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WO2021037150A1 - 无溶剂哑光聚脲涂料及用于生产该涂料的零件套装 - Google Patents

无溶剂哑光聚脲涂料及用于生产该涂料的零件套装 Download PDF

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Publication number
WO2021037150A1
WO2021037150A1 PCT/CN2020/111784 CN2020111784W WO2021037150A1 WO 2021037150 A1 WO2021037150 A1 WO 2021037150A1 CN 2020111784 W CN2020111784 W CN 2020111784W WO 2021037150 A1 WO2021037150 A1 WO 2021037150A1
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Prior art keywords
equal
coating
less
polyurea
solvent
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PCT/CN2020/111784
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English (en)
French (fr)
Inventor
迪特里希·彦
迟田田
李武松
李平
黄瑞
Original Assignee
深圳猿金刚新材料有限公司
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Application filed by 深圳猿金刚新材料有限公司 filed Critical 深圳猿金刚新材料有限公司
Priority to CN202080057466.9A priority Critical patent/CN114364759B/zh
Publication of WO2021037150A1 publication Critical patent/WO2021037150A1/zh
Priority to US17/678,862 priority patent/US20220177725A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02—Polyureas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/02—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a matt or rough surface
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0895—Manufacture of polymers by continuous processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3234—Polyamines cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3237—Polyamines aromatic
    • C08G18/324—Polyamines aromatic containing only one aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3237—Polyamines aromatic
    • C08G18/3243—Polyamines aromatic containing two or more aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/325—Polyamines containing secondary or tertiary amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3838—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing cyano groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/30—Processes for applying liquids or other fluent materials performed by gravity only, i.e. flow coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2503/00—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter

Definitions

  • This application relates to the technical field of coatings, in particular to a solvent-free matte polyurea coating and a set of parts for producing the coating.
  • Polymers are statistically significant molecules composed of repeatable monomers. In addition to their functional properties are determined by a complex parameter matrix, they are also determined by synthesis conditions, production techniques, processing methods and the additives used. While the latter can greatly affect characteristics such as UV stability, color, thermal stability and processability, the former has a significant impact on the basic properties of the polymer. In this way, for example, the mechanical properties of polymers can be specifically adjusted to the required degree in a wide range through this correlation, so that these substances can be used in medicine, cosmetics, construction materials, corrosion and anti-corrosion and consumer goods industries. Provide targeted solutions for a wide range of applications in such fields.
  • polyurea materials are particularly suitable for functional applications.
  • polyurea is considered to be a reaction system with fast reaction kinetics, which can provide a use time in the range of a few seconds in most applications.
  • other substances such as secondary amines
  • the obtained polyurea coating has good or very good chemical resistance, high elasticity and tear resistance.
  • it is difficult to obtain polyurea coatings with special surface properties because the addition of other substances that affect the appearance of the surface usually also interferes with the basic mechanical properties of the coating, making it difficult to maintain the required mechanical properties. It can individually change the performance of its surface.
  • the existing patent documents contain a variety of options for adjusting the surface properties of polyurea, which are achieved by adjusting the monomer units used or by adding other additives.
  • EP 2953990 B1 describes a non-aqueous coating composition, which contains:
  • An isocyanate reactive (reactive) agent comprising at least one secondary diamine, which is a reaction product of at least one diamine and an alkyl ester of 2-butenedioic acid;
  • At least one viscosity modifier wherein C) and D) account for less than about 35% of the total coating formulation, and wherein the gloss reducing agent includes fine-grained, organically treated precipitated silica.
  • EP 2588509 B1 discloses an aliphatic polyurea coating, which contains a product obtained by mixing components A, B and C:
  • EP 2 463 340 A1 the general polyurea functionalization treatment is involved.
  • This document discloses the use of a nucleating agent in the production of polyurea adducts from at least one amine and at least one isocyanate. The nucleating agent is combined with the resulting polyurea made of at least one amine and at least one isocyanate. The adduct is not isomorphic.
  • the purpose of this application is to provide a polyurea coating with improved mechanical properties and a matte surface and a set of parts for producing the coating.
