[go: up one dir, main page]

WO2004011246A1 - Procede de fabrication d'un stratifie en aluminium et stratifie en aluminium - Google Patents

Procede de fabrication d'un stratifie en aluminium et stratifie en aluminium Download PDF

Info

Publication number
WO2004011246A1
WO2004011246A1 PCT/JP2002/007724 JP0207724W WO2004011246A1 WO 2004011246 A1 WO2004011246 A1 WO 2004011246A1 JP 0207724 W JP0207724 W JP 0207724W WO 2004011246 A1 WO2004011246 A1 WO 2004011246A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
curable resin
aluminum
aluminum laminate
coating film
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.)
Ceased
Application number
PCT/JP2002/007724
Other languages
English (en)
Japanese (ja)
Inventor
Koichiro Haraguchi
Mitsuo Yasuda
Yasuhiro Mori
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jujo Chemical Co Ltd
Isimat Japan Ltd
Original Assignee
Jujo Chemical Co Ltd
Isimat Japan Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jujo Chemical Co Ltd, Isimat Japan Ltd filed Critical Jujo Chemical Co Ltd
Priority to JP2004524093A priority Critical patent/JP3863162B2/ja
Priority to PCT/JP2002/007724 priority patent/WO2004011246A1/fr
Priority to AU2002368134A priority patent/AU2002368134A1/en
Publication of WO2004011246A1 publication Critical patent/WO2004011246A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/068—Copolymers with monomers not covered by C09D133/06 containing glycidyl groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/064—Polymers containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation

Definitions

  • the present invention relates to a method for producing an aluminum laminate and an aluminum laminate, and more specifically, requires excellent concealing properties and flexibility, or excellent adhesion of a cured coating film, such as a pharmaceutical aluminum tube.
  • the present invention relates to a production method suitable for manufacturing an aluminum laminate to be manufactured and an aluminum laminate having such characteristics.
  • Aluminum tubes for pharmaceuticals which contain contents such as drugs and chemicals, need to be repeatedly bent and extended to take out the contents. For this reason, coating films provided on the inner and outer surfaces of aluminum tubes are required to have excellent flexibility and excellent adhesion to aluminum surfaces.
  • a heat-curing coating agent composed of an epoxy-based cured product and a urethane-based cured product containing a large amount of an organic solvent has been mainly used. Therefore, after coating these heat-curable coating agents on the aluminum surface, the coating is heated at, for example, 180 ° C. for about 1 minute to 10 minutes to evaporate the organic solvent and heat the coating. There is a method in which a curable coating agent is cured to form a coat film.
  • Such a heat-curable coating agent contains a large amount of an organic solvent, and problems such as the deterioration of the working environment, the burden on flameproofing equipment, and the effects of environmental release caused by the organic solvent have been raised. .
  • a prolonged heat treatment is required. Because of the necessity, there were many problems such as the production line becoming large-scale and consuming a large amount of production energy.
  • Japanese Patent Application Laid-Open No. Hei 9-140760 discloses an ultraviolet-curable resin composition capable of forming a coating film having excellent adhesion to plastic films and metals, and a coating agent containing the same. ing. More specifically, a UV-curable resin composition comprising the following components (A), (B) and (C) and a coating agent containing the same are disclosed.
  • the disclosed ultraviolet-curable resin composition has a problem that the curing speed of the liquid epoxy resin is low, and therefore, the productivity is low. In addition, when applied to an aluminum substrate and the aluminum substrate is bent, there is a problem that the cured coating film is easily peeled off. Furthermore, since the disclosed ultraviolet-curable resin composition uses a relatively large amount of liquid epoxy resin and other resins, it has a problem that it has a high viscosity and is difficult to handle and form a thin film.
  • Japanese Patent Application Laid-Open No. H10-1683885 discloses a UV-curable can coating composition capable of forming a coating film for can coating having excellent adhesion and abrasion resistance, and the like.
  • a method for producing a coated metal can using the ultraviolet-curable can coating composition is disclosed. More specifically, a UV-curable can coating composition comprising the following components (A), (B) and (C), and a method for producing a coated metal can using the UV-curable can coating composition Is disclosed.
  • the total amount of (A) and (B) is 100 parts by weight.
  • Japanese Patent Application Laid-Open No. 11-2466878 discloses an ultraviolet-curable coating composition capable of forming a coating film having excellent hardness and abrasion resistance. More specifically, an ultraviolet-curable coating composition comprising the following components (A) and (B) is disclosed. In Examples, an ultraviolet-curable coating composition containing 7% by weight of a photopolymerization initiator is disclosed. Is disclosed.
  • the coating composition for ultraviolet-curable cans disclosed in Japanese Patent Application Laid-Open No. 10-168385 uses a polyester (a) having a hydroxyl group, the resulting cured coating film has an ultraviolet ray. While the curability and flexibility tended to be insufficient, there was a problem that it was easily hydrolyzed due to the moisture present in the surroundings.
  • the ultraviolet-curable coating composition disclosed in Japanese Patent Application Laid-Open No. H11-2467888 requires a large amount of aluminum oxide to be added, and the resulting cured coating film has insufficient ultraviolet curing. On the other hand, aluminum oxide was easily precipitated, and it was difficult to obtain a cured coating film consisting of a uniform thin film.
  • the present invention solves the conventional problems, and includes a step of laminating a specific curable resin composition on an aluminum substrate.
  • an aluminum substrate such as a pharmaceutical aluminum tube is provided. Even if it is bent, the cured coating film is less likely to peel off easily. It is an object of the present invention to provide a method for producing an aluminum laminate, which can easily and quickly produce a film laminate, and an aluminum laminate. Disclosure of the invention
  • a method for producing an aluminum laminate which includes the following steps (1) and (2), and can solve the above-mentioned problems.
  • the epoxy acrylate oligomer has a polar group, particularly an acid group, compatibility with other components in the curable resin composition is improved, and adhesion to the aluminum base material can be improved.
  • another embodiment of the present invention provides a curable resin composition containing a polar group-containing epoxy acrylate oligomer, an acrylic monomer, and a curing agent on an aluminum substrate.
  • a curable resin composition containing a polar group-containing epoxy acrylate oligomer, an acrylic monomer, and a curing agent on an aluminum substrate.
  • It is an aluminum laminate characterized by having a cured coating film of 1 to 3 mm.
  • the curable resin composition can be easily handled, and can be easily obtained from thin films to thick cured films.
  • 1 (a) to 1 (C) are views provided for explaining a method for producing an aluminum laminate of the present invention.
  • FIG. 2 is a diagram provided to explain the influence of the acid value of an epoxy acrylate oligomer having a polar group.
  • FIGS. 3 (a) and 3 (b) are diagrams used to explain the effect of the type of acrylate monomer on the physical properties of the cured coating film.
  • FIG. 4 is a diagram showing a method of laminating the curable resin composition on a tubular aluminum substrate.
  • FIG. 5 (a) is a perspective view of the aluminum laminate of the present invention
  • FIG. 5 (b) is a cross-sectional view of the aluminum laminate of the present invention.
  • FIG. 6 is a diagram provided to explain the effect of the thickness of the cured coating film.
  • FIG. 7 is a cross-sectional view of an aluminum laminate provided with an inner resin layer. BEST MODE FOR CARRYING OUT THE INVENTION
  • the first embodiment is a method for producing an aluminum laminate 20 including the following steps (1) and (2).
  • a step of laminating a curable resin composition 12 containing a polar group-containing epoxy acrylate oligomer, an acrylic monomer and a curing agent on an aluminum substrate 10 (hereinafter referred to as a laminating step) In some cases.)
  • FIG. 1 (a) shows the stage where the aluminum base material 10 was prepared
