• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    high resistance surface coating film for paint strippers, composite structure, and method for making the composite structure. the surface coating film is formed by a curable resin composition containing a novolac epoxy resin, a tri-functional or tetra-functional epoxy resin, ceramic microspheres, an amine-based curing agent, particulate inorganic filler; and a hardening component. the surface coating film exhibits high tg and high crosslink density after curing, as well as high resistance to pickling solutions. the surface coating film is suitable for curing with fiber-reinforced resin composite materials. the surface coating film can optionally contain electrically conductive additives to provide sufficient conductivity for lightning protection (lsp) or shielding from electromagnetic interference (emi).
    公开号:BR112014007044B1
    申请号:R112014007044-0
    申请日:2012-12-06
    公开日:2020-09-24
    发明作者:Junjie Jeffrey Sang；Dalip Kumar Kohli
    申请人:Cytec Technology Corp.；
    IPC主号:
    专利说明:

    [0001] [0001] The present disclosure generally relates to composite surface coating films. More particularly, the present disclosure relates to surface coating films for fiber-reinforced polymer matrix composite structures.
    [0002] [0002] Fiber-reinforced polymer matrix composites (PMCs) are high-performance structural materials that are commonly used in applications that require resistance to aggressive environments, high strength and / or low weight. Examples of such applications include aircraft components (for example, crown, wings, fuselages, and propellers), high-performance automobiles, boat hulls, and bicycle structures.
    [0003] [0003] Conventional composite structures used in the aerospace industry typically include a surface coating film to provide the performance characteristics required for composite structures prior to painting. These surface coating films are used to improve the surface quality of structural parts, reducing labor, time and cost. The surface coating films are generally cured with polymer matrix composite materials during the manufacture of structural parts. However, conventional surface coating films are not very resistant to commercial stripping solutions, such as benzyl alcohol based solutions, for stripping purposes. Strippers can cause swelling and / or bubble formation of the surface coating film and can make the overcoating process more complicated. As such, there is a need for a surface coating film that can withstand repeated pickling using conventional pickling solutions to allow repainting of composite structures and durable ink adhesion over the lifetime, and can also withstand exposure to ultraviolet radiation (UV). SUMMARY
    [0004] [0004] The present disclosure provides a surface coating film formed from a curable composition that includes: a novolac epoxy resin having epoxy functionality of more than one; a trifunctional or tetrafunctional epoxy resin; ceramic microspheres; a latent amine-based curing agent; particulate inorganic fillers as a flow control agent; and at least one curing agent selected from the group consisting of: (a) a pre-reacted adduct formed by reacting an epoxy resin, a bisphenol and an elastomer; (b) a polyether sulfone (PES) and polyether sulfone copolymer (PEES); (c) core shell (CSR) rubber particles; and combinations thereof. After curing, the resulting thermoset surface coating film has a glass transition temperature (Tg) of> 180 ° C, and a pencil surface hardness of over 7H, as measured in accordance with ASTM D-3363.
    [0005] [0005] The present disclosure also provides a composite structure that has a surface coating film formed on a fiber-reinforced resin-based composite substrate and a method of producing the composite structure. The surface coating film can be cured with the resin-based composite substrate at a temperature within the range of 250 ° F to 355 ° F (or 120 ° C to 180 ° C). BRIEF DESCRIPTION OF THE DRAWINGS
    [0006] [0006] The characteristics of this disclosure will be more easily understood from the following detailed description of the various aspects of the disclosure taken in conjunction with the accompanying drawing that depicts various types of disclosure.
    [0007] [0007] Figure 1 schematically shows a composite structure with a surface coating film being formed in a molding tool according to an embodiment of the present disclosure. DETAILED DESCRIPTION
    [0008] [0008] Typical epoxy-based surface coating films for use with aerospace composite parts are often affected when exposed to conventional alcohol-based paint strippers, such as benzyl alcohol-based solutions, and ultraviolet (UV) radiation . An improved surface coating film is designed to overcome these problems. The improved surface coating film composition was formulated to produce high Tg and high crosslink density. It has been found that the combination of high Tg and high crosslink density makes the surface coating film resistant to alcohol-based stripping solutions, such as benzyl alcohol-based solutions. To achieve these properties, the surface coating film composition is based on a combination of certain multifunctional resins, a polymeric hardening component to harden the resin matrix, latent amine-based curing agent, ceramic microspheres as a component fluid barrier, and particulate inorganic fillers as a rheology modifying component. Multifunctional resins and ceramic microspheres make up more than 50% by weight of the total composition, preferably more than 60% by weight. The detailed description of the components for the surface coating film composition now follows. Multifunctional Resins
    [0009] [0009] The surface coating film composition contains at least two multifunctional epoxy resins, one of which is a novolac epoxy resin that has more than one epoxy functionality. The second epoxy resin is a non-novolac multifunctional epoxy resin, preferably tetra- or trifunctional epoxy resin (i.e., epoxy resin having three or four epoxy functional groups per molecule).