  • One aspect of this application provides a solvent-free matte polyurea coating, which is obtained by reacting at least the following components:
  • Main chain extender it is characterized by:
  • the coating further includes finely ground carbon fibers as a matting agent, the average fiber length of the carbon fibers is greater than or equal to 50 ⁇ m and less than or equal to 150 ⁇ m, the weight fraction is greater than or equal to 4.5% and less than or equal to 25%, and the main expansion Chain agent is selected from diethyltoluenediamine, 4,4-methylene bis(N-sec-butyl-cyclohexylamine), 4,4-diaminodiphenylmethane, 4,4-diaminodicyclohexyl Methane, 3-[[3-[[(2-cyanoethyl)amino]methyl]-3,5,5-trimethylcyclohexyl]amino]propionitrile and 1,3-cyclohexanedimethylamine One or two or more of the composition.
  • the main expansion Chain agent is selected from diethyltoluenediamine, 4,4-methylene bis(N-sec-butyl-cyclohexylamine
  • the polyisocyanate prepolymer is a multifunctional polyisocyanate prepolymer having at least two or more isocyanate functionalities.
  • the polyisocyanate prepolymer is selected from toluene-2,4-diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI, HMDI), polymerized diphenylmethane One of diisocyanate (PMDI), tetramethylm-xylylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (H12MDI) or Two or more compositions.
  • TDI toluene-2,4-diisocyanate
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • HMDI hexamethylene diisocyanate
  • PMDI tetramethylm-xylylene diisocyanate
  • IPDI isophorone diiso
  • the polyetheramine is a multifunctional polyetheramine having at least two or more amine functionalities, and has a molecular weight of 200-5000 g/mol.
  • the ratio of the number of moles of amine to the number of moles of isocyanate in the coating is 1-4.
  • the coating has a gloss value of greater than or equal to 10 and less than or equal to 70 measured at 60° according to DIN EN ISO 2813.
  • the coating has a luminosity value of greater than or equal to 10 and less than or equal to 70 measured at 85° according to DIN EN ISO 2813.
  • the weight fraction of the ground carbon fiber is greater than or equal to 7.5% and less than or equal to 15%.
  • the coating further includes a hindered amine resin with a weight fraction greater than or equal to 2.5% and less than or equal to 10%.
  • the coating further includes one or a combination of two or more of a deaerator, a dispersant, a UV stabilizer, a pigment, and a filler.
  • the ground carbon fiber has an average fiber diameter greater than or equal to 2.5 ⁇ m and less than or equal to 10 ⁇ m.
  • the solvent content of the coating is less than or equal to 1%.
  • the content of polyisocyanate in the coating is greater than or equal to 30% and less than or equal to 50%
  • the content of polyetheramine is greater than or equal to 20% and less than or equal to 80%
  • the content of chain extender More than or equal to 5% and less than or equal to 40%
  • the content of the matting agent in the form of finely ground carbon fiber is greater than or equal to 5% and less than or equal to 10%, wherein each component may also exist as a reaction product with each other.
  • the reaction is carried out by a spraying process.
  • kits of parts for the production of solvent-free matte polyurea coatings has at least one container for polyfunctional polyisocyanate prepolymer, one container for polyetheramine, and Mixing and extruding device, and at least one of the above containers has more than or equal to 2.5% by weight and less than or equal to 20% by weight of finely ground carbon fibers, and the fiber length is greater than or equal to 50 ⁇ m and less than or equal to 150 ⁇ m.
  • This application proposes a new application method for carbon fiber as a matting agent, which overcomes the limitations of the prior art on carbon fiber recognition, and obtains an unexpected matte effect.
  • the average fiber length of the carbon fibers is greater than or equal to 50 ⁇ m and less than or equal to 150 ⁇ m, and the weight fraction is greater than or equal to 4.5% and less than or equal to 25%;
  • the main chain extender is selected from diethyl Methyl toluenediamine, 4,4-methylene bis(N-sec-butyl-cyclohexylamine), 4,4-diaminodiphenylmethane, 4,4-diaminodicyclohexylmethane, 3-[[ 3-[[(2-cyanoethyl)amino]methyl]-3,5,5-trimethylcyclohexyl]amino]propionitrile, N,N'-isopropyl(3-aminomethyl- 3,5,5-trimethylcyclohexylamine) and 1,3-cyclohexanedimethylamine one or a combination of two or more.