  • FIG. 1 (b) shows a step of laminating the curable resin composition 12 on the aluminum base material 10 using the coating device 18.
  • FIG. 1 (c) shows a stage where the applied curable resin composition 12 is cured by irradiation 14 to form an aluminum laminate 20 having a cured coating film 13.
  • Examples of the epoxy acrylate oligomer having a polar group include an epoxy acrylate oligomer having at least one polar group selected from the group consisting of a phosphate group, a carboxyl group, a sulfonic acid group, and a hydroxyl group.
  • epoxy acrylate oligomers having an acid group such as a phosphate group, a carbonyl group, a sulfonic acid group and the like are more preferable because a cured film excellent in flexibility and adhesion can be obtained.
  • Epoxy acrylate oligomers having a phosphoric acid group are particularly preferred, since a cured coating film having further excellent properties can be obtained and the compatibility with other components is excellent.
  • the epoxy acrylate oligomer having such a polar group can be obtained by, for example, obtaining a reactant of a compound having a polar group and bisphenol A glycidyl ether in advance and then acrylizing the reactant. Obtainable.
  • the number average molecular weight (Mn) of the epoxy acrylate oligomer having a polar group is preferably set to a value within a range of 500 to 100,000.
  • the number average molecular weight of such an epoxy acrylate oligomer is more preferably set to a value within the range of 1,000 to 8,000, and more preferably to a value within the range of 1,500 to 5,000. More preferably, The number average molecular weight of each of the epoxy acrylate oligomer and the urethane acrylate oligomer described below can be measured using gel permeation chromatography (GPC).
  • the acid value of the epoxy acrylate oligomer having a polar group is preferably set to a value within the range of 5 to 50 mg KOH / g.
  • the acid value of such an epoxy acrylate oligomer is more preferably set to a value within a range of 10 to 45 mg KO HZ g, and further preferably set to a value within a range of 20 to 40 mg KO HZ g. .
  • the acid value of such an epoxy acrylate oligomer can be measured by a titration method using KOH.
  • FIG. Figure 2 shows the acid value (mg KO HZ g) of the epoxy acrylate oligomer having a phosphate group as a polar group on the horizontal axis, and the vertical axis shows the adhesion evaluation (relative value) of the cured coating film obtained. ) And chemical resistance evaluation (relative value).
  • adhesion evaluation resistance value
  • chemical resistance evaluation resistance value
  • evaluation ⁇ was obtained with three samples, and evaluation ⁇ was obtained with another three samples, the evaluation score of adhesion was set to four.
  • the acid value of such an epoxy acrylate oligomer to a value within the range of 10 to 50 mg KO HZ g, the adhesion and chemical resistance of the cured coating film are further improved, and a rating of 1 or more is obtained for each. It can be easily obtained.
  • the acid value to a value within the range of 20 to 40 mg KOHZg, a higher evaluation of 3 or more can be easily obtained.
  • acrylic monomer to be combined with the epoxy acrylate oligomer having a polar group examples include methyl (meth) acrylate, ethyl (meth) acrylate, acryloylmorpholine, and isobornyl acrylate.
  • acryl-based monomers it is more preferable to use a combination of acryloyl morpholine and isovonyl acrylate or one of the acryl-based monomers.
  • the reason for this is that by using such an acrylic monomer, the viscosity of the curable resin composition can be easily adjusted, the compatibility is improved, and even if the aluminum substrate is bent, This is because it is possible to more easily and quickly prepare an aluminum laminate in which the coating film is less likely to peel off. Also, by using such an acrylic monomer, the flexibility (elongation, etc.) of the cured coating film can be improved without changing the properties such as the strength of the cured coating film.
  • the horizontal axis is hard Of the three acrylic monomers (IB0A: isobonyl acrylate, TPGDA: tripropylene glycol diacrylate, 2-PEA: 2 monophenoxyl acrylate) in the curable resin composition (% by weight) ), And the vertical axis shows the value of the tensile strength (kgf Z cm 2 ) of the cured coating film.
  • the horizontal axis shows the amount (% by weight) of the acrylic monomer in the cured green resin composition, and the vertical axis shows the elongation of the cured coating film. (%).
  • isobonyl acrylate (IB0A) is 50% by weight or less of the total amount, that is, 100 parts by weight of epoxy acrylate oligomer.
  • Te, 0.1 - 1 0 0 Li by the used in a range of parts by weight, monitor and to be able to put that pull 5 0 kgf Roh cm 2 or more values strength to the cured coating film, cured
  • the elongation of the coating film can be maintained at a high value of 50% or more.
  • the amount of the acryl-based monomer is preferably set to a value within the range of 0.1 to 300 parts by weight based on 100 parts by weight of the epoxy acrylate oligomer.
  • the reason for this is that if the amount of such an acrylic monomer is less than 0.1 part by weight, it becomes difficult to adjust the viscosity of the curable resin composition, and printability and coating suitability may decrease. On the other hand, if the amount of the acrylic monomer exceeds 300 parts by weight, the resulting cured coating film may have a reduced degree of chemical resistance.
  • the addition amount of the acryl-based monomer be in the range of 5 to 200 parts by weight, and it is more preferable that the addition amount be in the range of 10 to 100 parts by weight.
  • the ratio of acryloyl morpholine and isobonyiacrylate used in the acrylic monomer is within a range of 50% by weight or more.
  • the proportion of Isoboniruakuri rate Bok and 5 5 by weight 0/0 or more values the 6 0 wt% or more More preferably, it is set to a value.
  • the ratio of W 1 ZW 2 is more preferably set to a value in the range of 2 to 50, and even more preferably to a value in the range of 5 to 20.
  • a curing agent for example, benzophenones, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, methyl compounds such as methylbenzoinfomate, and monoacylphosphinoxide And phosphorus compounds such as bis-nasyl phosphinoxide, thioxanthones and the like, alone or in combination of two or more.
  • benzoin benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl Toluene, benzoin isopropyl ether, benzoin n-butyl ether, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpronone-one, benzyldimethylketal, 1-hydroxycyclohexylphenylketone, 2-methyl-2-ene Morpholinol (4-thiomethylphenyl) propane-one-one, 2-benzyl-2-dimethylamino-111- (4-morpholinophenyl) butanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide Benzobenzone, o-benzoyl methyl benzoate, hydroxybenzophenone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-
  • thermal polymerization initiator preferred examples thereof include azobisisobutyronitrile (AIBN), benzoyl peroxyside, dicumyl peroxyside, g-butyl peroxyside, and di-t-butyl.
  • AIBN azobisisobutyronitrile
  • benzoyl peroxyside dicumyl peroxyside
  • g-butyl peroxyside and di-t-butyl.
  • Peroxy-1,3,3,5-trimethylcyclohexane t-butylmethyl peroxide
  • g-t-amyl peroxide t-butylhydroperoxide
  • 2,5-dimethyl-2,5-di- (t-butyl veroxy) — Hexane and the like.
