US2760431A - Lithographic plates and methods for manufacturing same - Google Patents
Lithographic plates and methods for manufacturing same Download PDFInfo
- Publication number
- US2760431A US2760431A US294489A US29448952A US2760431A US 2760431 A US2760431 A US 2760431A US 294489 A US294489 A US 294489A US 29448952 A US29448952 A US 29448952A US 2760431 A US2760431 A US 2760431A
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- US
- United States
- Prior art keywords
- coating
- weight
- water
- polyacrylic acid
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 238000000034 method Methods 0.000 title description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- 238000000576 coating method Methods 0.000 claims description 51
- 239000011248 coating agent Substances 0.000 claims description 46
- 229920002125 Sokalan® Polymers 0.000 claims description 45
- 239000004584 polyacrylic acid Substances 0.000 claims description 44
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 33
- 239000000945 filler Substances 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 28
- 239000002344 surface layer Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 20
- 230000002940 repellent Effects 0.000 claims description 19
- 239000005871 repellent Substances 0.000 claims description 19
- 239000011787 zinc oxide Substances 0.000 claims description 17
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- 229920000058 polyacrylate Polymers 0.000 claims description 12
- 230000002209 hydrophobic effect Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000003384 imaging method Methods 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- -1 HYDROPHOBIC Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 230000008030 elimination Effects 0.000 claims description 3
- 238000003379 elimination reaction Methods 0.000 claims description 3
- 239000002585 base Substances 0.000 description 37
- 239000008199 coating composition Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 239000000123 paper Substances 0.000 description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 12
- 239000000908 ammonium hydroxide Substances 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 11
- 239000004927 clay Substances 0.000 description 11
- 239000000084 colloidal system Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 239000011592 zinc chloride Substances 0.000 description 6
- 235000005074 zinc chloride Nutrition 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 150000004679 hydroxides Chemical class 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- OXIKLRTYAYRAOE-CMDGGOBGSA-N (e)-3-(1-benzyl-3-pyridin-3-ylpyrazol-4-yl)prop-2-enoic acid Chemical compound N1=C(C=2C=NC=CC=2)C(/C=C/C(=O)O)=CN1CC1=CC=CC=C1 OXIKLRTYAYRAOE-CMDGGOBGSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- MJWPFSQVORELDX-UHFFFAOYSA-K aluminium formate Chemical compound [Al+3].[O-]C=O.[O-]C=O.[O-]C=O MJWPFSQVORELDX-UHFFFAOYSA-K 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 3
- 229940007718 zinc hydroxide Drugs 0.000 description 3
- 241000842962 Apoda limacodes Species 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
- 229940071162 caseinate Drugs 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 244000265913 Crataegus laevigata Species 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical group N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 235000010985 glycerol esters of wood rosin Nutrition 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1091—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by physical transfer from a donor sheet having an uniform coating of lithographic material using thermal means as provided by a thermal head or a laser; by mechanical pressure, e.g. from a typewriter by electrical recording ribbon therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N3/00—Preparing for use and conserving printing surfaces
- B41N3/03—Chemical or electrical pretreatment
- B41N3/036—Chemical or electrical pretreatment characterised by the presence of a polymeric hydrophilic coating
-
- 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
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/136—Coating process making radiation sensitive element
Definitions
- lithographic plate manufactured at the present time, a coating formulated of a material such as casein and ester gum is applied to the paper in order to function as a base for the Water receptive hydrophilic colloid.
- the colloid composition formulated of such materials as clay, casein and other filler-s with formaldehyde is applied in one or more layers onto the base coat, depending upon the length of run desired of the plate.
- the surface is insolubilized with a wash coat of a polyvalent metal, such as a solution of aluminum chloride, Zinc chloride, aluminum formate or the like and then insensitized with a coating of sodium silicate or a hydrophilic colloid coat such as of albumen, alginate, guar gum or the like.
- a polyvalent metal such as a solution of aluminum chloride, Zinc chloride, aluminum formate or the like
- a coating of sodium silicate or a hydrophilic colloid coat such as of albumen, alginate, guar gum or the like.