  • the coating obtained by applying the above-mentioned paint has a very matt surface in addition to the particularly improved mechanical properties.
  • Carbon fiber is widely used in the manufacture of reinforced materials due to its high strength and high modulus.
  • the limitation of this understanding of carbon fiber is overcome, and the traditional thinking is broken, and a new method of carbon fiber as a matting agent is proposed.
  • Application method Due to the addition of carbon fiber, the strength and elasticity of the coating remain largely unchanged, and the light reflectivity of the surface can be adjusted in a wide range independently of the mechanical properties and manufacturing dynamics. Due to the addition of relatively large carbon fibers, the obtained polyurea coating is not bound by the rapid reaction theory.
  • carbon fiber provides a larger conjugated ⁇ -electron system, which is combined with the polyurea monomer used here to ensure a special interaction with light.
  • the carbon fiber itself has the ability to absorb in the visible light range, so in combination with the above interaction, the coating is colored black.
  • the composition and spatial configuration of the carbon fiber may be the source of the matting effect while maintaining the actual mechanical properties of the coating. This is in contrast to the matt polyurea layers from the state of the art, which are dyed black by, for example, blending or adding aromatic components in a chain extender.
  • Polyurea or polyurea refers to a polymer obtainable by addition polymerization of isocyanate and amine.
  • the polymer has at least part of the following structural elements:
  • the polyurea coating provided in the above embodiments is injection molded to produce an integral part or a part of the part, or the polyurea coating is used to coat all or only a part of the surface of the part to form a polyurea molded body or part of a molded body.
  • the polyurea molded body of the embodiment of the present application is preferably a "pure" polyurea molded body, that is, according to the polyurea development association (PDA) agreement on polyurea, the composition does not contain a component with a hydroxyl group.
  • PDA polyurea development association
  • the polyurea coating of the present application is matt, so the polyurea molded body or part of the molded body made has a non-smooth surface.
  • Standard methods can be used to determine the glossiness of the surface. If the coating has a value greater than or equal to 5 and less than or equal to 80 at an angle of 60°, it can be regarded as matt. If the coating solvent content is less than or equal to 5% by mass, the coating is judged to be solvent-free.
  • the solvent is water
  • the content of the solvent can be determined by Karl Fischer, for example, or when the solvent is an organic solvent, the content of the solvent can be determined by the HPLC method well known to those skilled in the art.
  • the coating involved in this application is obtained by reacting at least a polyisocyanate prepolymer, a polyetheramine, and a chain extender.
  • This means that the coating is mainly composed of polyurea.
  • polyurea is also composed of two main components, namely hardener and resin component. They are reacted to form a covalent bond including one or more of the components of the present application.
  • the resin component is called component B in the United States and component A in Europe.
  • the molded body may preferably comprise 70% by weight of polyurea, or more than 80% by weight of polyurea, or more than 85% by weight.
  • the molded body can have other conventional additives such as dyes, catalysts, rheology additives and adhesion promoters/adhesive promoters (amino-functional trialkoxysilanes), fillers (silicates), chain extenders and Desiccant (e.g. molecular sieve).
  • additives such as dyes, catalysts, rheology additives and adhesion promoters/adhesive promoters (amino-functional trialkoxysilanes), fillers (silicates), chain extenders and Desiccant (e.g. molecular sieve).
  • the coating is based on a three-dimensional network connected by covalent bonds formed by fully reacting at least bifunctional polyisocyanate prepolymer.
  • Difunctional isocyanate is generated by the general formula, Where R represents an aromatic, aliphatic or mixed hydrocarbon structure.
  • Possible difunctional polyisocyanate prepolymers are, for example, toluene-2,4-diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI, HMDI), polymerized diphenylmethane diisocyanate Isocyanate (PMDI), tetramethylm-xylylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (H12MDI), or the above isocyanate mixture.
  • TDI toluene-2,4-diisocyanate
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • HMDI hexamethylene diisocyanate
  • PMDI polymerized diphenylmethane diisocyanate
  • the quantitative ratio of the mixture prepared in step a) of the example method and the amount of isocyanate can be conveniently determined based on the functionality and isocyanate functionality of the premix from method step a).