    [0010] [00010] Suitable novolac epoxy resins include polyglycidyl derivatives of phenol-formaldehyde novolacs or cresol-formaldehyde novolacs having the following chemical structure (Structure I):
    [0011] [00011] A suitable tetrafunctional epoxy resin is a tetrafunctional aromatic epoxy resin having four epoxy functional groups per molecule and at least one glycidyl amine group. As an example, the tetrafunctional aromatic epoxy resin may have the following general chemical structure (Structure II), particularly tetraglycidyl methylene ether dianiline:
    [0012] [00012] The amine groups in Structure II are shown in the para- or 4.4 'positions of the aromatic ring structures, however, it should be understood that the other isomers, such as 2.1' 2.3 ', 2, 4 ', 3,3', 3, 4 'are possible alternatives. Suitable tetrafunctional aromatic epoxy resins include tetraglycidyl-4,4'-diaminodiphenylmethane commercially available as Araldite® MY 9663, MY 9634, MY 9655, MY-721, MY-720, MY-725 provided by Huntsman Advanced Materials. Examples of trifunctional epoxy resins include aminophenol triglycidyl ether, for example, Araldite® MY 0510, MY 0500, MY 0600, MY 0610 provided by Huntsman Advanced Materials.
    [0013] [00013] In a preferred embodiment, the combination of novolac epoxy resin and multifunctional epoxy resin (trifunctional and / or tetrafunctional) constitutes at least 30% by weight based on the total weight of the surface coating film composition. In certain embodiments, the combination of the novolac epoxy resin and multifunctional epoxy resin constitutes about 30% to about 60% by weight, based on the total weight of the surface coating film composition and in other embodiments, about 40% to about 50% by weight. The relative amounts of novolac epoxy resin and multifunctional epoxy resin can be varied, but it is preferred that the amount of novolac epoxy resin is in the range of 80 to 100 parts per 100 parts of multifunctional epoxy resin. The combination of novolac epoxy resin and multifunctional epoxy resin in the specified proportion contributes to the desired high Tg and crosslink density adapted by curing. Polymeric Hardening Component
    [0014] [00014] To harden the resin matrix based on the multifunctional resin blend discussed above, one or more polymeric curing agents are added to the surface coating film composition. The polymeric curing agents are selected from the group consisting of: (i) a pre-reacted adduct formed by the reaction of the epoxy resin, a bisphenol and an elastomeric polymer; (ii) a polyether sulfone (PES) and polyether sulfone copolymer (PEES); and (iii) core shell (CSR) rubber particles; and combinations thereof. In a preferred embodiment, a combination of two hardening agents from this group is used. The total amount of curing agent (s) is about 10% to about 20% by weight based on the total weight of the surface coating film composition.
    [0015] [00015] With respect to the pre-reacted adduct, suitable epoxy resins include Bisphenol A Diglycidylether, Bisphenol A Tetrabromo Diglycidylether, Bisphenol A hydrogenated diglicidyl ether or diglycidyl hydrogenated bisphenol F. Epoxy cycloaliphatic compounds, which include the compounds that contain the compounds at least one cycloaliphatic group and at least two oxirane rings per molecule are also suitable. Specific examples include cycloaliphatic alcohol diepoxide, hydrogenated Bisphenol A (Epalloy ™ 5000, 5001 supplied by CVC Thermoset Specialties) represented by the following structure:
    [0016] [00016] An example of such a cycloaliphatic epoxy resin is EPALLOY® 5000 (a cycloaliphatic epoxy prepared by hydrogenation of diglycidyl bisphenol A ether) available from CVC Thermoset Specialties. Other cycloaliphatic epoxies suitable for use in the pre-reacted adduct may include EPONEX cycloaliphatic epoxy resins, for example, EPONEX 1510 Resin provided by Momentive Specialty Chemicals;
    [0017] [00017] The bisphenol in the pre-reacted adduct functions as a chain extension agent for linear or cycloaliphatic epoxy. Suitable bisphenols include bisphenol A, tetrabromo bisphenol A (TBBA), Bisphenol Z and Tetramethyl Bisphenol A (TMBP-A).
    [0018] [00018] Elastomers suitable for forming the pre-reacted adduct include, but are not limited to, rubbers such as, for example, amine-terminated acrylonitrile (ATBN), carboxyl-terminated acrylonitrile butadiene (CTBN), carboxyl-terminated butadiene ( CTB), fluorocarbon elastomers, silicone elastomers, styrene-butadiene polymers. In one embodiment, elastomers used in the pre-reacted adduct are ATNB or CTBN.
    [0019] [00019] In one embodiment, the epoxy resin is pre-reacted with the bisphenol chain extension agent, and the elastomer polymer in the presence of a catalyst such as triphenyl phosphine (TPP) at about 300 ° F (or 148 , 9 ° C) for the chain bonding of epoxy resins and to form a pre-reacted adduct of high molecular weight, film-forming, high viscosity epoxy resin. The pre-reacted adduct is then mixed with the other components of the surface coating film composition.