- the paper base sheet is usually pretreated to render it substantially Water repellent as by the application of a resinous varnish, such as a phenol formaldehyde varnish, urea formaldehyde solution, melamine formaldehyde solution or the like.
- a resinous varnish such as a phenol formaldehyde varnish, urea formaldehyde solution, melamine formaldehyde solution or the like.
- the surfaces of the treated paper become less receptive to the hydrophilic coatings and, unless an intermediate anchoring coat is applied to the surface, a satisfactory bonding relation may not be established with the fibrous base sheet.
- 5 to 7 or more coatings are employed to produce a suitable lithographic surface on paper or the like.
- Another object is to produce and to provide a method for producing a lithographic plate of the type described which requires considerably fewer operational steps 1n its manufacture and markedly less material and which in operation is capable of supplying copy of good quality substantially immediately.
- a further object is to produce a low cost lithographic plate of the type described which is easy to manufacture and which becomes insensitive without the requirement of special treatments and it is a related object to produce a lithographic plate of the type described in a single coating process to provide considerable savings in time, labor and material; which is characterized by excellent stability, substantial insensitivity and which is capable of holding an ink receptive image having the properties of immediate reproduction of copy of good quality, and which continues to produce such copies for a considerable length of time.
- a lithographic surface of the type described may be produced in a singlecoating with a composition containing ammonia, a Water soluble polyacrylic acid and an inert filler in finely divided form in combinationwith an oxide or a hydroxide of a polyvalent metal capable of form ing an insoluble salt with the polyacrylic acid but which remains soluble in the presence of sufiicient ammonia in the form of ammonium hydroxide 'or a water soluble ammonia salt.
- Example 1 180 parts by weight finely divided clay and 18 parts by Weight zinc oxide in "finely divided form are mixed and formed into a slurry with about parts by weight water.
- parts 'by Weight of a 25 percent water solution of polyacrylic acid (Polyco 437, manufactured by American Polymer Company, or Acrysol CH144C, manufactured by Rohm & Haas) is neutralized With about 100 parts by Weight concentrated ammonium hydroxide and then the polyacrylic acid solution is combined with the slurry of clay and zinc oxide. This forms a relatively stable coating composition con taining about 40 percent solids.
- the composition is coated onto a high wet strength paper in coating weights of about 8-10 pounds per 3000 square feet of surface and then the coating may be allowed to air dry but it is preferably dried at an elevated temperature, such as a temperature within the range of ZOO-350 F. to accelerate the drying rate.
- the coating may be applied by a brush .coater, roller coater, or knife coater, but it is preferred to use an air knife applicator in order to achieve greater uniformity in coating weights and a smoother coated surface.
- the hydrophilic colloid material becomes highly insoluble possibly by reason of the fact that the ammonia ion is eliminated by volatilization with the result that an insoluble metal salt with the polyacrylate is formed.
- the resulting surface is highly receptive to water so that it is substantially immediately Wet out with repellent. in use, yet it is capable of receiving and holding an ink receptive, water repellent imaging material applied by various means common in the imaging of conventional lithographic surfaces.
- the lithographic surface that is formed on the paper base sheet does not cause excessive stiffening or embrittlement of the base sheet so that the composite structure can be readily used in a typewriter or the like for imaging in the usual manner for office duplication.
- the surface formed upon drying of the coating composition is insoluble yet readily wet out by Water or other repellent in the non-imaging areas and Water repellent and ink receptive in the areas imaged with a greasy composition or the like, the surface is sufficiently insensitive without further treatment to resist reproduction of areas which might giadvertently be touched as an incidence to normal harring.
- the amount of zinc oxide in the coating composition is preferably maintained within the range of 2 parts by weight zinc oxide to 47 parts by weight of the polyacrylic acid.
- the amount of zinc oxide in the coating composition is preferably maintained within the range of 2 parts by weight zinc oxide to 47 parts by weight of the polyacrylic acid.
- the formed surface appears to be less capable of resisting deterioration in use.
- the coating that is formed becomes brittle but greater amounts can be used when the coating composition is modified to include flexibilizing agents such as glycerine, ethylene glycol, polyethylene glycol and other polyhydric alcohols. Under any circumstances, it is not desirable to use zinc oxide in amounts in excess of the concentration of polyacrylic acid.