  • the functional group can be determined purely mathematically.
  • one mole of isocyanate functionality is used per mole of amine.
  • the mixing ratio cannot be stoichiometric.
  • the mixing ratio can be set to 1 to 4 (calculated as the number of moles of amine/mole of isocyanate).
  • Polyetheramines are polymers in which primary amine groups are present at the ends of the polyether main chain.
  • the polyether backbone is usually formed by propylene oxide, ethylene oxide or mixed ethylene oxide/propylene oxide structural units.
  • the polyetheramines used may be present in a monodisperse form, have a fixed molecular weight or have a more or less broad molecular weight distribution. Potentially existing side chains can also be occupied by other primary amine groups, so there are polyfunctional polyether amines with more than two amine functionalities.
  • the bifunctional polyetheramine can be represented by, for example, the following structural formula:
  • the molecular weight of the polyetheramine used is between 200 and 5000 g/mol.
  • the functionality of the polyetheramine may be preferably 2 to 4, particularly preferably 2 to 3.
  • other secondary polyetheramines can also be added to the mixture. This can prolong the reaction rate in the example treatment step b).
  • the main chain extender used in the embodiments of the present application is particularly suitable for obtaining coatings with excellent mechanical and optical performance.
  • the main chain extender is selected from diethyltoluenediamine, 4,4-methylene bis(N-sec-butyl-cyclohexylamine), 4,4-diaminodiphenylmethane, 4,4-diaminodiamine Cyclohexylmethane, 3-[[3-[[(2-cyanoethyl)amino]methyl]-3,5,5-trimethylcyclohexyl]amino]propionitrile, N,N'-isopropyl One or a combination of two or more of the group (3-aminomethyl-3,5,5-trimethylcyclohexylamine) and 1,3-cyclohexanedimethylamine. These chain extenders can help to obtain coatings with particularly suitable optical properties.
  • the coating contains finely ground carbon fibers having an average fiber length greater than or equal to 50 ⁇ m and less than or equal to 150 ⁇ m, and a weight fraction greater than or equal to 4.5% and less than or equal to 25% as a matting agent.
  • Carbon fibers of this ratio have proven to be particularly suitable for obtaining particularly flexible and stable coatings.
  • a very matte coating can be produced without excessively impairing the mechanical properties of polyurea.
  • the average fiber length of the carbon fiber can be determined, for example, by a microscopic image of the part of the coating.
  • the weight fraction can also be determined microscopically using the density of fibers and polyurea.
  • the coating has a gloss value measured at 60° according to DIN EN ISO 2813, which is greater than or equal to 10 and less than or equal to 70.
  • the coating of this embodiment may have particularly matt optical properties while retaining the required mechanical properties.
  • the coating has a gloss value measured at 85° according to DIN EN ISO 2813 greater than or equal to 10 and less than or equal to 70.
  • the paint of this embodiment is obtained by a common spraying method (non-spraying process), which can particularly maintain the required mechanical properties while obtaining matt optical properties.
  • the coating has a gloss value of less than or equal to 10 measured at 85° according to DIN EN ISO 2813.
  • the coating of this embodiment is obtained by a spray process, which can particularly maintain the required mechanical properties while obtaining better matt optical properties.
  • the weight fraction of the ground carbon fiber may be greater than or equal to 7.5% and less than or equal to 15%. This ratio of carbon fibers has proven to be particularly suitable for obtaining a special matt coating while maintaining the required mechanical properties.
  • a further preferred range may be greater than or equal to 8.5% and less than or equal to 12.5%, and further greater than or equal to 9.0% and less than or equal to 11%.
  • the coating material may further include a hindered amine resin with a weight fraction greater than or equal to 2.5% and less than or equal to 10%.
  • Hindered amine resins are also known as HALS (Hindered Amine Light Stabilizers), and can be liquid or solid piperidine derivatives, for example. These substances contribute to the formation of particularly durable coatings, the optical properties of which hardly change during the service life.
  • the hindered amine resin may have the following exemplary structure, in which R can be set independently of each other to adjust the solubility in the polyurea system used.