    [0020] [00020] A second option for the polymeric curing component is a thermoplastic curing material which is a copolymer of polyether sulfone (PES) and polyether ether sulfone (PEES) with an average molecular weight of 8,000 to 14,000. In one embodiment, the curing agent is poly (oxy-1,4-phenylenesulfonyl-1,4-phenylene), which has a Tg of about 200 ° C.
    [0021] [00021] The third option for the polymeric hardening component is rubber particles of the core shell type having a particle size of 300 nm or less. The core shell type (CSR) rubber particles can be any of the core shell type particles where a soft core is surrounded by a hard shell. Preferred CSR particles are those that have a polybutadiene rubber core or butadiene-acrylonitrile rubber core and a polyacrylate shell. CSR particles having a hard core surrounded by a soft shell can also be used, however. The CSR particles can be supplied as a 25 to 40% weight percentage of CSR particles dispersed in a liquid epoxy resin. CSR particles having rubber cores and polyacrylate shells are commercially available from Kaneka Texas Corporation (Houston, Tex.) Under the trade names Kane Ace MX. It is preferred, but not necessary, that the core shell rubber particles are added to the surface coating film composition as a particle suspension in a suitable liquid epoxy resin. Kane Ace MX 411 is a 25% by weight core shell rubber particle suspension in epoxy resin MY 721 and is a suitable source of core shell rubber particles. Kane Ace MX 120, MX 125, or MX 156, which contains 25 to 37% by weight of the same core shell rubber particles dispersed in the DER 331 resin, is also a suitable source of core shell rubber particles. Another suitable source of core shell rubber particles, such as MX 257, MX 215 and MX 451, can also be used. Another commercial source of core shell rubber particles is Paraloid ™ EXL-2691 from Dow Chemical Co. (methacrylate-butadiene-styrene CSR particles with an average particle size of about 200 nm). Ceramic Microspheres
    [0022] [00022] Ceramic microspheres are added to the surface coating film composition to improve the smoothness of the film surface. In one embodiment, hollow ceramic microspheres made of an inert silica-alumina ceramic material are used. Ceramic microspheres can have a crushing force of more than 60,000 psi, a dielectric constant of about 3.7 to 4.6, a softening point in the range of 1000 to 1100 ° C (or 1832 to 2012 ° F) and particle diameters ranging from 0.1 micron to 50 microns, or 1 to 50 microns. The high softening point of ceramic microspheres allows them to be non-absorbent to solvents, non-flammable, and highly resistant to chemicals. Microspheres with diameters ranging from 0.1 to about 20 microns, and preferably from about 1 to about 15 microns have been shown to be particularly suitable. An example of commercially available ceramic microspheres that are particularly suitable for use in the surface coating film composition is sold by Zeelan Industries, Inc. under the trade name Zeeospheres®, for example, G-200, G210 and W-200. These are spheres of silica-alumina, hollow with thick, odorless walls and in light gray color. In a preferred embodiment, the combination of the multifunctional resins and ceramic microspheres make up more than 50% by weight, preferably more than 60% by weight, of the surface coating film composition. In certain embodiments, the amount of ceramic microspheres is at least 20% by weight, preferably at least 25% or at least 30% by weight based on the total weight of the surface coating film composition. In some embodiments, the amount of ceramic microspheres can be within the range of 20% to 40% by weight, or 25% to 35% by weight. Healing Agent
    [0023] [00023] The multifunction epoxy resins can be cured by a variety of latent amine-based curing agents, which are activated at elevated temperatures (for example, temperature above 150 ° F (65 ° C). Suitable curing agents include dicyandiamide (DICY), guanamine, guanidine, aminoguanidine, and derivatives thereof Compounds in the imidazole and amine complex class can also be used. In one embodiment, the curing agent is dicyandiamide. amine content is present in an amount within the range of 1 to 5% by weight based on the total weight of the surface coating film composition.
    [0024] [00024] A curing accelerator can be used in conjunction with the amine-based curing agent to promote the curing reaction between epoxy resins and the amine-based curing agent. Suitable cure accelerators may include ureas substituted by alkyl and aryl (including aromatic or alicyclic dimethyl urea); bisureas based on toluenediamine or methylene dianiline. An example of bisurea is 4,4'-methylene bis (phenyl dimethyl urea) (commercially available as Omicure U-52 or CA 152 from CVC Chemicals), which is a suitable accelerator for dicyandiamide. Another example is 2,4-toluene bis (dimethyl urea) (commercially available as Omicure U-24 or CA 150 from CVC Chemicals). The curing accelerator can be present in an amount within the range of 0.5% to 3% by weight. Flow control agents
    [0025] [00025] Inorganic fillers in particulate form (for example, powder) are added to the surface coating film composition as a rheology modifying component to control the flow of the resin composition and to prevent agglomeration therein. Suitable inorganic fillers that can be used in the surface coating film composition include talc, mica, calcium carbonate, alumina, and smoked silica. In one embodiment, hydrophobic smoked silica (for example, Cab-O-Sil TS-720) is used as the inorganic filler. The amount of inorganic filler material can be within the range of 1 to 5% by weight based on the total weight of the surface coating film composition. Optional additives
    [0026] [00026] The surface coating film composition may additionally include one or more optional additives that affect one or more of the mechanical, electrical, optical, flame-resistant, and / or thermal properties of the cured or uncured surface coating film healed. The additives may comprise materials that chemically react with the epoxy resins of the composite substrate on which the surface coating film is formed or may be non-reactive with them. These additives include, but are not limited to, ultraviolet (UV) stabilizers, pigments / dyes, and conductive materials. When such additives are used, their total amount is less than 5% by weight based on the total weight of the surface coating film composition.
