EP0176475B1 - Compositions pour le revêtement sous forme de poudres - Google Patents

Compositions pour le revêtement sous forme de poudres Download PDF

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Publication number
EP0176475B1
EP0176475B1 EP85810379A EP85810379A EP0176475B1 EP 0176475 B1 EP0176475 B1 EP 0176475B1 EP 85810379 A EP85810379 A EP 85810379A EP 85810379 A EP85810379 A EP 85810379A EP 0176475 B1 EP0176475 B1 EP 0176475B1
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Prior art keywords
composition according
weight
parts
epoxy resin
bis
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Expired - Lifetime
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EP85810379A
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German (de)
English (en)
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EP0176475A3 (en
EP0176475A2 (fr
Inventor
Noel Sydney Moss
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Novartis AG
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Ciba Geigy AG
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Classifications

    • 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
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/02—Engraving; Heads therefor
    • B41C1/04—Engraving; Heads therefor using heads controlled by an electric information signal
    • B41C1/05—Heat-generating engraving heads, e.g. laser beam, electron beam
    • 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
    • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/934—Powdered coating composition

Definitions

  • the invention relates to new curable mixtures for powder coatings and their use for the production of printing plates, and the printing plates thus produced.
  • Printing plates e.g. For rotogravure printing, they have to be made of materials that can be easily engraved with the image to be printed. They must have good solvent resistance to be resistant to the printing ink components, they must also have good wear resistance to the abrasion by the paper and the squeegee used to remove excess printing ink; after all, they must also be dimensionally stable.
  • metal printing plates e.g. Copper, manufactured, which was acid-etched to form the patterns and electroplated for longer print cycles to achieve good wear resistance.
  • polymeric materials such as epoxy resins
  • the spots of the polymeric material that are hit by the laser beam are evaporated, so that these spots become recording points for the printing ink for later printing.
  • the depth of the engraving caused by the laser determines the amount of printing ink contained therein and thus the color strength of the print obtained.
  • non-patterned metal printing elements coated with a laser-engravable polymer is known and has been e.g. in British Patent Nos. 2,071,574 and 2,087,796. These patents describe both epoxy resin powder coating compositions which are applied to the substrate and then engraved with a laser. What is new about this process is the nature of the additives added to the powder coating compositions.
  • the mixtures contain 0-20% of a finely divided filler, preferably 1-5% carbon black.
  • the additives consist of graphite, molybdenum sulfide or polytetrafluoroethylene.
  • the epoxy resin mixtures used contain a bisphenol diglycidyl ether and a polyglycidyl derivative. These mixtures are hardened with an aromatic diaminodiphenyl sulfone as hardener and in the presence of an imidazole accelerator.
  • the mixture can - as is customary in powder coating technology - also agents which promote the escape of air from the coatings and thus prevent the formation of holes in the surface of the coating, such as e.g. Benzoin, or flow agent, e.g. Poly (butyl acrylate).
  • agents which promote the escape of air from the coatings and thus prevent the formation of holes in the surface of the coating such as e.g. Benzoin, or flow agent, e.g. Poly (butyl acrylate).
  • the invention also relates to a method for producing laser-engravable printing plates, especially for gravure printing, a base material made of metal being coated with the powder coating composition described above and the coating being melted to form a hardened continuous layer.
  • the invention further relates to the coatings obtained by this method and the use of the powder coating composition for the production of printing plates for laser engraving.
  • Suitable bifunctional epoxy resins that can be used as component (a) are known and commercially available. These include e.g. Bisphenol diglycidyl ether and its pre-extension products with dihydric alcohols and phenols.
  • the bisphenol diglycidyl ethers preferred as component (a) have a softening point between 50 ° and 140 ° C., particularly 65 ° and 80 ° C., (measured on the Kofler bench) and have an epoxy content of at least 0.5 equivalents / kg.
