EP0118552A1 - Schichtförmiges, zusammengesetztes papiergebilde und sein herstellungsverfahren - Google Patents
Schichtförmiges, zusammengesetztes papiergebilde und sein herstellungsverfahrenInfo
- Publication number
- EP0118552A1 EP0118552A1 EP19830903065 EP83903065A EP0118552A1 EP 0118552 A1 EP0118552 A1 EP 0118552A1 EP 19830903065 EP19830903065 EP 19830903065 EP 83903065 A EP83903065 A EP 83903065A EP 0118552 A1 EP0118552 A1 EP 0118552A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- thermoplastic resin
- paper product
- fibers
- cellulosic
- web
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title description 10
- 239000000835 fiber Substances 0.000 claims abstract description 87
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 62
- 229920005989 resin Polymers 0.000 claims abstract description 59
- 239000011347 resin Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims description 64
- 239000000203 mixture Substances 0.000 claims description 18
- -1 polyethylene Polymers 0.000 claims description 18
- 229920000098 polyolefin Polymers 0.000 claims description 14
- KKEBXNMGHUCPEZ-UHFFFAOYSA-N 4-phenyl-1-(2-sulfanylethyl)imidazolidin-2-one Chemical compound N1C(=O)N(CCS)CC1C1=CC=CC=C1 KKEBXNMGHUCPEZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000003490 calendering Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 11
- 239000000049 pigment Substances 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000035699 permeability Effects 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000009877 rendering Methods 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 229920001169 thermoplastic Polymers 0.000 abstract 1
- 239000004416 thermosoftening plastic Substances 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 68
- 239000000047 product Substances 0.000 description 67
- 239000010410 layer Substances 0.000 description 54
- 239000000463 material Substances 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 229920003002 synthetic resin Polymers 0.000 description 11
- 239000000057 synthetic resin Substances 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 239000011229 interlayer Substances 0.000 description 8
- 239000001913 cellulose Substances 0.000 description 7
- 229920002678 cellulose Polymers 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 5
- 238000007765 extrusion coating Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000036961 partial effect Effects 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000011436 cob Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003605 opacifier Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241000212384 Bifora Species 0.000 description 1
- 241001082241 Lythrum hyssopifolia Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical class OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical class NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 229920001291 polyvinyl halide Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/04—Physical treatment, e.g. heating, irradiating
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
- D21F11/02—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines of the Fourdrinier type
- D21F11/04—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines of the Fourdrinier type paper or board consisting on two or more layers
-
- 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
- D21H5/12—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials
- D21H5/1272—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of fibres which can be physically or chemically modified during or after web formation
- D21H5/129—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of fibres which can be physically or chemically modified during or after web formation by thermal treatment
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
- G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes
Definitions
- the present invention relates to a stratified composite paper product composed partly of cellulose and partly of synthetic resin materials .
- it relates to a stratified composite paper product having outer synthetic resin strata, which product is useful as a support for image-recording elements.
- This invention also relates to a method of making such a paper product.
- a common method of making a continuous laminated web of cellulosic and polymeric materials i s n extrusion coating process.
- this process typically includes extrusion of a molten synthetic resin through an extruder die onto a moving cellulosic web. After extrusion (sometimes called resin coating) , the resulting composite web is cooled and subjected to compression to increase interlayer adhesion.
- Another common way of improving interlayer adhesion is to treat the surface of the cellulosic substrate prior to resin coating to alter surface characteristics.
- the cellulosic substrate is subjected to corona discharge prior to resin coating to improve the interlayer adhesion.
- corona discharge prior to resin coating to improve the interlayer adhesion.
- Corona discharge also causes some degradation of the cellulosic materials and can result in shortened
- Another surface treatment technique known in the art involves the application of a primer layer on the cellulosic surface before resin coating.
- primers are generally very expensive, and careful selectivity is required in the conditions of their use.
- application of such primers typically requires wetting of the cellulosic substrate, which in turn can make low strength substrates difficult to handle and weaken high strength substrates .
- a stratified composite paper product which is substantially impermeable to liquids and gases .