- zinc oxide as a component of the filler system, but similar results with respect to the solibility of the acrylic acid in the presence of sufiicient ammonia and insolubilization of the polyacrylate upon loss of ammonia from the coating composition have been found to result from the use of zinc hydroxide in equivalent amounts on the molecular Weight basis.
- zinc oxide may be replaced by magnesium oxide or hydroxide and to a lesser extent by other alkaline earth metal oxides or hydroxides of the type calcium oxide, lead oxide and barium oxide.
- the ammonium ion maintains the solubility of the polyacrylic acid for formation of a complex double salt therewith in combination with a metallic component whereby the materials are maintained in solution in the composition but an insolubilized salt is formed upon release of ammonia during drying. It is also possible that the salt forming group of the polyacrylic acid is preferentially receptlve to the ammoma 10H to resist combination with the metallic ion in the formation .of the insoluble salt or it may be that the ammonium ion forms an insoluble salt with the metallic oxide or hydroxide having characteristics which militate against the formation of an insoluble salt with the polyacrylic acid.
- inert fillers such as diatomaceous earth, satin white, chalk, talc, silica and the like in substantially equivalent amounts may be used. Best results are secured when the ratio of inert filler to metal oxide is maintained within the range of 1 part by weight metal oxide or its equivalent weight of hydroxide to 2-20 parts by weight filler and when the ratio of filler and metal oxide or hydroxide to polyacrylic acid is maintained within the range of 1 part by weight polyacrylic acid to 2-10 parts by weight of the filler and metal oxide.
- ammonia is present in amounts sufficient to maintain the solubliity of the polyacrylic acid in the presence of metal oxide
- the amount for solubilization defines the minimum concentration thereof. Larger amounts of ammonia can be used further to increase the stability of the composition and larger amounts of ammonia are often preferred to lower the apparent viscosity of the coating composition to achieve heavier coating Weights.
- ammonium hydroxide use may be made of ammonium carbonate or the like in equivalent amounts on a molecular weight basis.
- the solids content of the coating composition may be varied over a fairly wide range, such as from 20 to 60 percent, depending upon the manner of application and the coating weight desired on the base sheet. Coating weights of 6 to 12 pounds per 3000 square feet of surface are capable of being secured by a single application to provide a lithographic surface suitable for use in the reproduction of up to 1000 or more copies. While it is preferred to rely on a single coating step in the manufacture of a low cost lithographic plate, multiple coatings may be applied when desired to achieve heavier coating weights and longer life in use for the reproduction of copies.
- Suitable supports for the lithographic surface may include paper, fiber board, textile fabrics, plastic sheet stock or metal strip preferably of such thin dimension as to provide for sufiicient flexibility for bending about a typewriter platen but with sufiicient strength to maintain dimensional stability for at least the number of copies that is desired to produce therefrom.
- the base sheet comprises paper or other sheet stock of fibrous character ordinarily having a high degree of water absorption
- water repellent materials such as resinous solutions of urea formaldehyde, melamine formaldehyde, phenol formaldehyde or alkyd resins, or by treatment of the fabric with wax, oils, fatty acid amines or other water repellent surfaces.
- compositions diluted with water to a solids content ranging from 40-60 per cent solids, may be applied as by an air blade applicator in amounts to provide a coating weight of 6-12 pounds per 3000 square feet of surface onto 40-pound high wet strength kraft paper.
- the coated paper may immediately be passed through an air drying oven heated to a temperature of about 250 F. whereupon the coating becomes substantially completely insolubilized to provide alithographic surface of the type described.
- insolubility of the coating and the life of the lithographic surface is further improved by the addition of water soluble bivalent metal salts of the type zinc chloride and zinc acetate to the coating composition.
- Incorporation may'be made by introduction of the zinc salt as an ingredient in the coating composition in amounts ranging from 1-10 per cent by weight thereof.
- the bivalent metal salt as an ingredient in the coating composition to provide a single coating process for the manufacture of lithographic plates, improved results may also be secured when the bivalent metal salt is applied as a wash coat on the formed surface.