  • Particularly preferred resins are those obtained by reaction with resorcinol, hydroquinone, bis (4-hydroxyphenyl) methane, 4-4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfone or 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] pre-extended diglycidyl ether of bis (4-hydroxyphenyl) methane, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfone, 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (3,5-dibromo) 4-hydroxyphenyl) propane.
  • epoxy resins with a functionality greater than 2 which are used as component (b) are polyglycidyl or Poly (beta-methylglycidyl) esters of polycarboxylic acids, such as trimellitic acid, or polyglycidyl or poly (beta-methylglycidyl) ethers of polyhydric phenols or alcohols, such as 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, or of novolaks from aldehydes, such as formaldehyde, acetaldehyde, chloral and furfurylaldehyde, and phenols such as the unsubstituted phenol and in the ring by chlorine atoms or alkyl groups with up to 9 C-substituted phenols, such as 4-chlorophenol, 2-methylphenol and 4-tert-butylphenol , and poly (N-glycidyl) compounds, such as triglycidyl isocyanurate, or compounds
  • the diaminodiphenyl sulfones which can be used as curing agent (c) are generally commercially available and correspond to the formula III wherein R1 represents a hydrogen atom or an alkyl group having 1-12 C atoms.
  • Preferred compounds of the formula III are those in which R 1 represents a hydrogen atom. 3,3'-diaminodiphenyl sulfone and 4,4'-diaminodiphenyl sulfone are very particularly preferred.
  • the imidazole accelerators which can be used as component (d) are generally commercially available and correspond to the general formulas IV or V. wherein the different R2 independently of one another denote hydrogen or halogen atoms, alkyl, alkoxy, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl or aralkyl groups with up to 15 carbon atoms.
  • R2 examples include methyl, ethyl, isopropyl, butyl, n-hexyl, n-octyl, n-undecyl, n-heptadecyl, methoxy, ethoxy, butoxy, allyl, cyclohexyl, cyclohexenyl, phenyl, tolyl and benzyl.
  • the particularly preferred imidazoles include, for example, 2-isopropylimidazole, 2,4-dioctylimidazole, 2-octyl-4-hexylimidazole, 4-butyl-5-ethylimidazole, 2-butoxy-4-allylimidazole, 2-cyclohexyl-4-methylimidazole, 2 -n-undecylimidazole, 2-n-heptadecylimidazole and 2-benzylimidazole.
  • imidazoles of the formula IV or V in which each radical R2 is hydrogen, or in which at least one group R2 is C1-C8-alkyl or phenyl, and the remaining groups R2 are hydrogen.
  • imidazoles include e.g. Imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, benzimidazole, 2-methylbenzimidazole and their salts with acids.
  • the proportions of the various components in the mixtures according to the invention can be varied depending on the type of the compounds and the properties desired in the cured or uncured compositions. Generally, based on 100 parts by weight of the bifunctional epoxy resin (a), 5-100 parts by weight of the polyfunctional epoxy resin (b), 5-35 parts by weight of the diaminodiphenyl sulfone (c) and 0.01-2.0 parts by weight of the imidazole (d) are used .
  • 100 to 50 parts by weight of the bifunctional resin (a) are preferably 5-50, in particular 10-40, and very particularly 15-35 parts by weight of the polyfunctional resin (b), and 5-25, in particular 10-20, parts by weight of the diaminodiphenyl sulfone (c), and 0.01-2.0, in particular 0.1-0.5, parts by weight of the imidazole (d).
  • Printing surfaces that are used when printing on cardboard generally have to have a higher solvent resistance than those that are used in paper printing; for the former substrate, printing inks are used which contain more effective solvents, against which the printing plate is said to be resistant.
  • compositions according to the invention are to be used to produce these surfaces, they preferably contain, per 100 parts by weight of the bifunctional resin (a), 35-80, in particular 40-70, parts by weight of the polyfunctional resin (b), 15-35, in particular 20-30 Parts by weight of the diaminodiphenyl sulfone (c) and 0.1-2.0, in particular O, 2-1.0, parts by weight of the imidazole (d).
  • the new mixtures can be obtained by simply mixing the components, e.g. in a ball mill. However, they can also be produced by melting the components together, preferably in an extrusion press, such as a Buss co-kneader, and then grinding the cooled mass.
  • the mixtures preferably have a particle size between 50 and 200 micrometers, particularly 75 and 125 micrometers.
  • a metallic substrate which is a flat sheet or usually an anilox roller, is heated to temperatures between 150 and 250 ° C., preferably 190 and 220 ° C.
  • the powder is then applied using conventional powder coating techniques, e.g. by electrostatic spraying processes or by fluid bed application processes.
  • the powder is then melted and cured by further heating, generally at temperatures between 150 and 250 ° C for 10 minutes to 2 hours, especially at temperatures between 190 and 220 ° C for 20 minutes to 2 hours. This results in uniform 300-450 micron thick coatings.