- This paper product comprises (1) an interior stratum consisting essentially of cellulosic papermaking fibers; (2) directly contiguous to each face of the interior stratum, an intermediate stratum containing intermingled thermoplastic resin fibers and cellulosic papermaking fibers; and (3) directly contiguous to each of the intermediate strata, a
- OMPI strongly adhering, continuous outer stratum of a thermoplastic resin.
- the stratified composite paper product has improved interlayer adhesion between cellulosic and the synthetic resin strata and less likely to suffer delamination during its useful life. Furthermore, the paper product of this invention has improved permanence, meaning that the materials making up the various strata are less likely to degrade during its useful life because they have not been subjected to high extrusion temperatures.
- the invention also provides a method for the preparation of the stratified composite paper product described above.
- This method comprises the steps of: (A) simultaneously flowing an aqueous slurry of cellulosic papermaking fibers and at least one aqueous slurry of thermoplastic resin fibers into a web-forming zone to form therein a stratified composite web comprising an interior stratum consisting essentially of cellulosic papermaking fibers, an intermediate stratum contiguous to each face of the interior stratum composed of intermingled thermoplastic resin fibers and cellulosic papermaking fibers, and an exterior stratum contiguous to each of the intermediate strata consisting essentially of thermoplastic resin fibers; (B) rendering the web substantially dry; and (C) subjecting the web to heat sufficient to fuse each exterior strata into a strongly adhering continuous layer of thermoplastic resin to each intermediate stratum.
- the novel method provide significant manufacturing advantages and results in an improved stratified paper product.
- the method can be practiced using conventional papermaking equipment (e.g. a Fourdrinier machine) which has been suitably
- the paper product can be used as a support material immediately after manufacture thereby eliminating the need for the extrusion coating operation.
- the avoidance of extrusion coating significantly reduces manufacturing costs, and eliminates resin degradation which can occur at high extrusion coating temperatures.
- the method of this invention produces a product that has improved permanence, i.e. extended useful life, with improved interlayer adhesion, thereby obviating the need for any surface treatment (e.g. corona discharge) or expensive primer layers.
- the stratified composite paper product described hereinabove is particularly useful as a support having thereon at least one image-recording layer or at least one photosensitive silver halide emulsion layer.
- FIG. 1 is a partial, sectional view of a stratified composite product prepared by the method of this invention but prior to the fusing step.
- FIG. 2 is a partial, sectional view of a stratified composite paper product of this invention prepared by subjecting the stratified composite product of FIG. 1 to the fusing step.
- FIG. 3 is a schematic diagram illustrating a preferred embodiment of the method of this invention.
- the stratified composite paper product of this invention is substantially impermeable to liquids and gases .
- substantially impermeable refers to the capability of such paper product to resist physical permeation by most commonly encountered liquids and gases .
- Liquid permeability of a substrate is typically characterized for paper substrates by a test known as the Cobb Test. This is a standard test which includes the steps of: (1) conditioning and weighing a sample of the substrate; (2) wetting the sample with 100 milliliters of water for 2 minutes; and (3) determining the weight gain of the sample. Further details of this test are described in TAPPI T441 os-77.
- Gas permeability of a substrate is typically characterized for paper substrates by a test known as the Sheffield Test. This is a standard test which includes measuring the air resistance of a substrate sample when it is subjected to a 1.5 psi (77.6 mm Hg) air column. Further details of this test are described in TAPPI U.M. 524.
- the paper product of this invention has a liquid permeability of less than 10 grams per square meter, and preferably of zero, as
- these products typically have a gas permeability of less than about 20 milliliters per minute as determined with a 1.5 inch (3.8 cm.) I.D. orifice plate, and preferably of zero, as measured by the Sheffield Test described hereinabove.
- the paper product of this invention has outer thermoplastic resin layers which are highly hydrophobic, i.e. the resin layers have a high tendency to repel water.