  • the coating further contains at least one or a combination of two or more of a deaerator, a dispersant, an ultraviolet stabilizer, a pigment, and a filler.
  • This group of additional additives can preferably be used to fine-tune the optical and mechanical properties of the coating.
  • the average fiber diameter of the ground carbon fibers may be greater than or equal to 2.5 ⁇ m and less than or equal to 10 ⁇ m. These carbon fibers have proven to be particularly suitable for obtaining particularly matt polyurea coatings. Only a small amount is needed to obtain a matte coating with mechanical properties that exceed the additive-free version.
  • the average diameter of the ground fibers can be determined on the layer cross-section, for example, by a microscope.
  • the coating may have a solvent content of less than or equal to 1%.
  • the coatings involved in this application can have a very low solvent ratio. Therefore, these coatings can actually be considered solvent-free.
  • the content of polyisocyanate in the coating is greater than or equal to 30% and less than or equal to 50%, and the content of polyetheramine is greater than or equal to 20% and less than or equal to 80%;
  • the content of chain extender is greater than or equal to 5% and less than or equal to 40%;
  • the content of matting agent in the form of fine carbon fiber is greater than or equal to 5% and less than or equal to 10%, and each component can also be the product of its reaction
  • the sum of the various components totals 100%. If the additives other than the above are used, the sum of the above-mentioned components and the sum of other additives can reach 100% by weight.
  • the composition of the coating has proven to be very flexible and can produce sufficient matte effects. In addition, the above composition guarantees a sufficient application period, so even manual application can guarantee reproducible mechanical properties.
  • the reaction can be carried out by a spraying method, such as mist spraying. It has been found that it is particularly advantageous to use the fog spray method to make the coatings referred to in this application. This method allows for a particularly successful and effective reaction between the individual components, so that a particularly matt layer can be obtained on the outermost layer. Without being bound by theory, this specific surface roughness can be attributed to the combination of the components according to the present application and the specific application technology.
  • Another aspect of the embodiments of the present application also relates to a set of parts for the production of solvent-free matte polyurea coatings, which has at least one container for polyfunctional polyisocyanate prepolymer, one container for polyetheramine, and mixing and Extrusion device, and at least one of the above containers has more than or equal to 2.5% by weight and less than or equal to 20% by weight of finely ground carbon fibers, and the fiber length is greater than or equal to 50 ⁇ m and less than or equal to 150 ⁇ m.
  • the viscosity of the mixture in the two containers is different or similar, and the carbon fiber is placed in a container with a mixture with a lower viscosity, or if the viscosity is similar, the two containers can be placed in both containers. carbon fiber.
  • the package can provide highly reproducible and reliable matte polyurea coatings in manual or machine equipment applications.
  • the protection of coatings involved in this application also applies to the parts kit for implementing this application.
  • a mixture of 69% by weight of polyetheramine (Huntsman Jeffamine D2000), 21% by weight of diethyltoluenediamine (Lonzacure DETDA 80) and 10% by weight of carbon fiber particles was produced by mechanical stirring at room temperature.
  • the average fiber length of the fiber particles is 75 to 85 ⁇ m, the density is 1.7 to 1.9 g/cm 3 , and the diameter is 6 to 8 ⁇ m.
  • the mechanical properties of the fiber are preferably a tensile strength of 2.5 to 4 GPa, an E modulus of 150 to 250 GPa, and an elongation at break of 1-2%. Choosing fibers in these areas can achieve good mechanical and optical properties. Mix until a homogeneous premix is obtained.
  • the reaction premix from processing step a) is placed in a container.
  • the other container contains polyisocyanate prepolymer (Huntsman Suprasec 2054).
  • the reaction premix and the polyisocyanate prepolymer are sprayed onto the workpiece with a sprayer, such as a Graco reactor, to obtain a surface coating.
  • the spray gun is moved quickly to generate mist, which results in the formation of a rough surface on the substrate.
  • the mixing ratio of the premix from the treatment step a) and the polyisocyanate prepolymer in this step is 1:1.