  • the amount of the curing agent added is preferably set to a value within the range of 1 to 20 parts by weight based on 100 parts by weight of the curable resin composition.
  • the reason for this is that if the amount of the curing agent added is less than 1 part by weight, the resulting curable resin composition has a low curing rate, resulting in reduced productivity and wrinkles during curing. Because there is. On the other hand, if the amount of the curing agent exceeds 20 parts by weight, the resulting cured coating film may have reduced flexibility and chemical resistance.
  • the amount of the curing agent added is set to 100% by weight of the curable resin composition. It is more preferable that the value be in the range of 2 to 15 parts by weight, and it is more preferable that the value be in the range of 3 to 10 parts by weight.
  • photosensitizers include, for example, triethylamine, triethanolamine, methyljetanolamine, methyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, And tertiary amines such as 4,4'-getylaminobenzophenone, alkylphosphines such as triphenylphosphine, and thioethers such as thiodiglycol, and the like, alone or in combination of two or more.
  • a urethane acrylate oligomer in order to further improve the chemical resistance and the scratch resistance in the obtained cured coating film, it is preferable to further add a urethane acrylate oligomer.
  • a urethane acrylate oligomer When a urethane acrylate oligomer is added, its average molecular weight is preferably set to a value within a range of 500 to 500,000. The reason for this is that if the average molecular weight of the urethane acrylate oligomer is less than 500, the curing rate of the curable resin composition will be low, the productivity will be low, and the hardness of the cured coating film will increase. This is because cracks may occur during bending. On the other hand, if the average molecular weight of the urethane acrylate oligomer exceeds 50, 000, the resulting cured coating film may have reduced chemical resistance.
  • the average molecular weight of the urethane acrylate oligomer is more preferably set to a value within the range of 2,500 to 10,000, and more preferably to a value within the range of 3,500 to 500,000. More preferably,
  • the amount of the urethane acrylate oligomer to be added should be within a range of 1 to 50 parts by weight based on 100 parts by weight of the epoxy acrylate oligomer. Good Good.
  • the reason for this is that if the amount of the urethane acrylate oligomer is less than 1 part by weight, the surface curability of the cured coating film is reduced, and the chemical resistance and the scratch resistance may be reduced. On the other hand, if the amount of the urethane acrylate oligomer exceeds 50 parts by weight, the adhesion of the obtained cured coating film is reduced, and cracking or peeling may occur at the time of bending and bending. is there.
  • the amount of the urethane acrylate oligomer to be added is more preferably set to a value in the range of 10 to 30, and even more preferably to a value in the range of 15 to 25.
  • a force coupling agent is defined as a compound having two or more different reactive groups in one molecule, and one of the reactive groups is an inorganic material obtained by hydrolysis, a dealcoholization reaction or a dehydration reaction.
  • An alkoxysilane group or an alkoxytitanium group capable of chemically bonding to an organic material or the like is preferable as another reactive group.
  • a vinyl group-containing silane coupling agent a (meth) acrylic group-containing silane coupling agent, an epoxy group-containing silane coupling agent, an amino group-containing silane coupling agent, and a mercapto group-containing silane
  • these coupling agents include: -aminopropyltriethoxysilane, r-glycidoxypropyltriethoxysilane. And r-mercaptopropyl trimethoxysilane, vinyltrimethoxysilane, r-aminopropyltriethoxytitanium, r-glycidoxypropyltriethoxyaluminum, r-mercaptopropyltrimethoxytitanium, vinyltrimethoxyaluminum and the like.
  • an epoxy acrylate oligomer having a phosphoric acid group is used as the epoxy acrylate oligomer having a polar group
  • a vinyl group-containing epoxy acrylate oligomer is used because a more excellent stability of the curable resin composition is obtained. It is preferable to use trimethoxysilane, (meth) acryl group-containing trimethoxysilane, and epoxy group-containing trimethoxysilane.
  • the amount of the coupling agent to be added is preferably set to a value within the range of 0.1 to 10 parts by weight based on 100 parts by weight of the curable resin composition.
  • the amount of the coupling agent is preferably set to a value within the range of 1 to 8 parts by weight with respect to 100 parts by weight of the curable resin composition, and 4 to 6 parts by weight. More preferably, the value is within the range.
  • an inorganic coloring pigment an organic coloring pigment, an inorganic filler, an organic filler, an inorganic matte powder pigment, an organic matte powder, and the like as a coloring agent.
  • the coloring agent when providing the curable resin composition with concealing properties, it is preferable to use titanium oxide, carbon black, or the like as the coloring agent. When it is desired to obtain more excellent hiding properties by adding an amount, it is more preferable to use rutile-type titanium oxide.
  • the amount of the coloring agent to be added is controlled by the curable resin composition; The value is preferably within a range of 0.0 to 40 parts by weight based on 100 parts by weight.
  • the reason for this is that if the amount of such a coloring agent is less than 0.1 part by weight, the cured film may not exhibit coloring properties. On the other hand, if the amount of the coloring agent exceeds 40 parts by weight, the curability of the curable resin composition may decrease, and the strength of the obtained cured coating film may decrease. .
  • the amount of the colorant is in the range of 1 to 40 parts by weight, and more preferably in the range of 3 to 35 parts by weight, based on 100 parts by weight of the curable resin composition. Is more preferable.
  • defoaming agents In the curable resin composition, defoaming agents, leveling agents, silicone oils, lubricants, surfactants, dispersants, antistatic agents, It is preferable to add a compound such as an antioxidant.
  • a cationic curing type monomer for example, an epoxy resin or an oxetane resin, together with the cationic curing agent.
  • the viscosity (measuring temperature: 25 ° C.) of the curable resin composition is preferably set to a value within the range of 100 to 50,000 mPa 2 sec. If the viscosity is less than 100 mPa'sec., The curable resin composition may be difficult to handle or the stability of the curable resin composition may be reduced. Because there is. Meanwhile, such viscosity If the ratio exceeds 50,000 OmPa secsec., The handleability of the curable resin composition may decrease, or the suitability for printing and coating may decrease.
  • the viscosity of the curable resin composition it is more preferable to set the viscosity of the curable resin composition to a value within the range of 500 to 100, OOO m P a ⁇ sec. It is more preferable that the value be within the range of.
  • the thickness of the aluminum base material is set to a value within a range of 10 U rr »to 5 mm depending on the use.