- This hydrophobicity can be conveniently determined by measuring the receding water contact angle, O R , established between a droplet of distilled water and the surface of any of the resin layers. Methods for determining O R are well known. A suitable method is the Sessile drop method described in Physical Chemistry of Surfaces by A. W. Adamson (published by Interscience Publishing Corp., 1967, pp. 352-375).
- the 0 R can be lower, typically the 0 R of the paper products of this invention, as determined by the Sessile drop method, is greater than about 75°, and preferably greater than about 80°. More preferably the 0-, is greater than about 90°.
- the amount of thermoplastic resin incorporated into the paper products of this invention can vary widely as long as the requisite requirements of liquid and gas impermeability are met.
- the amount of resin is within the range of from about 10 to about 70 percent, based on total solids weight (i.e. including cellulosic materials and any additives).
- the amount of resin is within the range of from about 30 to about 70 percent, and more preferably, from about 40 to about 60 percent, based on total solids weight.
- the amount of cellulose is typically within the range of from about 30 to about 90 percent, based on total solids weight.
- the amount of cellulose is within the range of from about 30 to about 70 percent, and more preferably, from about 40 to about 60 percent, based on total solids weight.
- Another way of characterizing the amounts of resin and cellulose in the described paper product is a weight ratio of resin to cellulose. This ratio is typically in the range of from about 1:4 to about 2:1, and preferably from about 1:3 to about 1:1.
- the thickness of the outer thermoplastic resin layers can vary greatly depending upon the resins used and the product end use, as long as the paper product has the desired liquid and gas impermeabilities. Each outer resin layer can be of the same thickness or one can be thicker than the other, as desired.
- the paper product of this invention has an interior stratum consisting essentially of cellulosic papermaking fibers. Typically, there are few, if any, resin or other noncellulosic fibers in the interior stratum.
- the cellulosic papermaking fibers therein are tightly packed together in the form of a sheet material.
- the types of cellulosic fibers useful in making the paper product of this invention are well known and are made, for example, by extensive "refining" of bleached sulfite wood cellulosic paper stocks to a desired fiber length and surface area.
- Such paper stocks can comprise hardwood or softwood fibers or mixtures of both. They can be treated in any suitable way prior to being formed into a stratum of a stratified composite web.
- additives can be incorporated into the cellulosic stratum if desired.
- additives include sizing agents, wet or dry strength agents, fillers, brighteners, opacifiers, pigments, antioxidants , dispersing aids, antifoamers, biocides and retention/drainage aids.
- a dispersing aid such as clay, in the slurry of cellulosic fibers from which the interior stratum is formed.
- the interior stratum of the paper product can be a single layer or be composed of a plurality of substrata, each having the same or different types of cellulosic papermaking fibers in order to provide particular desirable characteristics.
- the interior stratum is a single layer .
- the average thickness of the interior stratum can vary widely, but typically, it is within the range of from about 25 to about 350 micrometers. The stratum thickness can also vary within this range throughout a given sample of paper product.
- thermoplastic resins useful in preparing the paper products of this invention are generally synthetic resins which can be rendered soft or moldable with appropriate heat. Any suitable thermoplastic resin or mixture thereof can be used in the practice of this invention as long as it is capable of being formed into fibers and such fibers can be fused with heat and/or pressure.
- Typical useful thermoplastic resins include polyesters (e.g. polyesters formed from a diol and dicarboxylic acid or ester or anhydride derivative thereof, etc.); acrylic resins (e.g. poly(methyl methacrylate) , etc.); polyvinyl esters (e.g. polyvinyl acetate, polyvinyl propionate, etc.); polyvinylarenes (e.g.
- polystyrene, etc. polystyrene, etc.); polyvinyl halides (e.g. polyvinyl chloride, etc.); polyvinyl alcohol; polyolefins , and others known in the art.
- the preferred thermoplastic resins are polyolefins.
- polyolefin refers, first of all, to a homopolymer of an ⁇ -olefin having from 2 to 8 carbon atoms, such as ethylene, propylene, butylene, isobutylene, isoprene, amylene, etc., which can be halo-substituted (e.g. chloro, bromo, etc.) if desired.