- Such application may be made from solutions containing the bivalent metal salt in amounts ranging from 5-25 per cent by weight.
- zinc salts of the type described use may also be made of the water solublesalts of magnesium, nickel, cobalt, calcium, barium andthe like in the form of their chlorides, acetates and the like.
- Example 6 160 parts polyacrylic acid, 25% solids 120 parts ammonium hydroxide, concentrated 180 parts clay 15 parts Zinc oxide 5 parts zinc chloride
- the above composition may be applied onto a suitable base sheet in the manner previously described with respect to Examples 1-5 inclusive. Brushing the surface of the plate while wet but preferably while dry, as with a bristle brush, soft cotton pad or the like improves the lithographic properties of the plate, as by making correction easier, improving wet-out and decreasing penetration of repellent or moisture into the coating.
- hydrophilic lithographic surface formed of clay-zine polyacrylate in accordance with the practice of this invention may be formed on a surface previously coated with an insolubilized hydrophilic colloid.
- This modification to produce an excellent lithographic plate capable of immediate reproduction and long life may be illustrated by the following.
- Coating compositions to provide coating weights of about 14 pounds per 500 of 20 by 24 inch plates are applied to the surface of high wet strength paper in the form of a continuous web followed by drying at elevated temperature of about 250 F.
- the colloid coating After the colloid coating has dried, it is further treated by the application of a wash coat containing 86 per cent by weight aluminum formate and 14 per cent by weight butanol.
- the wash coat is applied in amounts of about 1.5 gallons per 500 sheets and then air dried or dried at elevated temperature by running through an air drying oven or in a festoon drier.
- compositions of Examples 1-6 may be applied in the manner described to produce
- the diazolith compound may be applied onto a zinc polyacrylate coating. formed directly on a base sheet, as in Examples 1-6, or onto a lithographic coating formed on an insolubilized hydrophilic coating, as in Example 7.
- Example 8 A sensitizing solution containing 1 percent by weight Diazolith #1 compound, marketed by Edwal Laboratories, 5 percent sodium acetate and 94- percent water is swabbed onto any of the surfaces prepared in accordance with Examples l-7 inclusive.
- Lithographic surfaces formed of zinc or other of the described polyacrylate compositions directly on a base sheet or upon an insolubilized hydrophilic colloid coating may also be presensitized with a diazolith compound to" produce a presensitized photolithographic plate.
- the following will specifically illustrate the manufacture of presensitized plates of the type described on zinc polyacrylate surfaces.
- Example 9 A- supercalendered kraft paper is rod coated with the following composition:
- the coating composition is prepared by dissolving the zinc chloride in water, adding the ammonium hydroxide and then incorporating the polyacrylic acid.
- the coating composition is applied to the paper base sheet in amount to provide coating weights of 20-30 pounds per 3000 square feet of surface area.
- the surface is swabbed with a 1 percent solution of the diazolith compound corresponding to that produced by Example 1 of the Schmidt Patent No. 2,063,631.
- the diazolith is incorporated with 4 percent sodium acetate in water solu-- tion.
- the plate formed with the above composition need not be desensitized after exposure and before running to produce copies.
- Example 10 High wet strength kraft paper is coated first with a composition containing the following:
- Colloid base coat composition is a composition of Colloid base coat composition:
- the colloid composition is brush coated onto a web of high strength paper to provide a coating weight of 30 pounds per 3000 square feet of surface area. After the coating has been dried as in a festoon drier at a temperature between 200 and 300 F., the surface is washed with a 65 percent solution of aluminum formate.
- Lithographic coating composition 10 grams sodium polyacrylate 10 grams zinc chloride 45 milliliters concentrated ammonium hydroxide face is brushed with bristle brushes and after the surface has been dried, preferably at elevated temperature, it is swabbed with a solution containing 1 percent Diazolith #1, marketed by Edwal Laboratories, percent sodium acetate and 94 percent Water. The applied solution is adjusted to a pH of about 6.3.
- diazolith compounds of the type described as the presensitizing composition for lithographic surfaces formed in accordance with the practice of this invention, it will be understood that other conventional sensitizing agents may also be used.