  • the thickness of the aluminum base material is less than 10 m, wrinkles may be easily formed or the mechanical strength of the obtained aluminum laminate may be insufficient. is there.
  • the thickness of the aluminum base exceeds 5 mm, handling becomes difficult, and lamination with the curable resin composition may become difficult.
  • the thickness of the aluminum base material is more preferably set to a value in the range of 5 OjUm to 3 mm, and even more preferably to a value in the range of 80 / im to 1 mm.
  • the aluminum substrate is annealed.
  • the reason for this is that by using an annealed aluminum substrate, the adhesion between the cured coating film and the aluminum substrate can be improved, and even when the aluminum substrate is bent. This is because it is possible to easily and quickly produce an aluminum laminate in which the cured coating film is less likely to peel off.
  • an annealing condition for the aluminum base material as an example, reheating by rapid heating of 1 ° CZ seconds or more to a temperature within a range of 380 to 530 ° C. After holding for 20 seconds or less, it is preferable to cool at a temperature lowering rate of, for example, 50 ° CZ or more.
  • At least one surface treatment of an ozone treatment, a plasma treatment, a corona treatment, an ultraviolet treatment and a gay acid flame treatment is applied to the surface of the aluminum base material.
  • a gay acid flame treatment is a preferable surface treatment because the adhesion between the aluminum base material and the cured coating film can be drastically improved.
  • a flame of a fuel gas containing a silane compound having a boiling point of 100 to 100 ° C is sprayed on the aluminum base material entirely or partially. Is preferred.
  • the method of laminating the curable resin composition and the aluminum base material is not particularly limited, and examples thereof include a roll coater, a knife coater, an applicator coater, a gravure coater, a screen printing method, a brush coating method, and the like. It is preferred to use
  • the unpainted tubular aluminum base material 56 is positioned at the position shown by the symbol S with respect to the rotary support plate 55 that rotates continuously in the direction of the arrow shown by the symbol B around the symbol C. Be attached. Not shown However, it is preferable that a fixing rod for fixing the tubular aluminum base material 56 be provided on the surface of the rotary support board 55.
  • the unpainted tubular aluminum base material 56 rotates from the position indicated by the symbol S to the position indicated by the symbol P, and presses against the surface of the roll coater 54.
  • the roll coater 54 rotates in a direction indicated by an arrow A to remove a predetermined amount of the curable resin composition 52 from a pan 53 provided below the roll coater 54. It is preferable that it is configured so that it can be lifted.
  • the curable resin composition 52 is transferred from a roll coater 54 holding a predetermined amount of the curable resin composition 52 on the surface thereof to a tubular aluminum base material 56 and laminated. Will be.
  • a blade for adjusting the amount of the curable resin composition 52 held on the surface of the mouth coater 54 is preferably provided.
  • the tubular aluminum laminate 30 on which the curable resin composition 52 has been laminated is rotated to the position indicated by the symbol F, detached from the rotary support board 55, and then moved to the next step. For example, it is transferred to a drying step or an ultraviolet irradiation step.
  • the curable resin composition 52 can be quickly and uniformly laminated to a uniform thickness using the roll coater 54 even for a tubular aluminum base material. .
  • the curable resin composition upon to radiation curing for example, using a Metaruhara I Doranpu or ultraviolet lamp, it is preferable that the lamp integrated quantity of light to a value within the range of 1 0 0 ⁇ 1, 5 0 0 m J cm 2 .
  • the integrated light amount of the lamp is less than 100 mJcm 2 , the curable resin composition may be insufficiently cured.
  • the accumulated light amount of the lamp exceeds 1,500 mJZ cm 2 , This is because the obtained cured coating film may turn yellow and change the hue. Therefore, it is more preferable that the integrated light amount of the lamp when the curable resin composition is radiation-cured is set to a value within the range of 250 to 1, 00 Om JZ cm 2 , and 300 to 75. 0 m and even more preferably to a value within the range of JZ cm 2.
  • the curable resin composition is cured by radiation or before the radiation curing.
  • the reason for this is that by performing such heat treatment, the adhesion between the cured coating film and the aluminum substrate can be further improved.
  • the heat treatment conditions are preferably a temperature of 50 to 200 ° C. and a treatment time of 1 to 120 minutes.
  • a cured coating film 12 made of a curable resin composition is formed on the surface of the aluminum base material 10. Is preferred.
  • the thickness of the cured coating film is preferably set to a value within the range of 0.001 to 3 mm. The reason for this is that if the thickness of the cured coating is less than 0.001 mm, the adhesion between the cured coating 12 and the aluminum substrate 10 will decrease, This is because the concealing property may be reduced, and further, the mechanical properties and the curing properties of the cured coating film may be reduced. On the other hand, if the thickness of the cured coating film exceeds 3 mm, poor curing may occur or the curing time may be excessively long.
  • the thickness of the cured coating film is more preferably set to a value in the range of 0.005 to 0.5 mm, and in a range of 0.01 to 0.2 mm (10 to 2000 ⁇ m). It is more preferable to set the value within.
  • the abscissa indicates the thickness (jum) of the cured coating
  • the ordinate indicates the adhesion evaluation (relative value) and the concealment evaluation (relative value) of the obtained cured coating. Shown.
  • the evaluation of adhesion and the evaluation of concealment were performed in the following examples, in which the evaluation ⁇ obtained in Example 5 was 5 points, the evaluation ⁇ was 3 points, the evaluation was 1 point, the evaluation X was 0 point, and the evaluation was divided. In the evaluation, the average of six evaluation samples was used as the evaluation point.
  • both the adhesion and the concealing property of the cured coating film are stable.
  • the thickness of the cured coating film is less than 1 m, the concealing property of the cured coating film is reduced.
  • the thickness of the cured coating film exceeds 50 / m, the adhesiveness of the cured coating film tends to decrease.
  • the thickness of the cured coating film be in the range of 1 to 50 m. In order to obtain a higher evaluation of 3 or more, it is more preferable that the value be in the range of 10 to 25 m.
  • the effect of the thickness of the cured coating film applies when rutile-type titanium oxide (high-concentration white) is used as a coloring agent. In the case of a clear or light-colored cured coating film, It is also possible to increase the thickness of the coating.
  • the form of the aluminum laminate is not particularly limited, but may be, for example, tubular, rectangular parallelepiped, polyhedral, cylindrical, elliptical, spherical, triangular pyramidal, conical, etc. It is preferable to mold it.