- the term also refers to copolymers of two or more of the described ⁇ -olefins including what are sometimes called polyallomers; and to copolymers prepared primarily (greater than about 50 weight percent) from one or more of the described ⁇ -olefins and one or more ethylenically unsaturated monomers copolymerizable with ⁇ -olefins, including but not limited to vinyl esters, ethylenically unsaturaced carboxylic acids and esters and amides thereof, styrene, vinyl amides and the like.
- polyethylene or polypropylene is used in the paper products of this invention, with polyethylene being more preferred.
- These resins typically have a density in the range of from about 0.90 to about 0.98 grams per cubic centimeter and a melting point in the range of from about 105° to about 135°C.
- the thermoplastic resins described herein are either readily available commercially or can be prepared by well known condensation or additive polymerization methods.
- the polyolefins can be prepared by conventional addition polymerization methods using a Ziegler catalyst. Any compatible mixture of thermoplastic resins can be used in the practice of this invention, including mixtures of two or more different types of resins (e.g. a mixture of a polyvinylarene and a polyolefin) , and mixtures of two or more resins of
- O PI -li ⁇ the same type (e.g. a mixture or blend of two or more polyolefins) .
- Either or both of the described outer thermoplastic resin layers can also contain various additives, including pigments, opacifiers, antioxidants, stabilizers, UV absorbers, plasticizers, brighteners, antistatic agents, dispersing aids, lubricants, etc. which do not adversely affect the properties desired for the present invention.
- a dispersing aid such as clay
- the resin layers also contain transparent or colored pigments, but preferably they contain white opacifying pigments, such as titanium dioxide (either rutile or anatase) , zinc oxide, talc, calcium carbonate, alumina, etc. in an amount in the range of from about 5 to about 25 percent, based on the total weight of resin in the paper product. Any other additives to such resins are generally present in an amount up to about 3 percent, based on total weight of resin.
- the outer thermoplastic resin layers can be composed of the same thermoplastic resin or mixture of resins, or each layer can be a different resin or mixture.
- one of the outer layers can consist essentially of a first thermoplastic resin and the other outer layer can consist essentially of a second thermoplastic resin of composition different than the first resin.
- both outer resin layers are of the same composition and therefore can be formed from the same slurry of resin fibers.
- the types and amounts of additives can be the same or different for the respective resin layers.
- each outer thermoplastic resin layer can be a single continuous layer or a composite of two or more substrata of the same or different resins .
- each outer resin layer is a single continuous layer .
- each outer thermoplastic resin layer can vary widely, but typically it is within the range of from about 25 to about 350 micrometers. Layer thickness can also vary within these limits throughout a given sample of paper product.
- an intermediate stratum containing intermingled thermoplastic resin fibers and cellulosic papermaking fibers. Both of these types of fibers have been described hereinabove.
- an intermediate stratum has more thermoplastic resin fibers near the outer resin layer and more cellulosic fibers near the interior stratum. In other words, there is generally a gradient of resin fibers decreasing from near the outer layer towards the interior stratum and a gradient of cellulosic fibers increasing towards the interior stratum.
- Each intermediate stratum can also contain the various additives which can be found in either the interior stratum or the continuous outer resin layers. The thickness of each intermediate stratum can vary greatly but is typically within the range of from about 10 to about 50 micrometers throughout a given sample of paper product.
- the paper product of this invention can have additional layers on either or both outer faces of the outer resin layers .
- additional layers include, but are not limited to,
- the method provided by the present invention for making the composite paper product utilizes conventional papermaking equipment. This equipment can be easily modified to accommodate multi-ply paper webs.
- the paper product of this invention is prepared from two or more aqueous slurries, i.e. an aqueous slurry for each type of fiber to be included in the paper product. For example, if three different paper stocks and two different thermoplastic resins are to be incorporated as distinct layers into the paper product, a total of five aqueous slurries are used.
- a photographic paper base is prepared with two aqueous slurries, one containing cellulosic fibers and the other containing polyolefinic fibers, whereby each outer resin layer is of the same composition.