- a planographic printing plate comprising a base sheet and a continuous, water insoluble lithographic surface layer on the base sheet in the form of a coating comprising the reaction product of the combination in admixture of an inert filler, polyacrylic acid and zinc oxide and an ink receptive, water repellent, hydrophobic imaging material in the form of a mechanically applied image anchored onto the underlying continuous, Water insoluble surface layer.
- a planographic printing plate comprising a base sheet and a continuous, water insoluble lithographic surface layer on the base sheet in the form of a coating comprising the reaction product of the combination in admixture of an inert filler, polyacrylic acid and zinc oxide present in the ratio of 2 parts by weight thereof to 4 to 7 parts by Weight of the polyacrylic acid and an ink receptive, water repellent, hydrophobic imaging material in the form of a mechanically applied image anchored onto the underlying continuous, water insoluble lithographic surface layer.
- a planographic printing plate comprising a base sheet and a continuous, water insoluble lithographic surface layer on the base sheet in the form of a coating comprising the reaction product of the combination in admixture of an inert filler, polyacrylic acid and zinc oxide present in the ratio of 1 part by weight thereof to 2 to 20 parts by Weight of the filler and 1 part by Weight polyacrylic acid to 2 to 10 parts by Weight of the filler plus base and an ink receptive, Water repellent, hydrophobic imaging material in the form of a mechanically applied image anchored onto the underlying continuous, water insoluble lithographic surface layer.
- a planographic printing plate comprising a base sheet and a continuous, water insoluble lithographic surface layer on the base sheet in the form of a coating comprising the reaction product of the combination in admixture of an inert filler, polyacrylic acid and a bivalent metal salt which forms a water insoluble polyacrylate and a water soluble, water stable complex double salt with the polyacrylate in the presence of suflicient ammonia and present in the ratio of 1 part by weight of the metal salt to 2 to parts by weight filler and 1 part by weight polyacrylic acid to 2 to 10 parts by weight of the filler plus metal salt and an ink receptive, Water repellent, hydrophobic imaging material in the form of a mechanically applied image anchored onto the underlying continuous, water insoluble lithographic surface layer.
- a planographic printing plate comprising a base sheet and a continuous, water insoluble lithographic surface layer on the base sheet in the form of a coating comprising the reaction product of the combination in admixture of an inert filler, polyacrylic acid and a metal base selected from the group consisting of the oxides and hydroxides of zinc, magnesium, calcium, lead and barium and mixtures thereof and present in the ratio of 1 part by weight of the metal base to 2 to 20 parts by Weight of the filler and 1 part by Weight polyacrylic acid to 2 to 10 parts by weight of filler and metal base and an ink receptive, water repellent, hydrophobic imaging material in the form of a mechanically applied image anchored onto the underlying continuous, Water insoluble lithographic surface layer.
- the method of manufacturing a planographic printing plate comprising the steps of coating a base sheet to provide a continuous lithographic surface layer with a composition containing inert filler, polyacrylic acid, a water soluble bivalent metal salt which forms a water insoluble polyacrylate and a Water soluble, water stable complex double salt with the polyacrylate in the presence of sufficient ammonia and present in the ratio of 1 part by weight metal salt to 2 to 20 parts by weight filler and 1 part by weight polyacrylic acid to 2 to 10 parts by Weight filler plus metal salt and sufficient ammonium ion present in the composition to maintain the metal salt and polyacrylic acid in solution, and drying the coating on the base sheet to form a hydrophilic, lithographic surface which becomes Water insoluble upon elimination of ammonia and mechanically applying to said continuous lithographic surface layer an image in the form of a water repellent, hydrophobic, ink receptive material.
- the method of manufacturing a planographic printing plate comprising the steps of coating :1 base sheet to provide a continuous lithographic surface layer with a composition containing inert filler, polyacrylic acid and a metal base selected from the group consisting of the oxides and hydroxides of zinc, magnesium, calcium, lead and barium and mixtures thereof and sufficient ammonium ion present to maintain the metal base and polyacrylic acid in solution, and drying the coating on the base sheet to form a hydrophilic, lithographic surface which becomes water insoluble upon elimination of ammonia and mechanically applying to said continuous lithographic surface layer an image in the form of a water repellent, hydrophobic, ink receptive material.