  • the coated substrate is cooled and polished with a diamond cutter or similar conventional means to an optically flat and smooth coating. In general, engraving is then carried out using a laser.
  • the printing plates obtained in this way have considerable wear resistance and are therefore suitable for long printing cycles. Such good wear resistance has so far not been achieved without the addition of finely divided hard fillers, which - as mentioned above - can cause difficulties during polishing and mixing.
  • Example 1 The following components are mixed at room temperature and then processed as a hot melt by the extrusion process at 90-130 ° C: 98 parts with bisphenol A up to an epoxy content of 1.4 equivalents / kg of pre-extended 2,2-bis (4th -glycidyloxyphenyl) propane, 2 parts poly (butyl acrylate) as flow agent, 25 parts polyglycidyl ether of a cresol-formaldehyde novolak with an epoxy content of 5.75 equivalents / kg, 16.7 parts 4,4'-diaminodiphenyl sulfone, 0.22 parts 2 -Methylimidazole and 2.1 parts benzoin.
  • the extruded material is cooled to 25 ° C and ground to a particle size below 150 microns. A sample of this powder gels in 105 seconds when heated to 200 ° C.
  • the powder is applied to steel plates heated to 210 ° C using the electrostatic spray method and adheres well to it.
  • the plates are heated for a further period of time, laser-engravable surfaces (printing plates) being obtained. These are tested for abrasion resistance at 23 ° C.
  • a Taber Abraser device (Taber Instrument Corp., North Tonawanda, New York, USA) with grinding wheels CS 17 at 1000 g load is used. The weight loss per 1000 revolutions is determined:
  • Solvent resistance is checked by rubbing the coatings with a cotton ball soaked in methyl ethyl ketone. No change is found after 100 rubs.
  • Example 2 Example 1 is repeated, but using 0.32 part of 2-methylimidazole.
  • the gel time at 200 ° C is 70 seconds.
  • the weight loss when grinding after curing at 210 ° C is as follows:
  • Examples 3-8 The following resins are used in these examples: Resin I: 2,2-bis- (4-glycidylphenyl) propane with an epoxide content of 1.4 equivalents / kg, pre-extended with bisphenol A. 99 parts of this resin are admixed with 1 part of poly (butyl acrylate) as a flow agent.
  • Resin II This is the polyglycidyl ether of a cresol-formaldehyde novolak with an epoxy content of 5.75 equivalents / kg and a softening point of 99 ° C.
  • Resin III This is the polyglycidyl ether of a bisphenol A formaldehyde novolak with an epoxy content of 4.9 equivalents / kg and a softening point of 50-60 ° C.
  • Resin IV this is a tetrakis (N-glycidyl) derivative of bis (4-aminophenyl) methane with an epoxide content of 7.8-8.2 equivalents / kg.
  • Resin V This is the polyglycidyl ether of a phenol-formaldehyde novolak with an epoxy content of 5.4 equivalents / kg.
  • compositions from resin I or one of the resins II to V, from 4,4'-diaminodiphenyl sulfone (DDS), an imidazole and benzoin are produced by mixing at room temperature and subsequent melt extrusion at 90-130 ° C (in the case of resin IV and resin V this is premixed with resin I before mixing with the other constituents).
  • the extrudate is cooled to 25 ° C. and ground to a powder that has a particle size of less than 150 ⁇ m.
  • This powder is applied by electrostatic spraying to steel plates heated to 210 o C, where it adheres well.
  • the plates become one heated for a further time, creating surfaces for laser engraving.
  • the gelation time of the powder at 180 ° C. is also determined. Furthermore, the solvent resistance of the coating is checked using the MEK rub test. The coating is rubbed 100 times with a cotton ball soaked in methyl ethyl ketone in both directions (forwards and backwards).
  • Example 9 The following ingredients are mixed at room temperature and then extruded in the melt at 90-130 ° C:
  • Example 1 As described in Example 1, the powder is applied to steel plates, a laser-engravable surface is produced and the Taber abrasion test is carried out.
  • the weight loss per 1000 revolutions is 20 mg. If the MEK rub test described in Examples 3-8 is carried out, the solvent resistance of the coating is determined to be O (excellent).
  • Example 10 The following components are mixed at room temperature and then extruded in the melt at 90-130 ° C:
  • Example 1 As described in Example 1, the powder is applied to steel plates, a laser-engravable surface is produced and the Taber rub test is carried out.
  • the weight loss per 1000 revolutions is 22 mg. If the MEK rub test described in Examples 3-8 is carried out, the solvent resistance of the coating is determined to be 0 (excellent).
  • the coating is immersed in a solvent consisting of 60 vol.% Toluene and 40 vol.% MEK, it shows no signs of softening, swelling or shrinkage.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Manufacturing & Machinery (AREA)
  • Paints Or Removers (AREA)
  • Epoxy Resins (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)