- a photographic paper base is prepared with three aqueous slurries, one containing cellulosic fibers and the other two containing polyolefinic fibers of the same composition.
- the slurries can have different consistencies (i.e. different percent solids) . All of these slurries are typically prepared using refining techniques well known in the papermaking art.
- the cellulosic slurry raw paper stock is dispersed in an aqueous medium with a refiner or other suitable equipment.
- Conventional additives e.g. pigments, strengthening agents, fillers, brighteners, etc.
- the synthetic resin is usually purchased in fibrous form having suitable
- OMPI fiber length and dispersed in an aqueous medium along with pigments or other desired additives.
- slurries Once the slurries have been prepared and their components have been uniformly admixed, they are delivered simultaneously to a web-forming zone to be formed into a stratified composite web.
- a web is multi-ply, meaning that it has three or more layers, at least one layer corresponding to each slurry delivered to the zone.
- Slurry delivery can be accomplished by any suitable means. For example, it can be accomplished by pumping the slurries to a plurality of conventional headboxes situated on suitable papermaking equipment (e.g. a Fourdrinier machine) in such a manner as to deliver the slurries substantially simultaneously to a web-forming wire.
- suitable papermaking equipment e.g. a Fourdrinier machine
- the slurries are pumped to a single headbox and delivered simultaneously to the web-forming zone with that headbox.
- a headbox has a main chamber divided into a plurality of subchambers by a dividing means. Each subchamber communicates with or is connected to the web-forming zone so that a specific slurry can flow to the zone simultaneously with the others but with minimal mixing of the slurries.
- cellulosic and thermoplastic resin fiber slurries are simultaneously delivered to a "slice opening" and onto a web-forming wire with a single headbox.
- one such headbox useful in the practice of this invention is the Strata-Flo ConverfloTM headbox, commercially available from Beloit Corporation, Beloit, Wisconsin.
- the cellulosic slurry is delivered by a first subchamber of such a headbox and the thermoplastic resin fiber slurry is divided and delivered through second and third
- CMPI subchambers on opposite sides of the first subchamber.
- separate resin slurries can be delivered through the second and third subchambers.
- This provides a web having an interior stratum (also known as a layer) predominantly of cellulosic fibers and strata of thermoplastic resin fibers on either side of the interior stratum.
- an intermediate stratum (could also be called a zone) containing intermingled resin and cellulosic fibers is formed between the interior stratum and each outer resin stratum.
- the composite multi-ply web is formed from dilute aqueous slurries, e.g. typically from about 0.3 to about 3 percent of fibers by weight, in accordance with conventional papermaking techniques, and the water is drawn off through the web-forming wire to yield a laminate structure which still has a substantial water content. Accordingly, the web must be rendered substantially dry prior to carrying out further steps of the manufacturing process. This can be done with conventional papermaking pressing or drying techniques or a combination thereof.
- xt may be advantageous in some instances for the cellulosic and thermoplastic resin slurries to have different consistencies. That is, the percentages, by weight, of fibers for the respective slurries may differ.
- thermoplastic resin slurry for one or both outer resin fiber strata to have a higher fiber weight percent (i.e. a higher consistency) than the cellulosic fiber slurry. It may also be advantageous for each resin layer to be formed from separate slurries having different consistencies .
- a composite multi-ply web is preferred from a single cellulosic fiber slurry and two thermoplastic resin slurries.
- thermoplastic resin slurries are delivered to the web-forming zone and the multi-ply web is formed on the papermaking wire, one of the resin slurries is located "above” the cellulosic slurry and the other is located “below” it.
- the consistency of the slurry "below" the cellulosic slurry is lower than the consistency of the cellulosic slurry, which in turn is lower than the consistency of the upper most resin slurry.
- the substantially dry stratified composite web is then subjected to heat and/or pressure sufficient to fuse the exterior thermoplastic resin fibers into strongly adhering continuous resin layers.
- This fusing step can be done in any suitable manner which does not degrade the resin or cellulose.