- the method of manufacturing a planographic printing plate comprising the steps of coating a base sheet to provide a continuous lithographic surface layer with a composition containing inert filler, polyacrylic acid, a zinc base selected from the group consisting of zinc oxide, zinc hydroxide and mixtures thereof and present in the ratio of 1 part by weight zinc base to 2 to 20 parts by weight filler and 1 part by weight polyacrylic acid to 2 to 10 parts by weight filler plus zinc base and ammonium ion present in amounts in excess of that necessary to maintain the solubility of the zinc base and the polyacrylic acid, and drying the coating to form a continuous, water insoluble hydrophilic, lithographic surface layer, and mechanically applying to said continuous lithographic surface layer an image in the form of a water repellent, hydrophobic, ink receptive material 9.
- the method of manufacturing a planographic printing plate comprising the steps of coating a base sheet to provide a continuous lithographic surface layer with a composition containing inert filler, polyacrylic acid, and a metal base selected from the group consisting of the oxides and hydroxides of zinc, magnesium, calcium, lead and barium and mixtures thereof and present in the ratio of 1 part by weight metal base to 2 to 20 parts by weight filler and 1 part by Weight polyacrylic acid to 2 to 10 parts by weight filler plus metal base and ammonium ion present in amounts in excess of that necessary to maintain the solubility of the metal base and the polyacrylic acid, drying the coating to form a continuous, water insoluble hydrophilic, lithographic surface layer and mechanically applying to said continuous lithographic surface layer an image in the form of a water repellent, hydrophobic, ink receptive material.
- a composition containing inert filler, polyacrylic acid, and a metal base selected from the group consisting of the oxides and hydroxides of zinc, magnesium,
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Printing Plates And Materials Therefor (AREA)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE557236D BE557236A (fi) | 1952-06-19 | ||
US294489A US2760431A (en) | 1952-06-19 | 1952-06-19 | Lithographic plates and methods for manufacturing same |
GB10632/57A GB812508A (en) | 1952-06-19 | 1957-04-01 | Lithographic printing plates and methods for manufacturing same |
FR1174778D FR1174778A (fr) | 1952-06-19 | 1957-05-03 | Cliché d'impression planographique et son procédé de fabrication |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US294489A US2760431A (en) | 1952-06-19 | 1952-06-19 | Lithographic plates and methods for manufacturing same |
Publications (1)
Publication Number | Publication Date |
---|---|
US2760431A true US2760431A (en) | 1956-08-28 |
Family
ID=23133660
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US294489A Expired - Lifetime US2760431A (en) | 1952-06-19 | 1952-06-19 | Lithographic plates and methods for manufacturing same |
Country Status (4)
Country | Link |
---|---|
US (1) | US2760431A (fi) |
BE (1) | BE557236A (fi) |
FR (1) | FR1174778A (fi) |
GB (1) | GB812508A (fi) |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2922715A (en) * | 1956-03-26 | 1960-01-26 | Polychrome Corp | Presensitized printing plate and method for preparing same |
US2951441A (en) * | 1956-01-16 | 1960-09-06 | Timefax Corp | Lithographic printing plates and coatings therefor |
US3061429A (en) * | 1956-12-28 | 1962-10-30 | Azoplate Corp | Diazo printing plates and method for the production thereof |
US3097097A (en) * | 1959-02-12 | 1963-07-09 | Gisela K Oster | Photo degrading of gel systems and photographic production of reliefs therewith |