  • polyetheramine 24.5% by weight of Huntsman Jeffamine D2000+19% by weight of Huntsman Jeffamine D400+7.5% by weight of Huntsman Jeffamine T5000+0.5% by weight of adhesion promoter
  • 39.5% by weight of polyetheramine are produced by mechanical stirring at room temperature.
  • the average fiber length of the fiber particles is 50 ⁇ m, the density is 1.7 to 1.9 g/cm 3 , and the diameter is 6 to 8 ⁇ m.
  • the mechanical properties of the fiber are preferably a tensile strength of 2.5 to 4 GPa, an E modulus of 150 to 250 GPa, and an elongation at break of 1-2%. Choosing fibers in these areas can achieve good mechanical and optical properties. Mix until a homogeneous premix is obtained.
  • the reaction premix from processing step a) is placed in a container.
  • the other container contains polyisocyanate prepolymer (Huntsman Suprasec 2067).
  • the reaction premix and the polyisocyanate prepolymer are sprayed onto the workpiece with a sprayer, such as a Graco reactor, to obtain a surface coating.
  • the spray gun is moved quickly to generate mist, which results in the formation of a rough surface on the substrate.
  • the mixing ratio of the premix from the treatment step a) and the polyisocyanate prepolymer in this step is 1:1.
  • polyetheramine 24.5% by weight of Huntsman Jeffamine D2000+19% by weight of Huntsman Jeffamine D400+7.5% by weight of Huntsman Jeffamine T5000+0.5% by weight of adhesion promoter
  • 39.5% by weight of polyetheramine are produced by mechanical stirring at room temperature.
  • the average fiber length of the fiber particles is 150 ⁇ m, the density is 1.7 to 1.9 g/cm 3 , and the diameter is 6 to 8 ⁇ m.
  • the mechanical properties of the fiber are preferably a tensile strength of 2.5 to 4 GPa, an E modulus of 150 to 250 GPa, and an elongation at break of 1-2%. Choosing fibers in these areas can achieve good mechanical and optical properties. Mix until a homogeneous premix is obtained.
  • the reaction premix from processing step a) is placed in a container.
  • the other container contains polyisocyanate prepolymer (Huntsman Suprasec 2067).
  • the reaction premix and the polyisocyanate prepolymer are sprayed onto the workpiece with a sprayer, such as a Graco reactor, to obtain a surface coating.
  • the spray gun is moved quickly to generate mist, which results in the formation of a rough surface on the substrate.
  • the mixing ratio of the premix from the treatment step a) and the polyisocyanate prepolymer is 1:1.
  • Example 2 Compared with Example 1, it is the same except that no carbon fiber is added.
  • Example 2 Compared with Example 2 and Example 3, it is the same except that no carbon fiber is added.
  • the extinction degree of the paint film surface formed by atomization spraying in each embodiment was measured at 85°, and the gloss of the paint film surface generated by spraying at 60° without the atomization method degree.
  • the coating formed by spraying the coating provided in the examples of this application has a very low gloss value, has a very matte surface, and can maintain the same
  • the existing coating has similar mechanical properties (see Example 2), and even has better mechanical properties than the existing coating (see Example 1, Example 3).