    [0027] [00027] Examples of UV stabilizers that can be added to the surface composition include butylhydroxytoluene (BHT), 2-hydroxy-4-methoxy-benzophenone (UV-9), 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine (CYASORB® UV-1164 light absorber), 3,5-di-tert-butyl-4-hydroxybenzoic acid, n-hexadecyl ester (CYASORB ® UV-2908 light stabilizer), Pentaerythritol Tetraquis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX 1010). The liquid hindered amine light stabilizer from Ciba Specialty Chemicals, such as 2- (2H-benzotriazol-2-yl) -4,6-ditherc-pentylphenol (TINUVIN 328), Methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (TINUVIN 292). Decanedioic acid, bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl ester (TINUVIN 123), can also be used as suitable UV stabilizers. In addition, nanometer zinc oxide (n-ZnO ), for example, NanoSunGuard 3015, and titanium oxide (n-TiO2) nanoparticles can also be used as a stabilizer UV users.
    [0028] [00028] Pigments and / or dyes known in the art for adding color to resin systems can be added to the surface coating film composition. Examples of pigments and / or dyes include, but are not limited to, red iron oxide, green chromium, carbon black, and titanium oxide. In one embodiment, the pigment is a (white) pigment of titanium oxide. In another embodiment, the pigment is carbon black.
    [0029] [00029] Conductive materials in particulate form, for example, particles or flakes, can also be added to the surface coating film composition to impart electrical conductivity to the completed surface film. Examples of suitable conductive materials include metals in the form of flakes or particles such as silver, gold, nickel, copper, aluminum, and alloys thereof. Carbon-based nanometric materials, such as carbon nanotubes (single-walled or multi-walled nanotubes), carbon nanofibers, graphene, bucky-paper, can also be used as conductive components to impart electrical conductivity to the film. resin. Nanofibers can have diameters ranging between 70 and 200 nanometers and a length of about 50 to 200 microns. Nanotubes can have an outer diameter of about 10 nanometers, the length of about 10,000 nanometers, and an aspect ratio (L / D) of about 1000.
    [0030] [00030] Table 1 shows various modalities of the surface coating film composition according to the present disclosure. All percentages (%) are percentages by weight.
    [0031] [00031] In one embodiment, the surface coating film composition has the following formulation, in weight percentages based on the total weight of the composition: 20% to 25% novolac epoxy phenol resin; 20% to 25% tetrafunctional epoxy resin; 10% to 15% pre-reacted adduct, 1% to 3% PES-PEES copolymer, 25% to 35% ceramic microspheres; 1% to 5% latent amine based curing agent; 0.5% to 3% cure accelerator; 1% to 3% inorganic filling materials; and, optionally, 0.1 to 1% color pigment. Formation of the Surface Coating Film and Composite Structure
    [0032] [00032] The components of the surface coating film composition can be added to a mixing vessel equipped to mix, heat and / or cool the components. In addition, one or more organic solvents can also be added to the mixture, as needed, to facilitate mixing of the components. Examples of such solvents can include, but are not limited to, methyl ethyl ketone (MEH), acetone, dimethylacetamide, and N-methylpyrrolidone. A surface coating film is subsequently formed from the surface coating film composition using conventional film-forming processes. The surface film thus formed can have a film weight ranging from about 0.01 to 0.45 psf (pounds per square foot), depending on the intended use.
    [0033] [00033] To facilitate the handling of the surface coating film, the surface coating film composition is applied to a carrier. Non-limiting examples of the carrier may include fibrous sheets made of thermoplastic polymer fibers or carbon fibers, metal sheets or sheets, non-woven mats, random mats, mesh carriers, metal coated carbon veils, and the like. Examples of metal sheets or sheets may include expanded metal sheets or sheets, and metal-coated veils. Such screens and sheets may include copper, aluminum, silver, nickel, and alloys thereof. Examples of non-woven mats, fabric or mesh liners may include carbon mats, polymer mats, and metal-coated carbon, glass, or polymer glass veils. The non-woven mat, fabric lining or mesh, can be coated with copper, aluminum, silver, nickel, and alloys thereof.
    [0034] [00034] The surface coating film thus formed can also be stored, in an uncured state, until it is ready for use. For example, the surface coating film can be stored in cold storage for the purpose of inhibiting the curing of the surface coating film and prolonging its shelf life. The removable protective paper can be applied to one or more surfaces of the surface coating film in order to inhibit the surface coating film from attaching to unwanted surfaces before its intended use.