- fusing can be accomplished by heat alone, e.g. by heating a polyolefin-containing web to a temperature in the range of from about 110 to about 135°C with infrared radiation from suitable infrared heaters. This heating can be preceded or followed by calendering the web under controlled temperature and pressure conditions.
- the fusing is accomplished by running the web through a series of heated calender rolls (i.e. a calender stack) under controlled temperature and pressure conditions.
- fusing thermoplastic resin fibers into a continuous film by calendering can be accomplished with widely varying temperatures and pressures. For example, as the temperature is increased, generally less pressure is necessary for
- calendering is accomplished at a temperature greater than the glass transition temperature and less than the melting temperature of all of the thermoplastic resins being used in a particular composite paper product.
- the useful temperature range is from about 90 to about 135°C.
- the preferred calendering temperature is in the range of from about 110 to about 130°C.
- the calendering pressure for any thermoplastic resin is in the range of from about 35 to about 210 kilonewtons per linear meter.
- the pressure is relatively low, for example, from about 40 to about 70 kilonewtons per linear meter, for calendering webs containing polyolefins where high opacity is desired.
- the opaque paper product described hereinabove is provided by calendering the dry composite web under temperature and pressure conditions controlled to maintain the desired opacity.
- the resulting stratified composite paper product can be treated further or coated with any desired coating composition.
- subbing, antistatic, antihalation, protective, image-recording layers can be applied to either or both sides of the paper product.
- Either surface of the paper product can be treated (e.g. corona, electron bombardment, plasma, etc.) prior to such coating to improve adhesion.
- the paper product is coated with one or more image-recording compositions, such as photosensitive silver halide emulsions.
- Web 1_ comprises interior stratum 2 which consists essentially of cellulosic papermaking fibers represented by the numeral 3_.
- intermediate stratum 4 composed of intermingled thermoplastic resin fibers represented by the numeral 5_ and cellulosic papermaking fibers represented by the numeral 3_.
- exterior stratum 7_ composed of thermoplastic resin fibers represented by the numeral 5_.
- FIG. 2 is an exaggerated partial sectional view of a stratified composite paper product of this invention which results when web 1 ⁇ of FIG. 1 is subjected to the fusing step described hereinabove in relation to the process of this invention.
- Composite paper product 8 ⁇ comprises interior stratum 2_ composed predominantly of cellulosic papermaking fibers represented by the numeral 3_.
- interior stratum 2_ composed predominantly of cellulosic papermaking fibers represented by the numeral 3_.
- intermediate stratum 4 composed of intermingled thermoplastic resin fibers represented by the numeral 5_ and cellulosic papermaking fibers represented by the numeral 3_.
- Directly contiguous to each of intermediate strata 4 is strongly adhering, continuous outer layer 9 of a thermoplastic resin.
- FIG. 3 is a schematic illustration of a preferred embodiment of the method of this invention.
- aqueous slurry 100 of cellulosic papermaking fibers and aqueous slurry 101 of thermoplastic resin fibers are prepared and delivered to single headbox 102.
- Cellulosic slurry 100 is delivered to web-forming zone 106 through subchamber 103 while resin slurry 101 is delivered to zone 106 through subchambers 104.
- Both slurries are then formed into stratified composite 108 on web-forming wire 110 which is part of Fourdrinier web-forming equipment 112.
- This web is then subjected to pressing with pressing rolls 114 and drying in drying zone 116.
- the web is subjected to calendering under controlled temperature and pressure conditions to fuse the outer resin fiber layers with calender stack 118 and becomes paper product 119 which is wound up on take up roll 120 for storage or subsequent treatment.
- the paper product of the present invention can be used in a variety of ways, such as packaging for foods, cardboard, paper board, shipping containers, bags, etc.
- this paper product is useful as a support material for image-recording elements.
- Such elements are known in the art and generally include a support having thereon one or more image-forming or image-receiving layers as well as any additional layers desired.
- Typical image-forming elements of this invention include photographic (both positive and negative working) , photothermographic, thermographic and radiographic elements and diffusion or image transfer film units.
- the paper products are used in what are known in the art as photographic papers useful in preparing reflection prints.