Claims (16)

  1. Produit de revêtement en poudre qui contient :
    a) une résine époxyde bifonctionnelle formée avec un bisphénol,
    b) une résine époxyde d'un degré de fonctionnalité époxydique supérieur à 2,
    c) une diaminodiphénylsulfone comme durcisseur pour durcir le mélange des composés a) et b), et
    d) un imidazole comme accélérateur de durcissement.
  2. Produit selon la revendication 1 qui contient 100 parties en poids de la résine époxyde bifonctionnelle a), 5 à 100 parties en poids de la résine époxyde polyfonctionnelle b), 5 à 35 parties en poids de la diaminodiphénylsulfone c) et 0,01 à 2 parties en poids de l'imidazole (d).
  3. Produit selon la revendication 2 qui contient 100 parties en poids de la résine époxyde bifonctionnelle a), 15 à 35 parties en poids de la résine époxyde polyfonctionnelle b), 10 à 20 parties en poids de la diamino-diphénylsulfone c) et 0,1 à 0,5 partie en poids de l'imidazole (d).
  4. Produit selon la revendication 2 qui contient 100 parties en poids de la résine époxyde bifonctionnelle a), 40 à 60 parties en poids de la résine époxyde polyfonctionnelle b), 20 à 30 parties en poids de la diamino-diphénylsulfone c) et 0,2 à 1 partie en poids de l'imidazole (d).
  5. Produit selon la revendication 1 dont l'éther diglycidylique de bisphénol (a) est un composé de formule I ci-dessous :
    Figure imgb0017
     dans laquelle
    Ar   désigne un groupe phénylène sans substituants ou bien avec 1 ou 2 atomes d'halogènes,
    X   une liaison covalente, un alkylène linéaire ou ramifié en C₁ à C₆, un groupe carbonyle ou sulfonyle ou un atome d'oxygène ou de soufre,
    Y   le radical d'un diol ou d'un diphénol résultant de l'élimination des deux groupes hydroxyliques, et
    n   un entier de 1 à 10.
  6. Produit selon la revendication 5 dont l'éther diglycidyliques de bisphénol (a) a un point de ramolissement de 50 à 140°C et une teneur en groupes époxy d'au moins 0,5 équivalent/kg.
  7. Produit selon la revendication 5 ou 6 dont l'éther diglycidylique de bisphénol (a) est un éther diglycidylique du bis-(4-hydroxyphényl)méthane, du 4,4'-dihydroxybiphényle, de la bis-(4-hydroxyphényl)sulfone, du 2,2-bis-(4-hydroxyphényl)-propane ou du 2,2-bis-(3,5-dibromo-4-dihydroxyphényl)-propane préallongés par réaction avec le résorcinol, l'hydroquinone, le bis-(4-hydroxyphényl)-méthane, le 4,4'-dihydroxybiphényle, la bis(4-hydroxyphényl)-sulfone ou le 2,2-bis-(4-hydroxyphényl)-propane.
  8. Produit selon la revendication 1 dont la résine époxyde (b) est un ester polyglycidylique ou poly-(bêtaméthylglycidylique) d'un acide polycarboxylique, un éther polyglycidylique ou poly-(bêta-méthylglycidylique) d'un polyphénol ou d'un polyol ou d'une novolaque formée d'un aldéhyde et d'un phénol, ou bien un composé poly-(N-glycidylique).
  9. Produit selon la revendication 8 dont la résine époxyde (b) est un éther polyglycidylique d'une novolaque phénolique ayant un point de ramolissement de 35 à 140°C ou un dérivé poly-(N-glycidylique) du bis-(4-aminophényl)-méthane.
  10. Produit selon la revendication 9 dont la résine époxyde (b) est un composé de formule II :
    Figure imgb0018
     dans laquelle R désigne un atome d'hydrogène ou d'halogène ou bien un alkyle ou un alcoxy en C₁-C₄ et m est un nombre entier de 0 à 10.
  11. Produit selon la revendication 1 dans lequel la diamino-diphénylsulfone (c) a la formule III :
    Figure imgb0019
     R¹ désignant un atome d'hydrogène ou un alkyle en C₁₋₁₂.
  12. Produit selon la revendication 11 dans lequel la diaminodiphénylsulfone est la 3-3'-diaminodiphénylsulfone ou la 4,4'-diaminodiphénylsulfone.
  13. Produit selon la revendication 1 dans lequel l'imidazole accélérateur (d) a la formule IV ou Y ci-dessous :
    Figure imgb0020
     formules dans lesquelles les divers radicaux R² représentent, indépendamment les uns des autres, des atomes d'hydrogène ou d'halogènes ou des alkyles, alcoxy, alcényles, cycloalkyles, cycloalcényles, aryles, alcaryles ou aralkyles pouvant avoir jusqu'à 15 atomes de carbone.
  14. Produit selon la revendication 13 dans lequel l'accélérateur (d) est l'imidazole, le 2-éthyl-4-méthylimidazole, le 2-méthylimidazole, le benzimidazole, le 2-méthylbenzimidazole, le 2-phénylimidazole ou un sel de l'un de ces composés et d'un acide.
  15. Procédé de fabrication de clichés d'impression pouvant être gravés avec un laser, procédé caractérisé en ce que l'on applique un produit de revêtement pulvérulent selon la revendication 1 sur un matériau de base métallique et on fond le revêtement pour en former une couche durcie en profondeur.
  16. L'emploi d'un produit selon la revendication 1 en vue de fabriquer des clichés d'impression pour la gravue au laser.
EP85810379A 1984-08-24 1985-08-19 Compositions pour le revêtement sous forme de poudres Expired - Lifetime EP0176475B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8421525 1984-08-24
GB848421525A GB8421525D0 (en) 1984-08-24 1984-08-24 Powder coating compositions