    [0035] [00035] The surface coating film is designed to be cured with a fiber-reinforced resin matrix composite substrate at a temperature above 150 ° F (65 ° C), more particularly, within the 250 ° range F to 350 ° F (or 120 ° C to 175 ° C). The fiber-reinforced resin matrix composite substrate is composed of reinforcement fibers that have been impregnated or infused with a matrix resin. The matrix resin can include one or more thermosetting resins such as epoxy resins. The composite substrate can be a pre-impregnated fold or a pre-impregnated tray. The pre-impregnated fold consists of reinforcement fibers in the form of a fabric or continuous, directionally aligned fibers that have been impregnated with a resin, for example, epoxy resin. Directionally aligned fibers can be unidirectional or multidirectional fibers. The pre-impregnated tray is composed of a plurality of pre-impregnated layers arranged in a stacking sequence. In general, the uncured surface coating film can be applied to a fiber-reinforced resin matrix composite substrate, which is in an uncured or partially cured state, followed by curing to form a fully cured composite substrate. having a thermoset surface coating film attached thereto.
    [0036] [00036] In one embodiment, the surface coating film is incorporated in an immobilization process to form a composite structure. As shown in figure 1, the surface coating film 10 is first placed in contact with a molding surface of a molding tool 20, and pre-impregnated layers are arranged sequentially, one on top of the other, on the coating film. surface 10 to form a pre-impregnated tray 30. Alternatively, the pre-impregnated layers can be assembled in a different location and then later placed on the surface coating film 10. One or more cores, for example foam or honeycomb structures , may be interposed between the layers of the pre-impregnated tray, as known in the art. The entire set is then subjected to heat and pressure to cure the pre-impregnated tray and the surface coating film in a final composite structure with a selected shape. When the composite structure is removed from the molding tool, the surface coating film becomes the extreme layer of the composite structure.
    [0037] [00037] In one embodiment, the surface coating film can be applied (by laminating or coating) to a single pre-impregnated layer to produce a pre-impregnated surface self-coating tape. This pre-impregnated surface self-coating tape is suitable for use in an Automatic Lamination (ATL) or Automatic Fiber Laying (AFP) system equipped with means for distributing and compacting pre-impregnated cut tapes directly on a molding surface ( as a mandrel surface) to form a part of the composite.
    [0038] [00038] After curing, the resulting cured surface coating film is a thermoset film with a high crosslink density, a high glass transition temperature (Tg) of> 180 ° C, a pencil hardness of 7H or greater according with ASTM D-3363. These properties allow the cured surface coating film to exhibit high resistance to conventional paint strippers (eg benzol alcohol-based paint strippers), as well as UV radiation and micro cracking. It has been found that, after being in contact with the benzyl alcohol stripping solution for 7 days at room temperature (20 ° C to 25 ° C), the cured surface coating film has less than 0.5% absorption of fluid, and the pencil hardness is not reduced by more than 2H of pencil degrees. In addition, the surface coating film has been shown to have a microcrack density of less than 0.3 cracks / em2 after being subjected to a 2000X thermal cycling test between -55 ° and 71 ° C. The surface coating film has high adhesion for painting coatings normally used for painting aerospace structures. The adhesion of the surface coating film to the coating paint is such that the painted surface exhibits substantially 0% ink loss after being subjected to an ink adhesion test in accordance with ASTM D3359 under a dry or wet condition ( after immersion in deionized water at 75 ° C for 7 days), with or without being exposed to UVA radiation of 1000 KJ / m2. EXAMPLES
    [0039] [00039] The following examples serve to provide specific modalities for surface films formed in accordance with the present disclosure, but should in no way limit the scope of the present disclosure.
    [0040] [00040] Nine samples of surface coating film were prepared based on the formulations (1 to 9) shown in Table 2. All amounts are in percent by weight.
    [0041] [00041] Each surface coating film was prepared by adding the components disclosed in Table 2 into a mixing vessel and mixing the components using a high speed shear laboratory mixer. Epoxy resins were added first. MEK was added as a solvent to the epoxy resin mixture, as needed, in order to adjust the rheology and solids content of the composition. Subsequently, the hardening agents (pre-reacted adduct and / or PES-PEES copolymer) were added to the epoxy resins. In certain surface coating films (Formulations 4 and 5), conductive additives (silver flakes or Ag-Cu flakes) were also added to the mixing vessel. Ceramic microspheres, smoked silica, and UV stabilizers (in some formulations) were additionally added to the mixing vessel. The MEK solvent was added, as needed, to control the viscosity of the above mixture to about 80% by weight of solids and the components of the composition were mixed for about 50 to 70 minutes at about 1000 to 3000 rpm. The temperature of the composition was kept below about 160 ° F. Additional MEK was added, as needed, to inhibit mixing from rising the mixing axis.
    [0042] [00042] The mixture was subsequently cooled to below about 120 ° F and curing agents (dicyandiamide (Dicy) and Bisureia) were added to the composition. The composition was then mixed until it was approximately homogeneous. The temperature of the mixture, during the addition of the curing agents, was kept below about 130 ° F.
    [0043] [00043] To form the surface coating films of the above compositions, each composition was filtered, de-aerated, and deposited as a film. The filtration was carried out using EP-15 filtration media. Deaeration was performed so that the solids content of the composition was about 80% by weight. The deaerated and filtered composition was then coated, like a film having a film weight of about 0.020 to 0.030 psf by a film applicator, and then dried to achieve less than 1% by weight of volatile compounds. . A selected non-woven polyester or random glass mat carrier or conductive carrier was pressed onto the film under slight pressure to incorporate the mat into the film.
    [0044] [00044] Composite panels were manufactured incorporating the surface coating films formed from the formulations in Table 2. For each panel, the surface coating film was placed on a tool, followed by the placement of pre-impregnated layers (CYCOM 5276-1 from Cytec Industries Inc., Cytec Industries Inc., carbon fiber / epoxy prepregs) to form a prepreg tray. The pre-impregnated tray was then cured at a temperature between about 350 ° F for 2 hours below 80 psi in autoclave conditions. Evaluation of the Surface Coating Film
    [0045] [00045] The glass transition temperature (Tg) of the cured surface coating films was determined using a modulated DSC (TA 2910) or a mechanical thermal analyzer (TMA 2940, TA Instruments) under nitrogen at elevation of 10 ° C / min in the temperature range from 30 ° C to 230 ° C.
    [0046] [00046] After curing, the composite panels coated with the surface coating films were inspected for surface appearance defects (holes, pin holes). Then, the composite panels were evaluated for their resistance to pickling, adhesion of dry and wet paint with or without UV exposure, and resistance to micro cracking. Stripping Resistance Test
    [0047] [00047] The stripping resistance of coated, unpainted composite panels (2 "x 2" sample size, 0.15 mm thick) was measured by measuring the pickling fluid intake and surface pencil hardness change over the immersion period (up to 168 hours at room temperature) of the stripping solution based on benzyl alcohol (Cee Bee 2012A available from McGean or Turkish 1270-6 available from Henkel) used for the stripping process of the structure aerospace composite. The weight of each test panel was measured before and after absorbing the paint stripper within 24 hours, 48 hours and up to 168 hours (7 days). The pickling fluid intake (change in weight over time of immersion, expressed in% by weight) of the panel tested was measured at the same test intervals up to 168 hours (7 days) immersion.
    [0048] [00048] The surface of each unpainted test panel was immersed in a benzyl alcohol stripping solution for up to 168 hours at room temperature, and then tested for pencil hardness change during the immersion period according to ASTM D3363. ASTM D3363 refers to a Standard Test Method for determining the surface hardness of the clear, pigmented organic coating film on a substrate. The pencil hardness scale is as follows: 6B (softer), 5B, 4B, 3B, 2B, B, HB, F, H, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9H (more rigid) . The pencil hardness of the test panel was measured before and after absorption in the paint stripper in the interval of 24 hours, 48 hours and up to 168 hours (7 days). The pencil hardness that changes more than the 2H level after the 24-hour immersion is not considered to have good resistance to pickling. Adhesion to Dry and Wet Paint with or without UV exposure
    [0049] [00049] The adhesion of the dry and wet trace paint to the painted composite panels (in the form of 3 "x 6" sample size, thickness 0.15 mm) coated with the surface coating film, with or without UV exposure before painting, were measured according to ASTM D3359. ASTM D3359 refers to a standard test method for assessing the surface adhesion of coating films to substrates by applying and removing pressure-sensitive tape over cuts made in the film (cross-trace tape test). The cured test panels were exposed to zero (without UV), 200 kJ / m2 or 1000 kJ / m2 of ultraviolet radiation (UV-A) in accordance with AATCC Test Method 16, Option 3. Instrument used for UV testing is a Xeno Weather-o-meter, such as Atlas CI3000 FadeoMeter. Each surface of the test panel was prepared (clean, with and without sanding) and applied with an external decorative paint coating used in aerospace paint (epoxy paint primer followed by a polyurethane based top coat). Subsequently, the dry paint adhesion test was performed in accordance with ASTM D3359. For wet paint adhesion, the test panels exposed to UV were painted and then immersed in deionized water at 75 ° F for 7 days. The paint adhesion test was then carried out in accordance with ASTM D3359. Electrical conductivity measurements surface coating films containing conductive additives
    [0050] [00050] Test panels with cured surface coating films were cut to form test bodies about 6 x 5 inches and their conductivity or surface resistivity (in ohm / square, or milliohm / square) was measured using an AVO® Ducter® DLRO10X four-point low resistivity Digital ohmmeter probe.
    [0051] [00051] Table 3 shows the surface properties and test results for test panels with surface coating films based on formulations 1-9 in table 2. The number of the test panel corresponds to the film formulation number surface coating.
    [0052] [00052] The surface coating films based on formulations 8 and 9 do not contain tri-functional or tetra-functional epoxy resin, as a result, their resistance to the paint stripper during the immersion period was not as good as seen in other films surface coating. However, all surface coating films exhibited good paint adhesion (10 + means 0% paint loss). Micro-crack resistance tests
    [0053] [00053] The resistance to micro-cracking of the coated and painted composite test panels (with a 4 "x6" sample size format, with a thickness of 0.15 mm), was also measured. The painted test panels were subjected to thermocycling between -55 ° C and 71 ° C until 2000X cycles. The surface of each test panel after thermocycling was examined under a microscope for the occurrence of microcracks after being exposed to 400X, 800X, 1200X, 1600X and 2000X thermal cycles. The crack density (number of cracks in the surface paint shown on the test panel the size of the area) is used to measure the micro crack strength of the coated composite test panel. The maximum crack length should be less than 0.1 inches. The results of the micro crack test after 2000 X thermal cycles are shown in table 4.
    [0054] [00054] Surface coating films based on formulations 6 and 7 do not contain the curing agents that were in other formulations. As a result, the micro-crack strength of test panels 6 and 7 was not as good as that of other test panels.
    [0055] [00055] The terms "first", "second", and so on, in this document do not indicate any order, quantity or importance, but are used to distinguish one element from the other and the terms "a" and "one" in this document they do not indicate a limitation of quantity, but denote the presence of at least one of the items referenced. The modifier "approximately" and "about" used in connection with a quantity is even the declared value and dictated the meaning by the context, (for example, it includes the degree of error associated with the measurement of the particular quantity). The suffix "(s)" in this document is intended to include both the singular and the plural of the term that it modifies, thus including one or more of that term (for example, the metal (s) includes one or more metals). Intervals disclosed in this document are inclusive and independently can be combined (for example, intervals of "up to approximately 25% by weight, or, more specifically, approximately 5% by weight of about 20% by weight", is inclusive of the end and all intermediate values of the scales, for example, "1% to 10% by weight" includes 1%, 2%, 3%, etc.
    [0056] [00056] While various modalities are described in this document, it will be appreciated from that report that various combinations of elements, variations or improvements can be made to it by persons skilled in the art, and are within the scope of the invention. In addition, many modifications can be made to adapt to a specific situation or material to the teachings of the invention without departing from its essential scope. Therefore, it is intended that the invention is not limited to the particular modality disclosed as the best mode envisaged for the realization of this invention, but that the invention will include all modalities falling within the scope of the added claims.
    权利要求:
    Claims (16)
    [0001]
    High resistance surface coating film for paint strippers, characterized by the fact that it has a glass transition temperature (Tg) of ≥180 ° C and a pencil hardness of 7H or higher according to ASTM D-3363, where, after being in contact with the etching solution based on benzyl alcohol, for 7 days the temperature within the range of 20 ° C to 25 ° C, said surface coating film presents less than 0.5% of fluid absorption, and the pencil hardness is not reduced by more than 2H pencil hardness, and wherein said surface coating film is formed by a curable resin composition comprising: a novolac epoxy resin having more than one epoxy functionality; a tri-functional or tetra-functional epoxy resin; ceramic microspheres; a latent amine-based curing agent; particulate inorganic filling material; and at least one curing agent selected from the group consisting of: (a) a pre-reacted adduct formed by the reaction of the epoxy resin, a bisphenol and an elastomer; (b) a polyether-sulfone (PES) and polyetherether sulfone (PEES) copolymer, (c) core-shell rubber (CSR); particles and their combinations.
    [0002]
    Surface coating film according to claim 1, characterized by the fact that it has a microfissure density of less than 0.047 cm-2 (0.3 inches / cracks2) after being subjected to an X 2000 thermal cycle test between -55 ° F and 71 ° F.
    [0003]
    Surface coating film according to claim 1 or 2, characterized in that the novolac epoxy resin has the following structure:
    [0004]
    Surface coating film according to any one of claims 1 to 3, characterized in that at least one hardening agent includes a pre-reacted adduct formed by the reaction of tetrabromo-bisphenol A diglycidyl ether, bisphenol A, and ATBN or CTBN elastomer.
    [0005]
    Surface coating film according to any one of claims 1 to 4, characterized in that at least one curing agent includes the pre-reacted adduct and PES-PEES copolymer.
    [0006]
    Surface coating film according to any one of claims 1 to 5, characterized in that the ceramic microspheres are hollow microspheres made of silica-alumina, ceramic material and having a particle size within the range of 1 μm to 50 μm (1 to 50 microns).
    [0007]
    Surface coating film according to any of statements 1 to 6, characterized by the fact that epoxy resin and ceramic microspheres make up more than 60% by weight of the total composition of the surface coating film.
    [0008]
    Surface coating film according to any one of claims 1 to 7, characterized in that it further comprises conductive materials in the form of particles, wherein the conductive materials in the form of particles are selected from the group consisting of the metals silver, gold , nickel, copper, aluminum and their alloys, in the form of flakes or particles.
