forth therein except that the self-cross linking acrylate resin is replaced by an equivalent amount of a copolymer ethyl hexyl acrylate and methyl methacrylate.
- the resultant products are flame retardant and have textile-like drape and softness of hand as determined subjectively by a panel of six laboratory technicians.
- the products have physical properties and characteristics comparable to those obtained for the products of Example I.
- the resultant products are flame retardant and have textile-like drape and softness of hand as determined subjectively by a panel of six laboratory technicians.
- the products have physical properties and characteristics comparable to those obtained for the products of Example I.
- the resultant products are flame retardant and have textile-like drape and softness of hand as determined subjectively by a panel of six laboratory technicians.
- the products have physical properties and characteristics comparable to those obtained for the products of Example I.
- a method of treating cellulosic papers and paper products to render them flame retardant and to provide them with improved tear resistance and tensile strength and enhanced drape and softness which comprises impreg n ag i pg the cellulosic papers and paper products "arfaqueoiis' treating bath comprising from about 3% by weight to about 30% by weight of a self cross-linking polymeric acryli 3m, from about 4% by weight to about 20% by w t of ammonium bromide, and from about 1% by weight to about 20% by weight of a weakly basic, water-soluble, aliphatic organic nitrogenous compound containing an amino group andndrying sai d impregnated cellulosic papers and paper products to remove substantially all of the water therefrom.
- aminocontaining compound is urea
- Flame retardant cellulosic papers and paper products having improved tensile strength, tear resistance, enhanced drape and softness comprising from about 35% by weight to about 75% by weight of the base cellulosic paper, from about 2% by weight to about 25% by weight of a self cross-linked polymeric acrylic resin, from about 7% by weight to about 15% by weight of ammonium bromide, and from about 1% by weight to about 25% by weight of a weakly basic, water-soluble, ali- 5.
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US81641469A | 1969-04-15 | 1969-04-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3667999A true US3667999A (en) | 1972-06-06 |
Family
ID=25220522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US3667999D Expired - Lifetime US3667999A (en) | 1969-04-15 | 1969-04-15 | Flame retardant cellulosic materials |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US3667999A (enExample) |
| AT (1) | AT298974B (enExample) |
| BE (1) | BE745308A (enExample) |
| DE (1) | DE2016823A1 (enExample) |
| DK (1) | DK126211B (enExample) |
| ES (1) | ES376020A1 (enExample) |
| FR (1) | FR2042901A5 (enExample) |
| GB (1) | GB1291133A (enExample) |
| NO (1) | NO131089C (enExample) |
| SE (1) | SE376031B (enExample) |
| ZA (1) | ZA70390B (enExample) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002038864A3 (en) * | 2000-11-10 | 2003-02-27 | Bromine Compounds Ltd | Flame-retarded paper products and method and apparatus for making them |
| US20060266483A1 (en) * | 2005-05-31 | 2006-11-30 | Roberts Timothy J | Disposable curtains, systems and methods to install a disposable curtain, and methods of manufacturing a disposable curtain |
-
1969
- 1969-04-15 US US3667999D patent/US3667999A/en not_active Expired - Lifetime
-
1970
- 1970-01-20 ZA ZA700390A patent/ZA70390B/xx unknown
- 1970-01-20 GB GB272570A patent/GB1291133A/en not_active Expired
- 1970-01-23 SE SE83470A patent/SE376031B/xx unknown
- 1970-01-23 DK DK30470A patent/DK126211B/da unknown
- 1970-01-29 ES ES376020A patent/ES376020A1/es not_active Expired
- 1970-01-30 BE BE745308D patent/BE745308A/xx unknown
- 1970-02-06 NO NO42970A patent/NO131089C/no unknown
- 1970-03-26 AT AT285270A patent/AT298974B/de not_active IP Right Cessation
- 1970-04-03 FR FR7012154A patent/FR2042901A5/fr not_active Expired
- 1970-04-09 DE DE19702016823 patent/DE2016823A1/de active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002038864A3 (en) * | 2000-11-10 | 2003-02-27 | Bromine Compounds Ltd | Flame-retarded paper products and method and apparatus for making them |
| US20040050512A1 (en) * | 2000-11-10 | 2004-03-18 | Yossef Gohary | Flame-retarded paper products and method and apparatus for making them |
| US20060266483A1 (en) * | 2005-05-31 | 2006-11-30 | Roberts Timothy J | Disposable curtains, systems and methods to install a disposable curtain, and methods of manufacturing a disposable curtain |
| US7523778B2 (en) | 2005-05-31 | 2009-04-28 | Hospital Therapy Products | Disposable curtains, systems and methods to install a disposable curtain, and methods of manufacturing a disposable curtain |
| US20090173458A1 (en) * | 2005-05-31 | 2009-07-09 | Roberts Timothy J | Disposable curtains, systems and methods to install a disposable curtain, and methods of manufacturing a disposable curtain |
| US7845387B2 (en) | 2005-05-31 | 2010-12-07 | Hospital Therapy Products | Disposable curtains, systems and methods to install a disposable curtain, and methods of manufacturing a disposable curtain |
Also Published As
| Publication number | Publication date |
|---|---|
| DK126211B (da) | 1973-06-18 |
| AT298974B (de) | 1972-05-25 |
| DE2016823A1 (de) | 1970-10-22 |
| NO131089B (enExample) | 1974-12-23 |
| ES376020A1 (es) | 1972-03-16 |
| BE745308A (fr) | 1970-07-30 |
| NO131089C (enExample) | 1975-04-02 |
| SE376031B (enExample) | 1975-05-05 |
| GB1291133A (en) | 1972-09-27 |
| ZA70390B (en) | 1971-08-25 |
| FR2042901A5 (enExample) | 1971-02-12 |
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