  • a tube-shaped aluminum laminate 30 as shown in FIG. 5 (a) it is assumed that the aluminum laminate 30 is bent or pressed in use, and the present invention has excellent chemical resistance and adhesion.
  • a hard coating with the required cured coating This is an optimal form because it is a laminated laminate.
  • the curable resin composition is also laminated (applied) to the screw portion 31 in order to increase the decorativeness.
  • the radiation-cured cured coating film is characterized by having excellent adhesion to common paints such as acrylic paints, epoxy paints, urethane paints, and polyester paints.
  • an inner resin layer 16 on the aluminum substrate 10 on the side opposite to the surface on which the cured coating film 12 made of the curable resin composition is formed.
  • the reason for this is that, for example, even when the aluminum substrate provided with the resin layer 16 is formed into a tube and the contents are contained therein, the contents and the aluminum substrate 10 are not This is because it is possible to prevent the reaction.
  • the used epoxy acrylate oligomer containing a polar polar group is referred to as epoxy acrylate oligomer A
  • the used urethane acrylate oligomer is referred to as urethane acrylate oligomer A.
  • Epoxy acrylate oligomer containing a phosphate group 100 parts by weight (average molecular weight: 2,000, acid value: 25)
  • the obtained curable resin composition was applied to the surface of a tube made of an annealed aluminum substrate (100 / m in thickness).
  • the coating conditions are as follows.
  • the curable resin composition on the aluminum tube was cured by ultraviolet rays to form a cured coating film. That is, the aluminum of Example 1 A laminate was made.
  • the UV curing conditions were as follows.
  • the ultraviolet curability and stability of the obtained curable resin composition and the cured coating film formed on the aluminum tube were evaluated as follows.
  • the number of samples used for evaluation was 6, and the average of each evaluation was taken as the evaluation result.
  • the curable resin composition was ultraviolet-cured while changing the integrated light amount of the lamp, the appearance of the obtained cured coating film was observed, and the ultraviolet curability of the curable resin composition was evaluated based on the following criteria.
  • the stability of the curable resin composition was evaluated based on the following criteria from the initial viscosity of the curable resin composition and the change in viscosity over time (room temperature, 168 hours).
  • ⁇ Change in viscosity is in the range of 0 to less than 20%.
  • ⁇ Change in viscosity is within the range of 20 to less than 50%.
  • ⁇ Change in viscosity is in the range of 50% to less than 100%.
  • the change in viscosity is more than 100%.
  • the resulting cured coating film was cross-cut into 100 square grids of 100 squares, and a 24 mm wide adhesive tape manufactured by Nichiban Co., Ltd. was applied. Next, the adhesive tape was peeled off, the number of grids peeled off was measured, and the adhesion of the cured coating film composed of the curable resin composition was evaluated based on the following criteria.
  • the number of strips in the grid is zero.
  • ⁇ The number of peels in the grid is 1 to 5 pieces.
  • the number of strips in the grid is from 6 to 10 pieces.
  • X The number of strips in the grid is equal to or greater than 11 pieces in the 100 grid.
  • a curable resin composition was prepared, coated, cured, and evaluated in the same manner as in Example 1 except that the number average molecular weight (Mn) and the acid value of the epoxy acrylate oligomer were changed. was done.
  • the number average molecular weight of the epoxy acrylate oligomer is set to a value in the range of 500 to 10,000, and the acid value of the epoxy acrylate oligomer is set to a value in the range of 5 to 5 Omg KO HZg.
  • the acid value of the epoxy acrylate oligomer is set to a value in the range of 5 to 5 Omg KO HZg.
  • a curable resin composition was prepared and evaluated in the same manner as in Example 1 except that the number average molecular weight (Mn) and the amount of the urethane acrylate oligomer were changed.
  • the number average molecular weight of the urethane acrylate oligomer was set to a value within a range of 500 to 500, and the amount of the urethane acrylate oligomer was set to 100 parts by weight.
  • the value within the range of 1 to 50 parts by weight more excellent flexibility, heat resistance and mechanical properties of the curable resin composition can be obtained.
  • the effect of the thickness of the resulting cured coating was studied. That is, as shown in Table 4, using the curable resin composition of Example 1, the thickness of the obtained cured coating film was changed and evaluated.
  • the thickness of the obtained cured coating film is set to a value within the range of 1 to 5 Oim, it is possible to obtain more excellent concealing property, curability, adhesion, and flexibility of the cured coating film. It was confirmed.
  • the present invention when producing an aluminum laminate, by providing a laminating step of a specific curable resin composition on an aluminum base material, even if the aluminum laminate is bent, It has become possible to easily and quickly produce an aluminum laminate in which the cured coating film is less likely to peel off.
  • an appropriate viscosity is obtained due to the excellent compatibility of each component, and a relatively large amount of a concealing agent such as titanium oxide is added. Even in this case, it is possible to effectively prevent excessive sedimentation and poor curing, and to provide an aluminum laminate having excellent concealing properties.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un stratifié en aluminium comprenant les étapes consistant: (1) à appliquer une composition de résine durcissable contenant un oligomère d'époxy acrylate, un monomère acrylique et un agent réactif sur un matériau à base d'aluminium, et (2) à mettre en oeuvre au moins un des traitements de durcissement suivants, notamment l'irradiation au moyen de rayonnement et de chaleur, en vue de cuire la composition de résine durcissable L'invention concerne également un stratifié en aluminium fabriqué au moyen de ce procédé. Le stratifié en aluminium peut être utilisé de façon avantageuse pour un tube en aluminium, notamment celui utilisé en médecine, nécessitant une flexibilité suffisante pour résister à des pliages et/ou allongements répétés.
PCT/JP2002/007724 2002-07-30 2002-07-30 Procede de fabrication d'un stratifie en aluminium et stratifie en aluminium Ceased WO2004011246A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2004524093A JP3863162B2 (ja) 2002-07-30 2002-07-30 チューブ状または円柱形状のアルミニウム積層体の作成方法およびチューブ状または円柱状のアルミニウム積層体
PCT/JP2002/007724 WO2004011246A1 (fr) 2002-07-30 2002-07-30 Procede de fabrication d'un stratifie en aluminium et stratifie en aluminium
AU2002368134A AU2002368134A1 (en) 2002-07-30 2002-07-30 Method for manufacturing aluminum laminate and aluminum laminate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2002/007724 WO2004011246A1 (fr) 2002-07-30 2002-07-30 Procede de fabrication d'un stratifie en aluminium et stratifie en aluminium