Publications (3)

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EP0176475A2 EP0176475A2 (fr) 1986-04-02
EP0176475A3 EP0176475A3 (en) 1988-03-16
EP0176475B1 true EP0176475B1 (fr) 1991-09-25

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EP85810379A Expired - Lifetime EP0176475B1 (fr) 1984-08-24 1985-08-19 Compositions pour le revêtement sous forme de poudres

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US (1) US4757117A (fr)
EP (1) EP0176475B1 (fr)
JP (1) JPS6164767A (fr)
CA (1) CA1260190A (fr)
DE (1) DE3584211D1 (fr)
GB (1) GB8421525D0 (fr)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1332017C (fr) * 1987-02-07 1994-09-13 Somar Corporation Composition de revetement a base de poudre de resine epoxydique
US5162450A (en) * 1989-02-17 1992-11-10 General Electric Company Curable dielectric polyphenylene ether-polyepoxide compositions
US5213886A (en) * 1989-02-17 1993-05-25 General Electric Company Curable dielectric polyphenylene ether-polyepoxide compositions
JPH0362821A (ja) * 1989-07-31 1991-03-18 Tonen Corp エポキシ樹脂組成物
US5212263A (en) * 1991-01-10 1993-05-18 Morton International, Inc. Textured epoxy powder coating
ES2060449T3 (es) * 1991-07-22 1994-11-16 Akzo Nobel Nv Composicion de revestimiento en polvo que contiene una resina, un agente de curado y zinc.
FR2693205B1 (fr) * 1992-07-02 1994-09-02 Inst Francais Du Petrole Compositions de revêtement gravables notamment pour rouleaux d'imprimerie, procédé d'enduction et objets fabriqués par ce procédé.
US6218483B1 (en) * 1996-05-06 2001-04-17 Rohm And Haas Company Powder coating of epoxy resin, imidazole-epoxy resin catalyst or polyamine, polyamine powder and amine scavenger
US5795927A (en) * 1996-05-17 1998-08-18 Morton International, Inc. Color stable wrinkle finish epoxy powder coating
US5688878A (en) * 1996-05-17 1997-11-18 Morton International, Inc. Epoxy powder coating with wrinkle finish
US5834565A (en) * 1996-11-12 1998-11-10 General Electric Company Curable polyphenylene ether-thermosetting resin composition and process
EP0857742B1 (fr) * 1997-02-07 2003-12-10 Vantico AG Revêtement sous forme de poudre
EP0916709B2 (fr) † 1997-11-04 2010-02-17 Morton International, Inc. Revêtement sous forme de poudre à un composant durcissable à basse température
US6197898B1 (en) 1997-11-18 2001-03-06 General Electric Company Melt-mixing thermoplastic and epoxy resin above Tg or Tm of thermoplastic with curing agent
US5932288A (en) * 1997-12-18 1999-08-03 Morton International, Inc. Wrinkle epoxy powder coating with acid and its homolog methylenedisalicylic
EP1142920B1 (fr) 1998-12-25 2011-08-03 Mitsubishi Rayon Co., Ltd. Composition de resine epoxyde, preimpregne, et rouleau a base de resine renforcee avec des fibres de renforcement
PT1245844E (pt) * 2001-03-29 2012-06-05 Georgia Pacific Consumer Prod Rolo para estampagem em relevo gravado a laser
WO2003040206A1 (fr) * 2001-11-07 2003-05-15 Toray Industries, Inc. Compositions de resine epoxy pour materiaux composites a fibres, procede de production de ces materiaux, et materiaux composites a fibres
GB2452545A (en) * 2007-09-07 2009-03-11 Fira Internat Ltd Lignocellulose coated with laser fused powder
CN101662902A (zh) * 2008-08-27 2010-03-03 深圳富泰宏精密工业有限公司 壳体及其制作方法
EP2522508A3 (fr) * 2011-05-12 2013-12-04 E. I. du Pont de Nemours and Company Forme d'impression et procédé de préparation de la forme d'impression utilisant une composition durcissable de résine époxy à base de bisphénol
US20120285930A1 (en) * 2011-05-12 2012-11-15 E. I. Du Pont De Nemours And Company Printing form and process for preparing the printing form with curable composition having epoxy novolac resin
US9096759B2 (en) 2011-12-21 2015-08-04 E I Du Pont De Nemours And Company Printing form and process for preparing the printing form with curable composition having solvent-free epoxy resin