- the characteristics and components of such elements and papers, including image-forming materials, are known in the art.
- Typical image-receiving elements of this invention are elements which "receive" an image which has been previously formed elsewhere, such as on an image-forming element.
- Such "receivers” as they are sometimes called can be used in integral intake transfer film units or two-sheet instant film products including those sometimes called “peel apart” products as well as in the products described in U. S. Patents 4,296,195 (issued October 20, 1981 to Bishop et al) and 4,297,432 (issued October 27, 1981 to Bowman et al) .
- a stratified composite paper was prepared in the following manner using conventional Fourdrinier papermaking equipment fitted with a Strata-Flo
- An aqueous slurry of hardwood kraft cellulosic fibers was prepared having 0.4 percent solids. The fines fraction of the fibers was believed to be about 20%. A yellow dye was added to the slurry to allow easy identification of cellulosic layers in the composite paper.
- An aqueous slurry of polyethylene fibers was also prepared having 0.4 percent polyethylene solids and 10% clay (based on polyethylene weight) . The two slurries were then fed to the paper-forming wire of the papermaking
- ItlVf equipment via the Strata-Flo Converflo headbox with the cellulosic slurry directed to a central chamber of the headbox and two portions of the polyethylene slurry directed respectively to two chambers one on each side of the central chamber .
- the resulting multi-ply web formed on the paper-forming wire and subsequently dried was substantially like the web illustrated in FIG. 1.
- the weight ratio of polyolefin to cellulose in the web was about 1:1.
- Samples of the multi-ply web so prepared were calendered under controlled temperature and pressure conditions to fuse the outer resin fiber layers.
- the calendering was done with a four-roll calender stack having a calender surface temperature of about 55°C and providing a maximum loading of about 87 kilonewtons of pressure per linear meter.
- the resulting stratified composite paper product was substantially like the element illustrated in FIG. 2 and had surface characteristics (e.g. hydrophobicity and liquid and gaseous impermeability) similar to those of a conventional resin-extruded paper product.
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Laminated Bodies (AREA)
- Paper (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US41782482A | 1982-09-13 | 1982-09-13 | |
| US417824 | 1982-09-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0118552A1 true EP0118552A1 (de) | 1984-09-19 |
Family
ID=23655530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19830903065 Withdrawn EP0118552A1 (de) | 1982-09-13 | 1983-09-12 | Schichtförmiges, zusammengesetztes papiergebilde und sein herstellungsverfahren |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0118552A1 (de) |
| WO (1) | WO1984001176A1 (de) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2066812A1 (en) * | 1991-04-23 | 1992-10-24 | R. Wayne Self | Method and apparatus for the production of multiply cellulosic board and product obtained thereby |
| DE19922390A1 (de) * | 1999-05-14 | 2000-11-16 | Voith Sulzer Papiertech Patent | Tiefdruck-Papier und Herstellungsverfahren für dieses Papier |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1009562B (it) * | 1974-01-15 | 1976-12-20 | Anic Spa | Procedimento per la fabbricazione di strutture composite costituite da materiali cellulosici e polime rici |
| IT1011142B (it) * | 1974-03-25 | 1977-01-20 | Montedison Spa | Procedimento per preparare accoppia ti di fogli di carta con pellicole di materiale polimerico |
| US4166001A (en) * | 1974-06-21 | 1979-08-28 | Kimberly-Clark Corporation | Multiple layer formation process for creped tissue |
| GB1603830A (en) * | 1977-11-10 | 1981-12-02 | Wiggins Teape Group Ltd | Photographic support |
| FR2516107B1 (fr) * | 1981-11-06 | 1985-06-28 | Du Pin Cellulose | Papiers et cartons, procede et dispositif de fabrication |
-
1983
- 1983-09-12 EP EP19830903065 patent/EP0118552A1/de not_active Withdrawn
- 1983-09-12 WO PCT/US1983/001375 patent/WO1984001176A1/en not_active Ceased
Non-Patent Citations (1)
| Title |
|---|
| See references of WO8401176A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1984001176A1 (en) | 1984-03-29 |
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