Publications (1)

Publication Number Publication Date
WO2004011246A1 true WO2004011246A1 (fr) 2004-02-05

Family

ID=30795880

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2002/007724 Ceased WO2004011246A1 (fr) 2002-07-30 2002-07-30 Procede de fabrication d'un stratifie en aluminium et stratifie en aluminium

Country Status (3)

Country Link
JP (1) JP3863162B2 (fr)
AU (1) AU2002368134A1 (fr)
WO (1) WO2004011246A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006051952A1 (fr) * 2004-11-15 2006-05-18 Bridgestone Corporation Matériau composite
JP2006137153A (ja) * 2004-11-15 2006-06-01 Bridgestone Corp 複合材
JP2012514659A (ja) * 2008-12-23 2012-06-28 ポスコ 透明着色塗装鋼板用紫外線硬化樹脂組成物及びそれを用いた鋼板
JPWO2020166391A1 (ja) * 2019-02-13 2021-12-16 大成化工株式会社 積層体および積層体の製造方法
JP2023521256A (ja) * 2020-04-13 2023-05-23 ブラジラータ・エシ／アー・エンバラゲンス・メタリカス 紫外線硬化した保護ワニスによる金属箔の表面の処理方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58204060A (ja) * 1982-05-25 1983-11-28 Asahi Chem Ind Co Ltd 感光性コ−チング材
JPH11105228A (ja) * 1997-10-08 1999-04-20 Nihon Tetrapak Kk アルミニウム積層物表面の清浄方法
JPH11256098A (ja) * 1998-03-06 1999-09-21 Hitachi Chem Co Ltd 透明塗膜形成用樹脂組成物及びこれを用いたカラーフィルター保護膜並びにカラーフィルター
JP2000203551A (ja) * 1999-01-14 2000-07-25 Tsutsumi Yotaro 熱硬化性樹脂組成物及びそれを用いた包装容器
JP2002030124A (ja) * 2001-06-08 2002-01-31 Hitachi Chem Co Ltd 光硬化型樹脂組成物及び塗料