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1643309U (de) * 1952-02-11 1952-09-04 Loewe Opta Ag Schallplattengeraet mit mitteln zur inbetriebnahme von schallplatten verschiedener laufgeschwindigkeit.
JPS5123600A (ja) * 1974-08-22 1976-02-25 Fujitsu Ltd Tainetsuseiehokishijushiseikeiyososeibutsu
GB1517714A (en) * 1974-11-18 1978-07-12 Crosfield Electronics Ltd Preparation of gravure printing surfaces
US4120913A (en) * 1976-12-10 1978-10-17 Westinghouse Electric Corp. Epoxy-amine adhesive compositions
US4169187A (en) * 1977-04-01 1979-09-25 E. I. Du Pont De Nemours And Company Powder coating composition of a mixture of epoxy resins
DE3027140A1 (de) * 1979-07-20 1981-02-19 Ciba Geigy Ag Haertbare epoxidharzgemische und ihre verwendung
EP0042852A1 (fr) * 1979-12-26 1982-01-06 The Polymer Corporation Revetements de resistance chimique
US4331582A (en) * 1980-01-14 1982-05-25 Hitco Epoxy latent catalyst
GB2071574B (en) * 1980-03-11 1984-09-05 Crosfield Electronics Ltd Printing members
JPS57501380A (fr) * 1980-08-22 1982-08-05
GB2087796B (en) * 1980-11-19 1984-11-28 Crosfield Elelctronics Ltd Improvements relating to printing members
JPS57141419A (en) * 1981-02-27 1982-09-01 Mitsubishi Petrochem Co Ltd Production of polyepoxide
US4440914A (en) * 1981-10-19 1984-04-03 Ciba-Geigy Corporation Solid epoxy resin systems
DE3270282D1 (en) * 1981-10-19 1986-05-07 Ciba Geigy Ag Solid epoxide resin
DE3365783D1 (en) * 1982-03-15 1986-10-09 Crosfield Electronics Ltd Printing member and method for its production
US4549000A (en) * 1983-03-09 1985-10-22 Vernicolor Ag Thermosetting powder lacquer for covering weld seams
JPS59217720A (ja) * 1983-05-26 1984-12-07 Toray Ind Inc エポキシ樹脂組成物
US4552814A (en) * 1984-05-21 1985-11-12 The Dow Chemical Company Advanced epoxy resins having improved impact resistance when cured

Also Published As

Publication number Publication date
JPS6164767A (ja) 1986-04-03
GB8421525D0 (en) 1984-09-26
US4757117A (en) 1988-07-12
DE3584211D1 (de) 1991-10-31
EP0176475A3 (en) 1988-03-16
CA1260190A (fr) 1989-09-26
EP0176475A2 (fr) 1986-04-02

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