US3107169A (en) * | 1958-12-18 | 1963-10-15 | Bruning Charles Co Inc | Processes of producing lithographic electrostatic printing plates |
US3136636A (en) * | 1950-12-06 | 1964-06-09 | Minnesota Mining & Mfg | Planographic printing plate comprising a polyacid organic intermediate layer |
US3211686A (en) * | 1959-06-18 | 1965-10-12 | Plastic Coating Corp | Aqueous composition for prewetting a master carrying an image prepared by electrophotographic reproduction containing polyacrylic acid |
US3220830A (en) * | 1961-10-02 | 1965-11-30 | Kenffel & Esser Company | Method of developing a negative electrostatic latent image |
US3228769A (en) * | 1961-05-04 | 1966-01-11 | Minnesota Mining & Mfg | Photosensitive copy-sheet comprising zinc oxide and a diazonium compound and method of copying |
US3232783A (en) * | 1958-10-03 | 1966-02-01 | Lithoplate Inc | Resinous coatings adapted to receive a light-sensitive layer in the production of lithographic printing plates |
US3256810A (en) * | 1964-03-09 | 1966-06-21 | Anthony L Ensink | Planographic printing plates |
US3258339A (en) * | 1964-05-28 | 1966-06-28 | Harris Intertype Corp | Lithographic plate and method of preparing same |
US3298852A (en) * | 1963-02-07 | 1967-01-17 | Dick Co Ab | Metal offset plate and method for manufacture |
US3349704A (en) * | 1965-01-28 | 1967-10-31 | Dick Co Ab | Coated paper duplicating master |
US3415187A (en) * | 1964-11-23 | 1968-12-10 | Mead Corp | Lithographic plate and method for manufacturing same |
US3471625A (en) * | 1957-02-15 | 1969-10-07 | Harris Intertype Corp | Electrophotographic coating containing finely divided photoconductor in a synthetic polymer having ionizable functional groups |
US3473926A (en) * | 1964-05-04 | 1969-10-21 | Eastman Kodak Co | Negative material for converting from letterpress to lithography |
US3511661A (en) * | 1966-07-01 | 1970-05-12 | Eastman Kodak Co | Lithographic printing plate |
FR2426457A1 (fr) * | 1978-05-22 | 1979-12-21 | Minnesota Mining & Mfg | Ciment chirurgical et procede de sa preparation |
US4221690A (en) * | 1977-07-12 | 1980-09-09 | Feldmuhle Aktiengesellschaft | Coating composition for acceptor sheets in carbonless copying |
US4271058A (en) * | 1978-07-01 | 1981-06-02 | Rohm Gmbh | Stable aqueous solutions of certain vinyl copolymers |
US5958647A (en) * | 1997-05-20 | 1999-09-28 | Morgan; David A. | Thermosensitive etch resist for forming a mask |
US6063528A (en) * | 1997-05-20 | 2000-05-16 | Morgan; David A. | Thermosensitive composition |
US20100068678A1 (en) * | 2008-09-12 | 2010-03-18 | Gc Corporation | Cement for sealer |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE606888A (fi) * | 1960-08-05 | 1900-01-01 |
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GB371041A (en) * | 1930-05-26 | 1932-04-14 | Ig Farbenindustrie Ag | Improvements in the treatment of fibrous materials |
US1981102A (en) * | 1932-08-10 | 1934-11-20 | Agfa Ansco Corp | Photographic material and process of making the same |
US2184310A (en) * | 1937-06-10 | 1939-12-26 | Du Pont | Photographic and printing media |
US2649373A (en) * | 1948-10-18 | 1953-08-18 | Warren S D Co | Paper printing foils for lithographic purposes and a process of preparing them |
-
0
- BE BE557236D patent/BE557236A/xx unknown
-
1952
- 1952-06-19 US US294489A patent/US2760431A/en not_active Expired - Lifetime
-
1957
- 1957-04-01 GB GB10632/57A patent/GB812508A/en not_active Expired
- 1957-05-03 FR FR1174778D patent/FR1174778A/fr not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB371041A (en) * | 1930-05-26 | 1932-04-14 | Ig Farbenindustrie Ag | Improvements in the treatment of fibrous materials |
US1981102A (en) * | 1932-08-10 | 1934-11-20 | Agfa Ansco Corp | Photographic material and process of making the same |