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58204060A (ja) * 1982-05-25 1983-11-28 Asahi Chem Ind Co Ltd 感光性コ−チング材
JPH11105228A (ja) * 1997-10-08 1999-04-20 Nihon Tetrapak Kk アルミニウム積層物表面の清浄方法
JPH11256098A (ja) * 1998-03-06 1999-09-21 Hitachi Chem Co Ltd 透明塗膜形成用樹脂組成物及びこれを用いたカラーフィルター保護膜並びにカラーフィルター
JP2000203551A (ja) * 1999-01-14 2000-07-25 Tsutsumi Yotaro 熱硬化性樹脂組成物及びそれを用いた包装容器
JP2002030124A (ja) * 2001-06-08 2002-01-31 Hitachi Chem Co Ltd 光硬化型樹脂組成物及び塗料

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006051952A1 (fr) * 2004-11-15 2006-05-18 Bridgestone Corporation Matériau composite
JP2006137153A (ja) * 2004-11-15 2006-06-01 Bridgestone Corp 複合材
JP2012514659A (ja) * 2008-12-23 2012-06-28 ポスコ 透明着色塗装鋼板用紫外線硬化樹脂組成物及びそれを用いた鋼板
US8921501B2 (en) 2008-12-23 2014-12-30 Noroo Holdings Co., Ltd. Ultraviolet curable resin composition for transparent color-painted steel sheet, and steel sheet using same
JPWO2020166391A1 (ja) * 2019-02-13 2021-12-16 大成化工株式会社 積層体および積層体の製造方法
JP7452865B2 (ja) 2019-02-13 2024-03-19 大成化工株式会社 積層体および積層体の製造方法
JP2023521256A (ja) * 2020-04-13 2023-05-23 ブラジラータ・エシ／アー・エンバラゲンス・メタリカス 紫外線硬化した保護ワニスによる金属箔の表面の処理方法
JP7749656B2 (ja) 2020-04-13 2025-10-06 ブラジラータ・エシ／アー・エンバラゲンス・メタリカス 紫外線硬化する保護ワニスによる金属箔の表面の処理方法

Also Published As

Publication number Publication date
AU2002368134A8 (en) 2004-02-16
JP3863162B2 (ja) 2006-12-27
JPWO2004011246A1 (ja) 2005-11-24
AU2002368134A1 (en) 2004-02-16

Similar Documents

Publication Publication Date Title
TWI409306B (zh) Hard coating
JP5455730B2 (ja) 加飾用ハードコートフィルム、加飾フィルムおよび加飾成形品
WO2006064884A1 (fr) Composition de résine durcissable sous un rayonnement actinique et utilisation de celle-ci
CN110225936B (zh) 含(甲基)丙烯酰基的丙烯酸改性醇酸树脂和无机材料薄膜用底涂剂
JP4967999B2 (ja) 転写シート及びその利用
JP2023116624A (ja) 活性エネルギー線硬化型被覆材組成物及び積層体
JP4374262B2 (ja) 積層フィルム
WO2004011246A1 (fr) Procede de fabrication d'un stratifie en aluminium et stratifie en aluminium
JP2022087177A (ja) 活性エネルギー線硬化性樹脂組成物及びコーティング剤
JP2008179693A (ja) 活性エネルギー線硬化型被覆材組成物及びこの組成物により被覆された成型物
JP2005240005A (ja) 硬化性樹脂組成物、転写材及び保護層の形成方法
JP4480970B2 (ja) 被覆材組成物、およびこの組成物を用いて得られる物品
CN110225932B (zh) 活性能量射线固化型水性树脂组合物及无机材料薄膜用底涂剂
JP5930261B2 (ja) 金属表面用被覆材組成物及び積層成型品
JP4863464B2 (ja) 虹彩色を発現する積層物の製造方法
JP2009155521A (ja) 活性エネルギー線硬化性組成物及びその硬化物が被覆された物品
JP2006083213A (ja) 保護層形成用シートおよび保護層の形成方法
JP4088487B2 (ja) 光硬化性樹脂コーティング、および硬化塗装膜
JPH11302562A (ja) 光硬化型塗料組成物
JP5394266B2 (ja) 金属蒸着用アンダーコート層形成用被覆材組成物及び樹脂成型物
JP2004107653A6 (ja) 被覆材組成物、およびこの組成物を用いて得られる物品
JPH0718203A (ja) 被覆材組成物
JP2011246515A (ja) 活性エネルギー線硬化型被覆材組成物及び成形物
JP3990913B2 (ja) 光硬化性樹脂組成物、光硬化性樹脂層積層金属板、該金属板から得られる高硬度保護皮膜積層金属部材およびその製造方法
JP2011194756A (ja) 加飾用ハードコートフィルム、加飾フィルムおよび加飾成形品

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2004524093

Country of ref document: JP

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LU MC NL PT SE SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase