coating

Abstract

To provide a high solids content primer coating composition.SOLUTION: An ultra-high solids content primer coating composition comprises: (i) 5.0 to 50 wt.% of at least one bisphenol F epoxy resin; (ii) 1.5 to 12 wt.% of at least one silane; (iii) 0 to 20 wt.% of at least one hydrocarbon resin; (iv) 0 to 15 wt.% of at least one reactive diluent; and (v) at least one curing agent; where the composition has a solids content of at least 90 wt.% according to ASTM D5201-05; where the composition has a viscosity of 200 to 800 cps at 23°C and 50% RH (ASTM D4287); and where the ratio between hydrogen equivalents in the curing agent and epoxy equivalents of the coating composition is in the range between 50:100 and 120:100.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a low-solvent or solvent-free epoxy primer coating composition that can be applied by a conventional aerosolar spraying device and produces a rapidly curing corrosion-resistant primer layer on a substrate. In particular, the primer may be a universal primer and can be applied in a single coat without the need for a topcoat. To provide a paint composition that allows for aerosol spraying and has a very low solvent content, the present invention requires a combination of a bisphenol F epoxy resin, a specific amount of silane crosslinking agent, and preferably a reactive diluent and a hydrocarbon resin. [Background technology]

[0002] Background of the Invention In the normal painting of ships, various parts of the ship are individually coated with anti-corrosion paint. Ships are constructed by manufacturing individual blocks and assembling them, and therefore the painting work must be done on each block before assembly.

[0003] Universal primers (single-layer primers), typically possessing excellent weather resistance, adhesion to various finishes, and corrosion resistance, are used to coat blocks (which are pre-treated). This simplifies the painting process and minimizes waste.

[0004] Known universal primers include those based on epoxy resin, vinyl chloride copolymer, and curing agent (JP211464 / 1998). However, this paint composition uses solid epoxy resin and solid amine curing agent, and therefore requires a large amount of solvent. Generally, for safety, economic, and environmental reasons, it is preferable to reduce the solvent content. High-solids-content universal primers have therefore been desired.

[0005] To solve the above problems, corrosion-preventive paint compositions have been developed that contain a main component comprising a bisphenol A type liquid epoxy resin and an amine-based curing agent, either alone or in combination, such as an aliphatic polyamine, alicyclic polyamine, aromatic polyamine, or polyamide (e.g., JP80563 / 2002). This high-solids content rust-preventive paint has a solids content of approximately 80% by weight and a solvent content of approximately 20% by weight.

[0006] EP-A-1788048 describes a rapidly curing, high-solids content anticorrosive coating composition. While this document refers to high-solids content of less than 100%, many examples contain large amounts of solvents such as benzyl alcohol (which is considered to contribute to VOCs under new regulations). The coatings of the present invention have lower VOCs, can be applied in conventional aerosol spraying equipment, and have a useful pot life of 1.5 hours or more. High-solids examples 16-18 have very poor pot lives, which may be due to the excessive viscosity of the mixture. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 10-211464 [Patent Document 2] European Patent Application Publication No. 1788048 [Overview of the project] [Problems that the invention aims to solve]

[0008] The inventors hereby introduce existing technologies, particularly in terms of practical pot life and flexibility. We have devised a novel high-solids content universal primer that exhibits superior performance. Therefore, the composition of our invention is not only more applicable over longer periods, but the resulting paint is also more flexible. While we do not wish to be limited by theory, we surmise that both of these effects are related to the lower viscosity achieved in our invention compared to other high-solids content paint compositions.

[0009] One of the main limitations on the service life of universal primers, such as those applied to water ballast tanks, is brittleness. There is a risk of the paint cracking because the steel structure of the vessel moves due to environmental stresses (waves, wind, currents, and temperature changes), and welding is considered the most sensitive area.

[0010] The solvent-free system of the present invention has proven to be far more flexible, which is expected to contribute significantly to reducing maintenance and repair work when the container is unavailable.

[0011] Another weakness of these tanks is the low DFT region, and the developed products show remarkably good performance even at low DFTs, such as 160 micrometers.

[0012] The developed coating has also been shown to have excellent corrosion resistance. Several accelerated testing methods have been used to evaluate the corrosion resistance of the developed product (such as rust creep and coating peeling from steel substrates). All tests conducted show that a single coating of the novel solvent-free epoxy is superior to two coatings of existing universal primer coatings when compared at the same total DFT (320 micrometers). In solvent-free systems, the maximum protective film interval tends to be rather short, making it another common challenge. The current formulation provides a maximum recoating interval of two weeks under outdoor exposure. This is comparable to existing solvent-free products and is considered suitable for solvent-free systems.

[0013] Another objective of this development is to develop a product that can be applied throughout the year with a good pot life using a conventional airless spraying device. To achieve this objective, much effort has been spent on reducing the viscosity while maintaining the anti-corrosion properties, and at least some success has been achieved in the temperature range from -5°C to 40°C.

[0014] Furthermore, it has been found that the current solvent-free epoxy paint composition provides excellent anti-corrosion properties, a long pot life, and good drying time. In contrast, most solvent-free systems exhibit significantly increased drying time and short pot life.

Means for Solving the Problems

[0015] Summary of the Invention Therefore, from one perspective, the present invention is (i) At least one bisphenol F epoxy resin of 5.0 to 50% by weight; (ii) At least one silane of 1.5 to 12% by weight; (iii) At least one hydrocarbon resin of 0.5 to 20% by weight; (iv) At least one reactive diluent of 1.0 to 15% by weight; and (v) At least one curing agent; a high-solids primer paint composition, wherein the composition has a solids content of at least 90% by weight measured according to ASTM D5201-05; the composition has a viscosity (ASTM D4287) of 200 to 800 cps at 23°C and 50% RH; and the ratio of the active hydrogen equivalent in the curing agent to the epoxy equivalent of the paint composition is in the range of 50:100 to 120:100, providing a high-solids primer paint composition.

[0016] Preferably, the paint composition has a solvent content of less than 5% by weight. From one perspective, the present invention is [[ID=3五十]](i) At least one bisphenol F epoxy resin of 5.0 to 50% by weight; (ii) 1.5 to 12% by weight of at least one silane; (iii) 0.5 to 20% by weight of at least one hydrocarbon resin; (iv) at least one reactive diluent in an amount of 0-15% by weight; and (v) A very high solids content primer coating composition comprising at least one curing agent, wherein the composition has a solids content of at least 90% by weight as measured according to ASTM D5201-05; The composition has a viscosity of 200 to 800 cps at 23°C and 50% RH; and, The ratio of the active hydrogen equivalent in the curing agent to the epoxy equivalent in the paint composition is in the range of 50:100 to 120:100. To provide a primer coating composition with an extremely high solid content.

[0017] From another perspective, the present invention is (i) 5.0 to 50% by weight of at least one bisphenol F epoxy resin; (ii) 1.5 to 12% by weight of at least one silane; (iii) 0 to 20% by weight of at least one hydrocarbon resin; (iv) at least one reactive diluent in an amount of 1.0 to 15% by weight; and (v) A very high solids content primer coating composition comprising at least one curing agent, wherein the composition has a solids content of at least 90% by weight as measured according to ASTM D5201-05; The composition has a viscosity (ASTM D4287) of 200-800 cps at 23°C and 50% RH; and The ratio of the active hydrogen equivalent in the curing agent to the epoxy equivalent in the paint composition is in the range of 50:100 to 120:100. To provide a primer coating composition with an extremely high solid content.

[0018] From another perspective, the present invention is (i) 5.0 to 50% by weight of at least one bisphenol F epoxy resin; (ii) 1.5 to 12% by weight of at least one silane; (iii) 0 to 20% by weight of at least one hydrocarbon resin; (iv) at least one reactive diluent in an amount of 0-15% by weight; and (v) A very high solids content primer coating composition comprising at least one curing agent, wherein the composition has a solids content of at least 90% by weight as measured according to ASTM D5201-05; The composition has a viscosity (ASTM D4287) of 200-800 cps at 23°C and 50% RH; and The ratio of the active hydrogen equivalent in the curing agent to the epoxy equivalent in the paint composition is in the range of 50:100 to 120:100. To provide a primer coating composition with an extremely high solid content.

[0019] From another perspective, the present invention is Component (A) comprising at least one bisphenol F epoxy resin; and A primer coating composition with an ultra-high solid content comprising component (B) containing at least one curing agent, The primer paint composition, at least one silane, and optionally at least one A hydrocarbon resin; further comprising optionally at least one reactive diluent; The aforementioned paint composition is (i) 5.0 to 50% by weight of at least one bisphenol F epoxy resin; (ii) 1.5 to 12% by weight of at least one silane; (iii) at least one hydrocarbon resin in an amount of 0 to 20% by weight, for example, 0.5 to 20% by weight; (iv) at least one reactive diluent in an amount of 0 to 15% by weight, for example, 1.0 to 15% by weight; The composition has a solid content of at least 90% by weight; The composition has a viscosity of 200-800 cps at 23°C and 50% RH; and The ratio of the active hydrogen equivalent in the curing agent to the epoxy equivalent in the paint composition is in the range of 50:100 to 120:100. To provide a primer coating composition with an extremely high solid content.

[0020] From another perspective, the present invention is Component (A) comprising at least one bisphenol F epoxy resin; and A kit comprising component (B) containing at least one curing agent, Components (A) and (B) are suitable for mixing before applying the resulting composition to a substrate: When components (A) and (B) are mixed, the resulting composition is (i) 10 to 50% by weight of at least one bisphenol F epoxy resin; (ii) 1.5 to 12% by weight of at least one silane; (iii) at least one hydrocarbon resin in an amount of 0 to 20% by weight, for example, 0.5 to 20% by weight; (iv) comprising 0 to 15% by weight, for example, 1.0 to 15% by weight, at least one reactive diluent; The composition has a solid content of at least 90% by weight; The composition has a viscosity of 200-800 cps at 23°C and 50% RH; and The ratio of the hydrogen equivalent in the curing agent to the epoxy equivalent in the paint composition is in the range of 50:100 to 120:100. We will provide the kit.

[0021] From another perspective, the present invention is (i) 20-60% by weight of at least one bisphenol F epoxy resin; (ii) At least one silane in an amount of 2.0 to 15% by weight; (iii) at least one hydrocarbon resin in an amount of 0.5 to 20% by weight; and (iv) Component (A) comprising 0-15% by weight, for example 1.0-15% by weight, at least one reactive diluent; The kit provides a component (B) containing at least one curing agent.

[0022] From another perspective, the present invention is (i) 20-60% by weight of at least one bisphenol F epoxy resin; (ii) At least one silane in an amount of 2.0 to 15% by weight; (iii) 0 to 20% by weight of at least one hydrocarbon resin; and (iv) Component (A) comprising 1.0 to 15% by weight of at least one reactive diluent; The kit provides a component (B) containing at least one curing agent.

[0023] From another perspective, the present invention is (i) 20-60% by weight of at least one bisphenol F epoxy resin; (ii) At least one silane in an amount of 2.0 to 15% by weight; (iii) 0 to 20% by weight of at least one hydrocarbon resin; and (iv) Component (A) comprising 0-15% by weight, for example 1.0-15% by weight, at least one reactive diluent; The kit provides a component (B) containing at least one curing agent.

[0024] From another viewpoint, the present invention provides a substrate coated with the primer composition defined above.

[0025] From another viewpoint, the present invention provides a substrate coated with a cured primer coating composition as defined above.

[0026] From another perspective, the present invention provides a method for producing the above-defined paint composition, comprising the step of mixing component (A) and component (B).

[0027] From another perspective, the present invention provides a method for applying a paint composition to a substrate (for example, by aerosol spraying and optionally by curing the paint), comprising the steps of mixing component (A) and component (B) to form a mixture, and applying the mixture to a substrate.

[0028] From another perspective, the present invention is (I) A step of mixing component (A) and component (B) as defined above to form a mixture, and a step of applying the mixture to a substrate (for example, by aerosol spraying); (II) A step of applying the second coating of the mixture to the coated substrate before the mixture hardens on the substrate; A process in which process (II) is arbitrarily repeated; and (III) A method for applying a paint composition to a substrate, comprising the step of curing the paint composition.

[0029] In all embodiments, it is preferable that the coating composition contains at least one reactive diluent in an amount of 1.0 to 15% by weight.

[0030] In all embodiments, it is preferable that the coating composition contains at least one hydrocarbon resin in an amount of 0.5 to 20% by weight.

[0031] [Definition] The present invention relates to a high-solidity primer coating composition. The term "coating composition" is used to define a composition formed from a combination of a first composition (A) and a second composition (B). To prevent premature curing, the primer coating composition of the present invention is provided in two parts: a first composition (A) containing an epoxy resin and a second composition (B) containing a curing agent. Other components of the composition are preferably present in component (A), but may be added via component (B). [Modes for carrying out the invention]

[0032] [Detailed description of the invention] The present invention relates to a corrosion-preventive primer coating composition for substrates (such as metal substrates, particularly steel substrates). The steel substrate may be located on any object on which the coating of the present invention is useful. In particular, the substrate may be exposed to components (e.g., wind, rain, ice, or snow) or to water, particularly seawater. The substrate may be located on offshore platforms, wind turbines, chimneys, power plants or other industrial units, bridges, cranes, ships, vehicles, etc. Important areas include spaces, decks, superstructures outside the hull spray band on offshore facilities, and normally outer superstructures on offshore facilities, where long service lives are required.

[0033] In its most preferred embodiment, the substrate is part of a ship, particularly a ship's water ballast tank or portable water tank.

[0034] The primer coating composition forms an epoxy primer layer on the substrate. Ideally, the composition of the present invention is a universal primer, but the primer layer may be topcoated as desired. The universal primer provides good corrosion resistance protection. If further antifouling properties, color stability, or UV resistance are required, a protective film may be applied.

[0035] In a preferred embodiment, the primer coating composition is applied as a single layer and is not overcoated. The properties of any protective film layer are not characteristic of this invention, and therefore any known protective film layer may be used. Alternatively, the primer layer may be the only layer present in the substrate. It is noted that it is preferable for the coating composition to be applied as a single coat, that is, as a single application step. Therefore, it is not necessary to apply the primer composition in multiple coats.

[0036] <Primer coating composition> The primer layer coating composition comprises a binder based on at least one epoxy resin. The combination of epoxy resins in the primer layer composition is referred to as the binder in this text. Shortly before applying the primer layer composition to the substrate, the first composition is mixed with a second composition containing a curing agent to form the primer layer composition. The primer layer composition is then cured on the substrate to form the primer layer.

[0037] The binder in the primer layer composition may contain one or more epoxy resins. Ideally, the primer layer composition contains at least one liquid epoxy resin. The term "liquid" refers to the state of the epoxy resin at room temperature, 23°C, and 1 atm. A distinctive feature of the coating system of the present invention is its high solids content, which results in a low content of volatile organic compounds (VOCs). The solids content of the primer layer coating composition is preferably at least 90% by weight, for example, at least 95% by weight, and more preferably at least 99% by weight.

[0038] A distinctive feature of the coating system of the present invention is its high volume solids percentage ("VS%") (volume after the coating has dried), which results in a low content of volatile organic compounds (VOCs). The primer layer coating composition preferably has a volume solids percentage of at least 90%, for example, at least 95%, more preferably at least 99%, and particularly 100%.

[0039] The first composition preferably has at least 80%, for example, at least 90% volume solid. The second composition preferably has at least 80%, for example, at least 90% volume solid.

[0040] The aforementioned volume solid (expressed as a percentage) is often referred to as "VS%". VS% is determined according to D5201-05.

[0041] The primer composition of the present invention has, for example, less than 5% by weight of solvent, more specifically less than 2% by weight of solvent, more specifically less than 1.0% by weight of solvent, for example, a very low solvent content of 0.5% by weight or less. Ideally, there is no solvent at all in our high-solids coating composition.

[0042] The first composition may contain, for example, less than 5.0% by weight of solvent, more specifically less than 2.0% by weight of solvent, more specifically less than 1.0% by weight of solvent, for example 0.5% by weight or less, or a very low level of solvent. Ideally, the first composition should contain no solvent at all. The second composition may contain, for example, less than 5.0% by weight of solvent, more specifically less than 2.0% by weight of solvent, more specifically less than 1.0% by weight of solvent, for example 0.5% by weight or less, or a very low level of solvent. Ideally, the second composition should contain no solvent at all.

[0043] A higher solids content and lower solvent content result in a lower VOC content. The VOC content is preferably less than 250 g / L, more preferably less than 100 g / L, and most preferably less than 50 g / L. In some embodiments, the VOC content may be 25 g / L or less, for example, 10 g / L or less. In this regard, the volatile organic compound includes benzyl alcohol.

[0044] Very low VOC content makes it possible to establish a rapid-curing coating system with a very short "T2" time (i.e., non-stick time) and a very short "T3" time (curing dry time). The T2 time may be less than 20 hours, for example less than 17 hours. The T3 time may be less than 24 hours (ASTM D5895, measured at 10°C at 50%RH on a 350 micron thick coating). In certain preferred embodiments, the "T2" time is less than 12 hours at 23°C / 50%RH. The T3 time under the same conditions may be 14 hours or less, for example 12 hours or less.

[0045] The pot life of the coating composition of the present invention is preferably at least 1 hour, for example 1 to 3 hours, for example 1.5 to 2.5 hours. Pot life means the time after mixing of the first and second components during which the composition is still applicable to a substrate by an aerosol spraying method. If the composition cures very quickly, the coating composition will have a very short pot life. A pot life of less than 30 minutes is commercially difficult, considering the time required to coat large objects such as ship blocks and houses with a volume of 150 m³ or less to supply to a spray gun.

[0046] Many of the key properties of the compositions of the present invention are a result of the high solids content and relatively low viscosity of the claimed compositions.

[0047] The viscosity of the paint composition measured immediately after combining the two components may be in the range of 80-130 KU, for example 90-120 KU (at 5°C) or 60-105 KU at 23°C, for example 70-100 KU.

[0048] Alternatively, the viscosity measured immediately after combining the two components may be 200-800 cps at 23°C, for example, 200-700 cps, and more specifically, 250-600 cps. The viscosity of the first composition may be in the range of 300 to 800 cps, for example, 350 to 750 cps, at 23°C.

[0049] The composition hardens over time, and therefore, it can be understood that the viscosity of the composition increases during the hardening process. The measured viscosity in claim 1 is obtained immediately after mixing, and therefore before a significant hardening process occurs. "Immediately after mixing" means within 5 to 10 minutes of mixing.

[0050] <Epoxy resin> The epoxy binder system comprises one or more bisphenol F epoxy resins. It contains lipids. By using multiple epoxy groups in the resin (i.e., at least two such groups), it can be ensured that a crosslinked network can be formed.

[0051] The bisphenol F epoxy resin in the primer composition may have an EEW value of 100 to 350. However, the EEW of the epoxy resin in the primer layer composition is 300 or less, for example, 100 to 300, more specifically 150 to 250, and more specifically 170 to 200, which is particularly preferable. Ideally, the epoxy resin is liquid.

[0052] This level of EEW is important because it makes it possible to produce a primer layer composition having a desired mixing ratio between the epoxy resin component (first composition A) and the curing agent component (second composition B) (e.g., 1:1 to 4:1 volume solid, e.g., 3:1 volume solid).

[0053] Furthermore, it is well known that resins with low Mw (often correlated with low EEW) have lower viscosity and therefore require less solvent for production. This reduces VOC content and enables the high solids content of the present invention. However, care must be taken to avoid excessively low Mw, as there is a risk of crystallization if the Mw is too low. The Mw of the bisphenol F resin may be higher than 170 g / mol.

[0054] Preferred bisphenol F (4',4'-methylenebisphenol) resins are derived from combinations of bisphenol F and epichlorohydrin. The use of bifunctional resins is particularly preferred.

[0055] The use of bisphenol F resin is important because it is known to reduce the viscosity of this coating composition compared to coating compositions containing the more common bisphenol A resin. One or more epoxy resins, such as a mixture of two liquid epoxy resins, can be used. Therefore, two types of bisphenol F resins may be used.

[0056] These resins are commercially available products such as YDF-170 (Kukdo), GY285 (Huntsman), DER354 (Dow), EPIKOTE 862 (Momentive), BFE-170 (CCP), or KF8100 (Kolon).

[0057] Similar to the bisphenol F group, the composition may also include a further epoxy resin selected from aromatic or non-aromatic epoxy resins, which contains one or more epoxy groups per molecule, arranged internally, at the terminals, or on a cyclic structure. Suitable further epoxy binder systems include epoxy and modified epoxy resins selected from bisphenol A, novolac epoxy, dimer-modified epoxy, alicyclic epoxy, glycidyl ester and epoxy-functionalized polyacrylate, or any combination thereof.

[0058] <Solid epoxy> In a more preferred embodiment, the liquid epoxy primer is combined with a semi-solid or solid epoxy resin in the binder composition. The combination of solid and liquid epoxy resins results in an ideal drying / curing time while minimizing VOCs. By adding solid and liquid epoxy resins, the solvent can be reduced, thus providing an ideal balance between drying / curing time, ease of handling, and VOC requirements.

[0059] Solid epoxy resins have one or more epoxy groups. Suitable epoxy binder systems are thought to include epoxy resins and modified epoxy resins selected from bisphenol A, novolac epoxy, non-aromatic hydrogenated epoxy, dimerized epoxy, alicyclic epoxy, glycidyl ester and epoxy-functional polyacrylate or any combination thereof.

[0060] Preferred solid epoxy resins include bisphenol A resins, such as 4,4'-isopropylidenediphenol-epichlorohydrin resin and novolac resin.

[0061] Most preferred is a solid epoxy resin with an equivalent epoxy weight (EEW, epoxy equivalent) of 300 to 1000. However, most preferred is a solid epoxy resin with an EEW in the range of 350 to 750, for example, 400 to 700, and more specifically, 500 to 670. The use of bisphenol A type resin is most preferred.

[0062] From another perspective, in a preferred embodiment, the EEW of at least one epoxy resin component is less than 300, and the EEW of the second epoxy resin is greater than 300.

[0063] When both liquid and solid epoxy resins are present in the binder of the primer layer, it is preferable that the liquid epoxy resin is present in excess of the solid epoxy resin. Typically, the weight ratio of the liquid epoxy resin to the solid epoxy resin in the binder is in the range of 2:1 to 1:1, for example, 2:1 to 1.1:1.

[0064] However, it is preferable that the primer layer composition and therefore the first composition contain only a liquid epoxy resin.

[0065] As shown below, the primer layer composition may contain other components in addition to the epoxy resin that forms the binder component. The binder component preferably forms 10 to 50% by weight, for example 10 to 40% by weight, more specifically 20 to 40% by weight, and most specifically 25 to 35% by weight of the primer layer composition.

[0066] Preferably, the binder component makes up 25 to 70% by weight of the first composition forming the primer layer composition, for example, 25 to 60% by weight of the first composition.

[0067] <Billa> The coating composition of the present invention also comprises at least one silane. The silane can improve low-temperature drying properties, flexibility, adhesion to substrates, and corrosion resistance. The silane may be provided as part of the first composition, or as part of the second composition, preferably as the first composition. Ideally, the silane contains an epoxy group. The silane used in the present invention is typically a low MW silane, such as less than 400 g / mol. Suitable silanes are those of general formula (I) or (II).

[0068] YR (4-z) SiX z (I) or YR (3-y) R 1 SiX y (II) In the formula, z is an integer between 1 and 3. y is an integer between 1 and 2. R is a hydrocarbonyl group having 1 to 12 C atoms, optionally containing an ether or aminolinker. R 1 This is a hydrocarbonyl group having 1 to 12 carbon atoms; Y is a functional group bonded to R that can react with the corresponding curing agent or binder functional group, and is preferably an amine or epoxy group. Each X independently represents either a halogen group or an alkoxy group.

[0069] The functional group Y is preferably an isocyanate, epoxy, amino, hydroxy, carboxy, acrylate, or methacrylate group. The Y group can be bonded to any part of the chain R. If Y means an epoxy group, then it will be understood that R has at least two carbon atoms and can form an epoxide ring system.

[0070] It is particularly preferable that Y is an amino group or an epoxy group. The amino group is preferably NH2. i. Y is preferably an epoxy group.

[0071] If the Y group is a polyamine and reacts with an epoxy binder, the silane is preferably provided as part of component (B) in this situation. Generally, in the kit of the present invention, the silane should not react with any of the kit components in which the silane is present.

[0072] It is particularly preferable that X is an alkoxy group, such as a C1-6 alkoxy group, especially a methoxy or ethoxy group. It is also particularly preferable that there are two or three alkoxy groups. Therefore, z is ideally 2 or 3, especially 3. The subscript y is preferably 2.

[0073] R 1 C 1-4 It is preferable that the alkyl group be, for example, methyl. R is a hydrocarbonyl group having 12 or fewer carbon atoms. Hydrocarbonyl means a group containing only C and H atoms. It may include an alkylene chain or a combination of an alkylene chain and a ring (e.g., a phenyl or cyclohexyl ring). The term "optionally containing an ether linker or amino linker" means that the carbon chain is interrupted in the chain by an -O- or -NH- group, e.g., silane, e.g., [3-(2,3-epoxypropoxy)propyl]trimethoxysilane:H2COCHCH2OCH2CH2CH2 This means that Si(OCH3)3 may be formed. It is preferable that group Y does not bond to a carbon atom that is bonded to a linker such as -O- or -NH-.

[0074] R may therefore mean (C6H5)-NH-(CH2)3- or Ph-NH-(CH2)3- or (C6H5)-(CH2)3, etc.

[0075] R is preferably an unsubstituted (clearly other than Y), unbranched alkyl chain having 2 to 8 carbon atoms, optionally containing an ether or aminolinker.

[0076] The preferred general formula for silane is therefore structure (III). Y’-R’ (4-z') SiX’ z' (III) [In the above formula, z’ is an integer from 2 to 3, R’ is an unsubstituted, unbranched alkyl chain having 2 to 8 carbon atoms, optionally containing an ether or amino linker, Y’ is an amino functional group or epoxy functional group bonded to the R’ group, X’ means an alkoxy group.

[0077] Examples of such silanes are many representative ones, products manufactured by Degussa in Rheinfelden marketed under the trade name Dynasylan(R)D, Silquest(R) silanes manufactured by OSi Specialties, and GENOSIL(R) silanes manufactured by Wacker.

[0078] Detailed examples include methacryloxypropyltrimethoxysilane (Dynasylan MEMO, Silquest A-174NT), 3-mercaptopropyltri(meth)ethoxysilane (Dynasylan MTMO or also 3201; Silquest A-189), 3-glycidoxypropyltrimethoxysilane (Dynasylan GLYMO, Silquest A-187), tris(3-trimethoxysilylpropyl)isocyanurate (Silquest Y-11597), gamma-mercaptopropyltrimethoxysilane (Silquest A-189), beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Silquest A-186), gamma-isocyanatopropyltrimethoxysilane (Silquest A-Link 35, Genosil GF40), (methacryloxymethyl)trimethoxysilane (Genosil XL 33), isocyanato ​​​(N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Genosil XL 43), aminopropyltrimethoxysilane (Dynasylan AMMO; Silquest A-1110), aminopropyltriethoxysilane (Dynasylan AMEO), or N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Dynasylan DAMO, Silquest A-1120) or N-(2-aminoethyl)-3-aminopropyltri Ethoxysilane, triamino-functional trimethoxysilane (Silquest A-1130), bis(ga N-trimethoxysilylpropylamine (Silquest A-1170), N-ethyl-gamma- Aminoisobutyl (isobytyl)trimethoxysilane (Silquest A-Link 15), N-phenyl-gamma-aminopropyltrimethoxysilane (Silquest Y-9669), 4-amino This includes -3,3-dimethylbutyltrimethoxysilane (Silquest Y-11637), (N-cyclohexylaminomethyl)triethoxysilane (Genosil XL 926), (N-phenylaminomethyl)trimethoxysilane (Genosil XL 973), Deolink Epoxy TE and Deolink Amino TE (DOG Deutsche Oelfabrik), and mixtures thereof.

[0079] Other specific silanes of interest include 3-aminopropyltriethoxysilane. 3-aminopropyltrimethoxysilane, N-(aminoethyl)-aminopropyltrimethoxysilane H2NCH2CH2NHCH2CH2CH2Si(OCH3)3, 3,3-aminopropylmethyldiethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, (H2NCH2CH2NHCH2CH2CH2SiCH3(OCH3)2), [3- [2,3-Epoxypropoxy]propyl]triethoxysilane (H2COCHCH2OCH2CH2CH2Si(OCH2CH3)3, containing [3-(2,3-epoxypropoxy)propyl]trimethoxysilane (H2COCHCH2OCH2CH2CH2Si(OCH3)3) .

[0080] The use of silane GLYMO is particularly preferred. Mixtures of silanes may also be used. The amount of silane present in the first composition may be 2.0 to 15% by weight, preferably 2.0 to 10% by weight, more preferably 2.0 to 8.0% by weight, and ideally 2.0 to 7.0% by weight, based on the total weight. The amount of silane in the paint composition may be 1.5 to 12% by weight, preferably 1.5 to 8.0% by weight, more preferably 1.5 to 6.0% by weight, and ideally 2.0 to 6.0% by weight, based on the total weight. Normally, silane is not present in the second composition. The amount of silane in the combined composition is determined by the amount in the first composition, taking into account the amount of the second composition to be added next. As the silane content increases, the viscosity of the composition tends to decrease. Therefore, the combination of bisphenol F and a relatively high silane content (minimum 1.5% by weight) yields a paint composition with remarkably low viscosity, considering the very low level of solvent used.

[0081] <Reactive Diluent> The primer layer composition preferably further contains a reactive diluent, preferably a reactive diluent formed from a modified epoxy compound.

[0082] Examples of such reactive diluents include phenyl glycidyl ether, alkyl glycidyl ether (number of carbon atoms in the alkyl group: 1-16), and glycidyl esters of versatic acid (R 1 R 2 R 3 C-COO-Gly, where R 1 R 2 R 3This is an alkyl group, for example, a C8-C10 alkyl group, and Gly (This is a glycidyl group), olefin epoxide (CH3-(CH2) n -Gly, during the ceremony The following are examples of these compounds: n=11-13, Gly: glycidyl group), 1,6-hexanediol diglycidyl ether (Gly-O-(CH2)6-O-Gly), neopentyl glycol diglycidyl ether (Gly-O-CH2-C(CH3)2-CH2-O-Gly), trimethylol propane triglycidyl ether (CH3-CH2-C(CH2-O-Gly)3), and C1-20-alkylphenyl glycidyl ether (preferably C1-5 alkylphenyl glycidyl ether), such as methylphenyl glycidyl ether, ethylphenyl glycidyl ether, propylphenyl glycidyl ether, and glycidyl neodecanoate esters. Another preferred option is Cardolite NC-513, derived from the reaction of oil obtained from cashew nut shells with epichlorohydrin. Of course, the above reactive diluent is preferably an aliphatic reactive diluent, such as 1,6-hexanediol diglycidyl ether or 1,4-butanediol diglycidyl ether. Aliphatic glycidyl ethers with 8 to 14 chains are also preferred. The preferred reactive diluent would be aliphatic because it contributes to the flexibility of the paint. The use of p-TBPGE (para-tert-butylphenyl glycidyl ether) is also possible.

[0083] When the reactive diluent is polyfunctional, the opposite of monofunctional, this is preferable because it speeds up the drying process and increases the crosslinking density. This also contributes to better corrosion resistance.

[0084] The above-mentioned reactive diluents can be used alone or in combination of two or more diluents.

[0085] The reactive diluent is preferably present in the first composition together with the epoxy resin.

[0086] Overall, the reactive diluent is preferably present in the primer layer composition in an amount of 0.5 to 20% by weight, preferably 1.0 to 20% by weight, for example 1.0 to 15% by weight, and more specifically 2.0 to 12% by weight.

[0087] In the first composition, the reactive diluent is preferably present in an amount of 2.0 to 30% by weight, preferably 5.0 to 20% by weight, for example 5.0 to 15% by weight, and more particularly 6.0 to 12% by weight.

[0088] By adding the above-mentioned reactive diluent in the above amount, the viscosity of the main primer layer composition is reduced, enabling the production of a high-solids composition.

[0089] Preferably, the viscosity of the reactive diluent is <50 cP, preferably <30 cP, and most preferably <20 cP at 23°C and 50% RH. The method is a conical plate viscometer, according to ISO 2884-1:2006.

[0090] <Hydrogen resins> The coating composition of the present invention may also contain a hydrocarbon resin, which is preferably formulated as part of the first composition. Typically, all types of hydrocarbon resins can be used, such as solid or liquid pure C5 and C9 hydrocarbon resins, C5 / C9 mixtures, aliphatic / aromatic raw materials, and epoxy or hydroxyl-modified hydrocarbon resins. The C5 resin is typically an oligomer or polymer having five carbon atoms. The C9 resin is typically an oligomer or polymer of a nine-carbon aromatic monomer. Preferably, the hydrocarbon resin has a molecular weight of less than 1000 g / mol, most preferably less than 500 g / mol.

[0091] In the most preferred embodiment, the hydrocarbon resin is a xyleneformaldehyde resin (e.g., EPODIL LV5).

[0092] Ideally, the hydrocarbon resin is a petroleum resin. The petroleum resin is a polymer which may contain hydroxyl groups and is formed using, as the main raw materials, a fraction produced as a by-product in petroleum refining from petrochemical products and carbon raw materials.

[0093] Examples of petroleum resins that can be used in the present invention include aromatic petroleum resins obtained by polymerizing a C9 fraction (e.g., styrene derivatives, e.g., alpha-methylstyrene, o,m,p-cresol, indene, methylindene, cumene, napthalene, or vinyltoluene) obtained from heavy oil produced as a by-product of naphtha cracking; aliphatic petroleum resins obtained by polymerizing a C5 fraction such as 1,3-pentadiene or isoprene, 2-methyl-2-butene, cyclopentadiene, dicyclopentadiene, or cyclopentene. In addition, copolymer petroleum resins obtained by polymerizing the C9 and C5 fractions; aliphatic petroleum resins in which a portion of the conjugated diene of the C5 fraction (e.g., cyclopentadiene or 1,3-pentadiene) is cyclically polymerized; resins obtained by hydrogenating aromatic petroleum resins; and alicyclic petroleum resins obtained by polymerizing dicyclopentadiene can also be used. Mixtures of diaryl and triaryl compounds obtained from the reaction of a C9 blend under catalytic conditions can also be used. Hydroxyl groups are introduced into these petroleum resins. Of course, the above petroleum resins and hydroxyl group-containing aromatic petroleum resins are particularly preferred from the viewpoint of water resistance and seawater resistance.

[0094] Another possible hydrocarbon resin is xylene resin synthesized from 1,3-dimethylbenzene and formaldehyde (e.g., Epodil LV5). Phenol-modified xylene resins, such as those with difunctional phenols (e.g., phenol, para-t-butylphenol, p-cumylphenol, o,p-dicumylphenol), are also usable. Another option is coumarone resin, which is a copolymer containing coumarone units, indene units, and / or styrene units in its main chain.

[0095] The indene-coumarone resin may be modified at its ends with phenol, and at least some of the aromatic rings of the coumarone resin may be hydrogenated. Such a coumarone resin may include a liquid product with a number-average molecular weight Mn (measured by GPC, with polystyrene as the unit, the same applies hereinafter) of 200 to 300, and a solid product with a number-average molecular weight Mn of 600 to 800, and either one of these may be used alone or in combination.

[0096] The use of solid hydrocarbon resins should generally be avoided. Preferably, the hydrocarbon resin forms 0.5 to 20% by weight, preferably 1.0 to 20% by weight, for example 1.0 to 15% by weight, and more specifically 2.0 to 12% by weight of the paint.

[0097] In the first composition, the hydrocarbon resin is preferably included in an amount of 2.0 to 30% by weight, more preferably 2.0 to 15% by weight, for example, 3.0 to 10% by weight.

[0098] Most preferably, the hydrocarbon resin has an OH content of 0 to 5% by weight, or xyleneformaldehyde has an OH content of <3%.

[0099] Hydrocarbon resins based on hydrogenated natural resins (e.g., gum rosin, wood rosin, and barrel rosin) can also be used. Hydrocarbon resins are rosin esters. Esterified compounds may also be used.

[0100] <Additives> The primer layer composition may also contain various other components, such as components that improve its anticorrosive properties. In particular, the primer layer composition may contain metal oxides, metal carbonates, talc, feldspar, etc., and can function as an anticorrosive material. Specific anticorrosive functional pigments include zinc phosphate, zinc oxide, zinc powder, aluminum flakes, and lead oxide. Zinc powder or zinc flour is well known to be included in epoxy primers to form zinc epoxy primers, and is of great interest in this respect. Zinc powder or zinc flour can be replaced in whole or in part with zinc alloys, for example, those described in International Publication WO2008 / 125610. Auxiliary rust inhibitors, such as molybdates, phosphates, tungstates or vanadates, ultrafine titanium dioxide and / or zinc oxide and / or fillers (e.g., silica, calcined clay, aluminum silicate, talc, barite or mica).

[0101] A preferred filler package is one with an extender having a low oil absorption value (e.g., BaSO4, G The material comprises lath spheres, feldspar, calcite, silica, aluminum oxide, zirconium oxide, dolomite, kaolin, or wollastonite, and optionally thin-layer fillers (e.g., mica, talc, aluminum flakes, chlorite, and kaolin).

[0102] The primer layer composition or the first composition may contain 30 to 70% by weight of an anticorrosive agent. Ideally, these substances form more than 45% by weight of the primer layer composition.

[0103] Other components besides those listed above include anti-sagging / anti-hardening agents, plasticizers, inorganic or organic dehydrating agents (stabilizers), anti-fouling agents, dyes, and other film-forming components, which may be added as needed.

[0104] As anti-sagging / anti-hardening agents (thixotropes), thixotropes such as polyamide waxes, polyethylene waxes, or bentonite-based thixotropes can be used. Examples of such anti-sagging / anti-hardening agents include Cryvallac Ultra, Crayvallac LV (both from Arkema), Thixatrol ST and Thixatrol Max (both from Elementis), and Disparlon 6650 (from Kusumoto Chemicals Ltd). Examples of coloring pigments include titanium white, red iron oxide, iron yellow, carbon black, and organic coloring pigments. Specific colors may be produced using various paints.

[0105] The total amount of the various additive components described above depends on the application and cannot be determined indiscriminately, but they are often included in the first composition in a total amount of 10 to 65% by weight. Furthermore, they are often included in a total amount of 10 to 65 parts by weight per 100 parts by weight of the paint composition.

[0106] If present, suitable solvents are hydrocarbons such as xylene. If present, the solvent is preferably added to the first composition used to produce the primer layer composition. Some solvents may be present with the curing agent or among some of the additives used. The properties of the solvent in the primer layer are not limited, but known solvents with a wide range of boiling points can be used. Examples of such solvents include xylene, toluene, MIBK, methoxypropanol, MEK, butyl acetate, benzyl alcohol, octylphenol, resorcinol, n-butanol, isobutanol, and isopropanol. The solvents may be used alone or in combination of two or more.

[0107] <Hardening agent> To cure the first composition containing the epoxy binder, polyamides, polyamines, epoxy-amine adducts, phenalkamine, or phenalkamide curing agents may be used, as is well known in the art. These are also known as crosslinking agents or curing agents. In order to function as a curing agent, the compound must contain at least two "reactive" hydrogen atoms bonded to nitrogen. Thus, the curing agent typically contains at least two amines (which may be primary or secondary).

[0108] Suitable curing agents are thought to include amines or amino-functional polymers selected from aliphatic amines and polyamines (e.g., alicyclic amines and polyamines), polyamidoamines, polyoxyalkyleneamines (e.g., polyoxyalkylenediamines), amination polyalkoxy ethers (e.g., those marketed as "Jeffamines"), alkyleneamines (e.g., alkylenediamines), aralkylamines, aromatic amines, Mannich bases (e.g., those marketed as "phenalkamines"), amino-functional silicones or silanes, and their epoxy adducts and derivatives.

[0109] Examples of suitable commercially available hardeners are as follows: o Cardolite NC-541, ex Cardanol Chemicals (USA), Mannich base o Cardolite Lite 2001, ex Cardanol Chemicals (USA), Mannich base o Sunmide CX-105X, ex Sanwa Chemical Ind. Co. Ltd. (Singapore), Mannich salt basis o Epikure 3090 hardener, ex Resolution Performance Products (USA), epoxy and epoxies riamidamine adduct o Epikure 3140 Hardener, ex Resolution Performance Products (USA), Polyamide Epikure 3115X-70 Hardener, ex Resolution Performance Products (USA), Polyamide Amine o SIQ Amin 2015, ex SIQ Kunstharze GmbH (Germany), Polyamidoamine o SIQ Amin 2030, ex SIQ Kunstharze GmbH (Germany), Polyamidoamine o Polypox VH 40309 / 12, ex Ulf Prummer Polymer-Chemie GmbH (Germany), Polyoxyalkyleneamine o Polypox VH 40294, ex Ulf Prummer Polymer-Chemie GmbH (Germany), Mannich base Ancamine 2609, ex Air Products (UK), Mannich base Ancamine 2695, ex Air Products (UK), polyamine; Ancamine 2738, ex Air Products (UK), polyamine o Adeka curing agent, ex Adeka Corporation (Japan), Mannich base o AP1077, Admark, Mannich base o CeTePox 1490 H, ex CTP Chemicals and Technologies for Polymers (Germany), Poly Oxyalkyleneamine o Epoxy curing agent MXDA, ex Mitsubishi Gas Chemical Company Inc (USA), aralkylamine o Diethylaminopropylamine, ex BASF (Germany), aliphatic amine o Gaskamine 240, ex Mitsubishi Gas Chemical Company Inc (USA), Aalkylamine o Cardolite Lite 2002, ex Cardanol Chemicals (USA), Mannich base o Aradur 42 BD, ex Huntsman Advanced Materials (Germany), Alicyclic amine o Isophorondiamin, ex BASF (Germany), alicyclic amine o Crayamid E260 E90, ex Cray Valley (Italy), polyamidoamine adduct with epoxy o Aradur 943 CH, ex Huntsman Advanced Materials (Switzerland), Epoxy and Alkylene Amine adduct.

[0110] The use of modified polyamines is most preferred. Phenalkamine can also be used. It will be understood that the curing agent is transported separately from the epoxy resin and mixed with the epoxy resin only shortly before application. The curing agent of the present invention is therefore transported as a second composition, which is combined with the first composition to form the primer layer composition. The second composition may consist of the curing agent.

[0111] An important parameter for the curing agent of interest is a viscosity lower than 300 cP, for example, a viscosity of 100-300 cP.

[0112] In a preferred embodiment, the curing agent is used without the use of a separate catalyst to facilitate the crosslinking process. However, some known curing agents are used in combination with catalysts such as tertiary amine catalysts, which falls within the scope of this invention. The curing agent is supplied neat or in a solvent, and it will be understood that it can ideally be supplied neat.

[0113] An epoxy binder system that cures at room temperature is preferred. The number of "active hydrogen equivalents" associated with one or more curing agents is the sum of the contributions from each of the one or more curing agents. The contribution of each of the one or more curing agents to the active hydrogen equivalents is defined as the grams of the curing agent divided by the weight of the active hydrogen equivalents of the curing agent. The weight of the active hydrogen equivalents of the curing agent is determined as the grams of the curing agent equivalent to 1 mole of active hydrogen. For adducts with epoxy resins, the contribution of the reactant before the adduct is used to determine the number of "active hydrogen equivalents" in the complete epoxy binder system. The number of "epoxy equivalents" is the sum of the contributions from each of the one or more epoxy resins and other epoxy-containing components such as the silane and reactive diluent. The contribution of each of the one or more epoxy resins to the epoxy equivalents is defined as the grams of the epoxy resin divided by the weight of the epoxy equivalents of the epoxy resin. The weight of the epoxy equivalents of the epoxy resin is determined as the grams of the epoxy resin equivalent to 1 mole of epoxy groups. With respect to adducts with epoxy resins, the contribution of the reactant before addition is used to determine the number of "epoxy equivalents" in the epoxy binder system.

[0114] Preferably, the ratio of the total hydrogen equivalent to the total epoxy equivalent of the curing agent is in the range of 50:100 to 120:100.

[0115] In detail, a preferred epoxy coating composition has a ratio of the active hydrogen equivalent of the curing agent to the epoxy equivalent of the composition in the range of 60:100 to 110:100, for example, 70:100 to 105:100, for example, 80:100 to 90:100.

[0116] The mixing ratio of the first composition and the second composition is, of course, influenced by the relative amounts of epoxy and active hydrogen present. Ideally, the mixing ratio is 1:1 to 10:1, for example, 5:1 to 2:1, in terms of solid volume, of the first composition to the second composition. Unless otherwise specified, all quantities expressed as % by solids volume are understood as % by solids volume of the mixed primer layer composition prepared for application.

[0117] The curing agent composition (second composition) and the first composition are mixed shortly before being applied to the substrate.

[0118] <Preparation of the primer composition> The primer composition can be manufactured by any suitable technique commonly used in the field of paint manufacturing. Therefore, various components may be mixed together using a high-speed dispenser, ball mill, pearl mill, three-roll mixer, inline mixer, etc. The paint according to the present invention can be filtered using a bag filter, patron filter, wire gap filter, wedge wire filter, metal edge filter, EGLM turnoclean filter (ex Cuno), DELTA strain filter (ex The filter may be filtered using a Cuno or Jenag Strainer filter (ex Jenag), or by vibration filtration.

[0119] The primer composition used herein is typically manufactured by mixing its components. For example, the first composition and the curing agent component (the second composition) can be mixed by adding the curing agent to the first epoxy composition and stirring well until the mixture is homogeneous. The mixture is ready for immediate application (e.g., spray application), but a curing time may be given before application.

[0120] <Application of the Primer Composition> The primer composition can be applied to a substrate (particularly a steel structure substrate) by a conventional air spray device, airless spray device, or Airmax spray device, or by a well-known standard application method such as a 2K aerosol spray pump (or, instead, using a brush or roller, especially when used as a stripe coat). Preferably, the composition is applied under ambient conditions without preheating the paint composition. A normal pressure, for example, 3 to 5 bar, can be used.

[0121] <Film thickness> The coating is typically applied with a total dry film thickness of 100 to 500 μm, for example, 150 to 350 μm. The dry film thickness of the primer layer is preferably at least 100 μm. The applied film thickness may vary depending on the properties of the substrate to be coated and the expected exposure conditions.

[0122] <Curing> Once the substrate is coated with the paint, the paint is forced to harden. The primer layer may harden naturally. Irradiation and heating may be used to accelerate hardening, but the composition of the present invention hardens at room temperature without further interference.

[0123] Because the volatility content of the paint of the present invention is very low, it is preferable to apply a single paint, but it is possible to apply additional paints while the primer layer is "wet". Therefore, it is not necessary to wait for the first paint to cure before applying additional paints. It is known that multiple layers of the primer paint are applied to build up the layer thickness, but typically each layer is cured (dried) before applying the subsequent layers. In the present invention, the application of additional layers can be done on a wet (or uncured) primer layer. This accelerates the application process.

[0124] Thus, from a further aspect, the present invention includes a method of applying a further coat of the primer layer coating composition to the undercoat of the primer layer composition without an intermediate curing step. Alternatively, the present invention includes a method of applying a further coat of the primer layer coating composition to the undercoat of the primer layer composition before the undercoat cures. The present invention will be described with reference to the following examples, which are not intended to be limiting.

[0125] <Analysis method> General method for the production of the composition Component (I) of the primer layer was produced by mixing all the indicated components (in parts by weight) in a conventional manner known to those skilled in the art. Component (I) was then mixed with component (II) / curing agent before application. The primer layer was typically applied to a steel substrate by conventional airless spraying.

[0126] <Measurement of viscosity using a cone and plate viscometer> The viscosity of the binder and paint composition was measured using a cone and plate viscometer set at a temperature of 23°C and 50% RH, and providing viscosity measurements in the range of 0 - 10 P at 10000 s -1 in accordance with ISO2884 - 1:2006 (ASTM D4287). Stormer viscosity (KU) was performed at 23°C using a Stormer viscometer in accordance with ASTM D 562.

[0127] <Measurement of drying time using a Beck and Koller (BK) drying time recorder> The applied film was exposed while measuring the drying time at 23°C / 50% RH (or other specified conditions). The Beck Koller drying time was tested using a Beck and Koller drying time recorder in accordance with ASTM D5895. T2 - semi - dry (tack - free), T3 - cured drying time. For this test, a 300 micron DFT was used.

[0128] <Measurement of pot life> The pot life of the paint is determined by directly measuring the viscosity increase after mixing a minimum of 100 g of the paint composition at 23°C. Viscosity is measured every 15 minutes at 23°C using a Stormer viscometer according to ASTM D 562. The pot life is defined as the time at which the viscosity reaches 110 KU.

[0129] <Elongation: Conical mandrel bending test. Method: ASTM D 522.> Each paint was applied to a conical panel (110 × 170 × 1T) to a thickness of 600 μm using an applicator. The drying conditions before bending were 4 weeks at room temperature (23°C, 50% RH).

[0130] <Measurement of Dry Film Thickness (DFT)> The dry film thickness is measured using an Elcometer 456FBSI.

[0131] <Measurement of the solid content of the above composition> The solid content in the composition is calculated according to ASTM D5201-05. Calculation of the volatile organic compound (VOC) content of the aforementioned paint composition The volatile organic compound (VOC) content of the aforementioned paint composition shall be calculated in accordance with ASTM D5201-05.

[0132] [Examples] In all examples, the ratio of the active hydrogen equivalent in the curing agent to the epoxy equivalent in the coating composition is 100:100. The calculated VOCs in all these examples are 0, and therefore the solids content is 100%.

[0133] The following examples were prepared.

[0134] [Table 1]

[0135] Stoichiometric amounts of hardening agent and binder are used.

[0136] Types of epoxy resins 1. BPF liquid epoxy: Bisphenol-F epoxy resin 2. BPA liquid epoxy: Bisphenol-A epoxy resin 3. BPA(n=0) epoxy: Bisphenol-A(n=0) epoxy resin

[0137] [ka]

[0138] The viscosity of the aforementioned resin is shown in Table 2.

[0139] [Table 2]

[0140] The data indicates that bisphenol F is a preferred choice because it provides a paint with lower viscosity than recipe C2. Bisphenol A, which has a lower molecular weight in recipe C3, tends to crystallize more readily at low temperatures.

[0141] [Effects of silane coupling agents]

[0142] [Table 3]

[0143] [Table 4]

[0144] [Table 5]

[0145] [Table 6]

[0146] [Table 7]

[0147] Silane coupling agents contribute to shortening drying time, and this effect becomes more pronounced as the level increases.

[0148] The drying time is slightly longer than that of commonly used solvent-based (born) universal primers, but as a single-coat system, the total application time of the system is significantly reduced. Ro. Increasing the amount of silane A-187 (epoxy functional silane) reduces the viscosity of the paint (see recipes 4-9).