    [0009]
    Surface coating film according to any one of claims 1 to 8, characterized in that it is supported by a non-woven conveyor, selected from a polyester mat, a glass mat or a carrier conductor.
    [0010]
    Surface coating film according to any one of claims 1 to 9, characterized in that the curable resin composition further comprises a bisurea as a curing accelerator.
    [0011]
    Composite structure, characterized by the fact that it comprises a composite substrate having a coating film as defined in claim 1 formed thereon, wherein the composite structure comprises a matrix resin and reinforcement fibers.
    [0012]
    Composite structure according to claim 11, characterized in that said composite substrate comprises a pre-impregnated tray, the pre-impregnated tray is comprised of a plurality of pre-impregnated layers arranged one after another, each layer comprising reinforced fibers impregnated with the matrix resin, and the surface coating film is formed on the outer surface of the pre-impregnated tray.
    [0013]
    Composite structure according to claim 11 or 12, characterized in that it further comprises a layer of paint applied on the surface coating film, in which the adhesion of the surface coating film to the paint coating is such that substantially painted surface exhibits 0% paint loss after (a) being subjected to an ASTM D-3359 paint adhesion test under dry condition or (b) immersing in deionized water at 23.9 ° C (75 ° F) for 7 days after being subjected to a paint adhesion test in accordance with ASTM D-3359.
    [0014]
    Composite structure according to claim 11 or 12, characterized in that the adhesion of the surface coating film to the coating is such that the painted surface substantially exhibits 0% paint loss as determined by the following process: subjecting the film of unpainted surface coating at 1000KJ / m2 from UVA radiation exposure, followed by submitting the painted surface with a paint adhesion test according to ASTM D-3359 under a dry condition.
    [0015]
    Composite structure according to claim 13, characterized by the fact that the adhesion of the surface coating film to the coating is such that the painted surface exhibits substantially 0% loss of paint, as determined by the following process: submitting the film of unpainted surface coating at 1000 KJ / m2 from exposure to UVA radiation, followed by submitting the painted surface to immersion in 75 ° F (23.9 ° C) deionized water for 7 days and a paint adherence test in accordance with ASTM D-3359.
    [0016]
    Method to make the structure of the composite, characterized by the fact of understanding: (a) supplying the moldable pre-impregnated tray comprising a plurality of pre-impregnated layers arranged in a stacking arrangement, each pre-impregnated layer comprising the matrix resin and uncured or partially cured resin reinforcing fibers; (b) forming the surface coating film of the curable resin composition comprising: a novolac epoxy resin having more than one epoxy functionality; a tri-functional or tetrafunctional epoxy resin; ceramic microspheres; a latent amine-based curing agent; particulate inorganic fill material; and at least one hardening agent selected from the group consisting of: (a) a pre-reacted adduct formed by the reaction of the epoxy resin, a bisphenol and an elastomer; (b) a polyether-sulfone (PES) and polyetherether sulfone (PEES) copolymer, (c) core-shell rubber (CSR); particles and their combinations; (c) application of the surface coating film in contact with the pre-impregnated tray; and (d) co-curing the surface coating film and the pre-impregnated tray at a temperature within the range of 250 ° F to 350 ° F (120 ° C-175 ° C), whereby the cured surface coating film has a glass transition temperature (Tg) of ≥180 ° C and a pencil hardness of 7H or greater in accordance with ASTM D-3363 and where, after being in contact with the etching solution based on benzyl alcohol, for 7 days at a temperature within the range of 20 ° C to 25 ° C, said cured surface coating film has less than 0.5 % fluid absorption, and pencil hardness is not reduced by more than 2H pencil hardness.
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    同族专利:
    公开号 | 公开日
    JP2015507648A|2015-03-12|
    MY171334A|2019-10-09|
    MX358605B|2018-08-28|
    WO2013086063A3|2014-01-16|
    CA2858549C|2019-03-26|
    JP6046739B2|2016-12-21|
    CA2858549A1|2013-06-13|
    KR101984198B1|2019-05-30|
    IN2014CN04162A|2015-07-17|
    RU2014127858A|2016-01-27|
    BR112014007044A2|2017-04-11|
    US9676961B2|2017-06-13|
    CN103987751A|2014-08-13|
    US20170182719A1|2017-06-29|
    TW201329154A|2013-07-16|
    AU2012347889B2|2016-04-07|
    MX2014006534A|2014-07-10|
    WO2013086063A2|2013-06-13|
    CN103987751B|2017-09-12|
    TWI558759B|2016-11-21|
    EP2825579B1|2017-03-15|
    RU2608400C2|2017-01-18|
    KR20140109855A|2014-09-16|
    US20130149934A1|2013-06-13|
    EP2825579A2|2015-01-21|
    ES2626499T3|2017-07-25|
    US9925729B2|2018-03-27|
    AU2012347889A1|2014-02-06|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-08-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-09-24| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161569129P| true| 2011-12-09|2011-12-09|
    US61/569129|2011-12-09|
    PCT/US2012/068058|WO2013086063A2|2011-12-09|2012-12-06|Surfacing film for composite structures and method of making the same|
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