US2184310A (en) * | 1937-06-10 | 1939-12-26 | Du Pont | Photographic and printing media |
US2649373A (en) * | 1948-10-18 | 1953-08-18 | Warren S D Co | Paper printing foils for lithographic purposes and a process of preparing them |
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3136636A (en) * | 1950-12-06 | 1964-06-09 | Minnesota Mining & Mfg | Planographic printing plate comprising a polyacid organic intermediate layer |
US2951441A (en) * | 1956-01-16 | 1960-09-06 | Timefax Corp | Lithographic printing plates and coatings therefor |
US2922715A (en) * | 1956-03-26 | 1960-01-26 | Polychrome Corp | Presensitized printing plate and method for preparing same |
US3061429A (en) * | 1956-12-28 | 1962-10-30 | Azoplate Corp | Diazo printing plates and method for the production thereof |
US3471625A (en) * | 1957-02-15 | 1969-10-07 | Harris Intertype Corp | Electrophotographic coating containing finely divided photoconductor in a synthetic polymer having ionizable functional groups |
US3232783A (en) * | 1958-10-03 | 1966-02-01 | Lithoplate Inc | Resinous coatings adapted to receive a light-sensitive layer in the production of lithographic printing plates |
US3107169A (en) * | 1958-12-18 | 1963-10-15 | Bruning Charles Co Inc | Processes of producing lithographic electrostatic printing plates |
US3097097A (en) * | 1959-02-12 | 1963-07-09 | Gisela K Oster | Photo degrading of gel systems and photographic production of reliefs therewith |
US3211686A (en) * | 1959-06-18 | 1965-10-12 | Plastic Coating Corp | Aqueous composition for prewetting a master carrying an image prepared by electrophotographic reproduction containing polyacrylic acid |
US3228769A (en) * | 1961-05-04 | 1966-01-11 | Minnesota Mining & Mfg | Photosensitive copy-sheet comprising zinc oxide and a diazonium compound and method of copying |
US3220830A (en) * | 1961-10-02 | 1965-11-30 | Kenffel & Esser Company | Method of developing a negative electrostatic latent image |
US3298852A (en) * | 1963-02-07 | 1967-01-17 | Dick Co Ab | Metal offset plate and method for manufacture |
US3256810A (en) * | 1964-03-09 | 1966-06-21 | Anthony L Ensink | Planographic printing plates |
US3473926A (en) * | 1964-05-04 | 1969-10-21 | Eastman Kodak Co | Negative material for converting from letterpress to lithography |
US3258339A (en) * | 1964-05-28 | 1966-06-28 | Harris Intertype Corp | Lithographic plate and method of preparing same |
US3415187A (en) * | 1964-11-23 | 1968-12-10 | Mead Corp | Lithographic plate and method for manufacturing same |
US3349704A (en) * | 1965-01-28 | 1967-10-31 | Dick Co Ab | Coated paper duplicating master |
US3511661A (en) * | 1966-07-01 | 1970-05-12 | Eastman Kodak Co | Lithographic printing plate |
US4221690A (en) * | 1977-07-12 | 1980-09-09 | Feldmuhle Aktiengesellschaft | Coating composition for acceptor sheets in carbonless copying |
FR2426457A1 (fr) * | 1978-05-22 | 1979-12-21 | Minnesota Mining & Mfg | Ciment chirurgical et procede de sa preparation |
US4288355A (en) * | 1978-05-22 | 1981-09-08 | Minnesota Mining And Manufacturing Company | Surgical cement composition |
US4271058A (en) * | 1978-07-01 | 1981-06-02 | Rohm Gmbh | Stable aqueous solutions of certain vinyl copolymers |
US5958647A (en) * | 1997-05-20 | 1999-09-28 | Morgan; David A. | Thermosensitive etch resist for forming a mask |
US6063528A (en) * | 1997-05-20 | 2000-05-16 | Morgan; David A. | Thermosensitive composition |
US20100068678A1 (en) * | 2008-09-12 | 2010-03-18 | Gc Corporation | Cement for sealer |
US8642679B2 (en) * | 2008-09-12 | 2014-02-04 | Gc Corporation | Dental cement composition |
Also Published As
Publication number | Publication date |
---|---|
BE557236A (fi) | |
GB812508A (en) | 1959-04-29 |
FR1174778A (fr) | 1959-03-16 |
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