[0149] [Effects of epoxy-reactive diluents]

[0150] [Table 8]

[0151] [Table 9]

[0152] Aliphatic diluents are preferred because they contribute to the flexibility of the coating. Bifunctional reactive diluents are preferred over monofunctional diluents because they can increase the drying rate, and the increased crosslinking density contributes to better corrosion resistance.

[0153] [Table 10]

[0154] [Table 11]

[0155] [Effects of hydrocarbon resins]

[0156] [Table 12]

[0157] Types of hydrocarbons and their substitutes 1. Epodil LV5: Formaldehyde containing 1,3-dimethylbenzene, with OH content (0%). 2. Novares LC15:OH content (1.5%), phenol-modified hydrocarbon 3. Novares LS500: OH content (7.3%), phenol-modified hydrocarbon 4. Novares TL10: OH content (0%), C9 hydrocarbon 5. Novares LR600:OH content (0%), epoxy-functionalized hydrocarbon, EEW=295 6. Evonik Albidur EP2240: Epoxy-functionalized silicone rubber, EEW=300

[0158] [Table 13]

[0159] [Table 14]

[0160] Increasing the amount of hydrocarbon resin increases the pot life. As the amount of Epodil LV5 increases, the viscosity decreases in both composition A and the mixture of composition A and composition B. Epodil Lv-5 appears to be more effective than other hydrocarbon resins. Novares LR600 (recipe 8) came closest in viscosity reduction.

Claims

1. (i) 5.0 to 50% by weight of at least one bisphenol F epoxy resin; (ii) 1.5 to 12% by weight of at least one silane; (iii) 0 to 20% by weight of at least one hydrocarbon resin; (iv) at least one reactive diluent in an amount of 1.0 to 15% by weight; and (v) A very high solids content primer coating composition comprising at least one curing agent, wherein the composition has a solids content of at least 95% by weight as measured according to ASTM D5201-05; The above composition has a pot life of more than 80 minutes at 23°C. The composition has a viscosity (ASTMD4287) of 200 to 800 cps at 23°C and 50% RH; and The ratio of the amount of active hydrogen equivalent in the curing agent to the amount of epoxy equivalent in the paint composition is in the range of 50:100 to 120:

100. The silane is tris(3-trimethoxysilylpropyl) isocyanurate or of general formula (I) or (II). A primer paint composition with an extremely high solid content. Y-R (4-z) SiX z (I) or Y-R (3-y) R 1 SiX y (II) [In the formula, z is an integer between 1 and 3, y is an integer between 1 and 2. R is a hydrocarbyl group having 1 to 12 carbon atoms, or a hydrocarbyl group having 1 to 12 carbon atoms containing an ether or an aminolinker. R1 is a hydrocarbyl group having 1 to 12 carbon atoms; Y is a functional group bonded to R that can react with the corresponding curing agent or epoxy resin functional group. Each X independently represents either a halogen group or an alkoxy group.

2. The ultra-high solids content primer coating composition according to Claim 1, comprising 0.5 to 20% by weight of at least one hydrocarbon resin.

3. A paint composition according to claim 1 or 2, wherein the composition has a viscosity of 300 to 600 cps at 5°C and 50% RH.

4. A paint composition according to any one of claims 1 to 3, wherein the bisphenol F has an epoxy equivalent weight of 300 or less.

5. A paint composition according to any one of claims 1 to 4, wherein the bisphenol F has an epoxy equivalent weight of 100 to 300.

6. A paint composition according to any one of claims 1 to 5, wherein the silane is an epoxy-functionalized silane.

7. The silane is Methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri(me)ethoxysilane, 3-Glycidoxypropyltrimethoxysilane, Tris(3-trimethoxysilylpropyl) isocyanurate, Gamma-mercaptopropyltrimethoxysilane, Beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, Gamma-isocyanate propyltrimethoxysilane, (Methacryloxymethyl)trimethoxysilane, Isocyanate methyl)trimethoxysilane, aminopropyltrimethoxysilane, Aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, Triamino-functional trimethoxysilane, Bis(gamma-trimethoxysilylpropyl)amine, N-ethyl-gamma-aminoisobutyltrimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, (N-cyclohexylaminomethyl)triethoxysilane, (N-phenylaminomethyl)trimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(aminoethyl)-aminopropyltrimethoxysilane, 3,3-aminopropylmethyldiethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, (H2NCH2CH2NHCH2CH2CH2SiCH3(OCH3)2), [3-(2,3-epoxypropoxy)propyl]triethoxysilane, A paint composition according to any one of claims 1 to 6, selected from [3-(2,3-epoxypropoxy)propyl]trimethoxysilane and mixtures thereof.

8. A paint composition according to any one of claims 1 to 7, wherein the composition has a solvent content of less than 5% by weight.

9. A paint composition according to any one of claims 1 to 8, wherein the composition has a solvent content of less than 1.0% by weight.

10. A paint composition according to any one of claims 1 to 9, wherein the silane forms 2.0 to 10% by weight of the paint composition, and / or the hydrocarbon resin forms 2 to 10% by weight of the paint composition.

11. A paint composition according to any one of claims 1 to 10, wherein the reactive diluent is 1,6-hexanediol diglycidyl ether or 1,4-butanediol diglycidyl ether.

12. A paint composition according to any one of claims 1 to 11, wherein the curing agent is phenalkamine or a polyamine curing agent.

13. A paint composition according to any one of claims 1 to 12, wherein the reactive diluent has a viscosity of 50 cPs or less.

14. A paint composition according to any one of claims 1 to 13, wherein the reactive diluent is an aliphatic reactive diluent and is bifunctional.

15. A paint composition according to any one of claims 1 to 14, wherein the conical plate viscosity measured at 23°C is less than 500 cPs.

16. A paint composition according to any one of claims 1 to 15, wherein the VOC content is 100 g / L or less.

17. The paint composition according to any one of claims 1 to 16, wherein the VOC content is 50 g / L or less.

18. (i) 20 to 60% by weight of at least one bisphenol F epoxy resin; (ii) 2.0 to 15% by weight of at least one silane; (iii) 0 to 20% by weight of at least one hydrocarbon resin; and (iv) Component (A) comprising 1.0 to 15% by weight of at least one reactive diluent; The component (B) includes at least one hardening agent, The silane is tris(3-trimethoxysilylpropyl) isocyanurate or of general formula (I) or (II), Components (A) and (B) are mixed, and the resulting composition has a solids content of at least 95% by weight as measured according to ASTM D5201-05, and a pot life of more than 80 minutes at 23°C. kit. Y-R (4-z) SiX z (I) or Y-R (3-y) R 1 SiX y (II) [In the formula, z is an integer between 1 and 3, y is an integer between 1 and 2. R is a hydrocarbyl group having 1 to 12 carbon atoms, or a hydrocarbyl group having 1 to 12 carbon atoms containing an ether or an aminolinker. R1 is a hydrocarbyl group having 1 to 12 carbon atoms; Y is a functional group bonded to R that can react with the corresponding curing agent or epoxy resin functional group. Each X independently represents either a halogen group or an alkoxy group.

19. The kit according to claim 18, wherein the hydrocarbon resin comprises a reaction product of formaldehyde and 1,3-dimethylbenzene.

20. The kit according to claim 18 or 19, wherein component (A) comprises 0.5 to 20% by weight of at least one hydrocarbon resin.

21. The kit according to any one of claims 18 to 20, wherein component (A) comprises at least one reactive diluent in an amount of 1.0 to 15% by weight.

22. A metal substrate, wherein a coating composition according to any one of claims 1 to 17 is applied thereon.

23. Use of the coating composition according to any one of claims 1 to 17 for protecting a metal substrate.

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