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Abstract

一种无溶剂哑光聚脲涂料，该涂料可通过使至少下列组分反应而获得：a)聚异氰酸酯预聚体；b)聚醚胺和c)主扩链剂；其中该涂料还包含磨细的碳纤维作为消光剂，其平均纤维长度大于或等于50μm且小于或等于150μm，且重量分数大于或等于4.5％且小于或等于25％。用于生产该无溶剂哑光聚脲涂料的零件套装，包括至少具有一个用于多官能聚异氰酸酯预聚体的容器，一个用于聚醚胺的容器以及混合和挤出装置，并且以上至少一个容器内具有磨细的碳纤维。

Description

无溶剂哑光聚脲涂料及用于生产该涂料的零件套装
Solvent-free matt polyurea coating and kit of parts for producing the coating
本申请要求在2019年8月30日提交德国专利局、申请号为202019104767.4、名称为“无溶剂哑光聚脲涂料”的德国实用新型的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及涂料技术领域，具体地，涉及一种无溶剂哑光聚脲涂料及用于生产该涂料的零件套装。
背景技术
聚合物，即由可重复性单体组成的统计学意义的分子，其功能特性除由复杂的参数矩阵决定之外，还由合成条件、生产工艺、加工方式及其所用助剂来决定的。而后者能极大的影响如紫外射线稳定、颜色、热学稳定和可加工性等特性，而前者对聚合物的基本性能有重大影响。以此，举例来说，可以通过这种相互关系在很宽的范围内将聚合物的机械性能专门调节到所需的程度，从而使这些物质为医药、化妆品、建筑材料、腐蚀防腐和消费品行业等领域的广泛应用提供有的放矢的解决方案。
因为其基础材料可用于生产具有非常高的层厚且具有特别有利的机械性能的涂层，聚脲材料特别适用于功能化应用。特别地是，聚脲被认为是具有快速反应动力学的反应体系，在大多数应用中可以提供几秒钟范围内的使用时间。通过添加其他物质，例如仲胺，还可以建立反应活性明显较低的体系，从而也使手动处理成为可行。而得到的聚脲涂层具有良好甚至非常好的耐化学性能以及高弹性能和抗撕裂性能。但是另一方面，得到具有特殊表面性能的聚脲涂层是很难的，因为添加影响表面外观的其他物质通常也会干扰 涂层的基本机械性能，使其难以维持所需的机械性能而只能单独改变其表面的性能。
现有的专利文献中包含多种用于聚脲的表面性能调节的选择，通过调整所使用的单体单元或者通过添加其他添加剂来实现。
例如，EP 2 953 990 B1描述了一种非水性涂料组合物，其包含：
A.一种异氰酸酯活性(反应)剂，其包含至少一种仲二胺，所述仲二胺是至少一种二胺与2-丁烯二酸的烷基酯的反应产物；
B.至少一种聚异氰酸酯树脂；
C.至少一种光泽减少剂；和
D.至少一种粘度调节剂；其中C)和D)占总涂料配方的量少于约35％，并且其中减光泽剂包括细粒的，有机处理的沉淀二氧化硅。
此外，EP 2 588 509 B1公开了一种脂肪族聚脲涂层，其包含通过混合A，B和C组分获得的产物：
A)30-50重量份的NCO封端的聚碳酸酯二醇改性的异佛尔酮二异氰酸酯(IPDI)预聚物和/或聚醚多元醇改性的异佛尔酮二异氰酸酯(IPDI)预聚物；
B)3-15重量份六亚甲基二异氰酸酯(HDI)低聚物；和
C)10-25重量份的氨基树脂，其包含受空间位阻效应影响的仲脂肪族二胺。
在另一专利文件EP 2 463 340 A1中涉及的通常的聚脲的功能化处理。该文献公开了成核剂在由至少一种胺和至少一种异氰酸酯生产聚脲加合物时的使用，该成核剂与所得的由至少一种胺和至少一种异氰酸酯制成的聚脲加合物不是同构的。
尽管已经存在用于调整聚脲涂层的性能的可能性，但是人们对其他可同时满足机械性能要求和无光泽的表面状态的解决方案仍然非常感兴趣，尤其是确定有效的和结果可再现的手段。
发明内容
本申请的目的是提供一种具有改善的机械性能和无光泽表面的聚脲涂料及用于生产该涂料的零件套装。
本申请一方面提供一种无溶剂哑光聚脲涂料，通过使至少以下组分反应而获得：
a)聚异氰酸酯预聚体；
b)聚醚胺；
c)主扩链剂；其特征在于：
所述涂料还包括作为消光剂的磨细的碳纤维，所述碳纤维的平均纤维长度大于或等于50μm且小于或等于150μm，重量分数大于或等于4.5％且小于或等于25％，并且所述主扩链剂选自二乙基甲苯二胺、4,4-亚甲基双(N-仲丁基-环己胺)、4,4-二氨基二苯甲烷、4,4-二氨基二环己基甲烷、3-[[3-[[(2-氰基乙基)氨基]甲基]-3,5,5-三甲基环己基]氨基]丙腈和1，3-环己二甲胺中的一种或两种以上的组合物。
作为优选，所述聚异氰酸酯预聚体为至少具有两个以上异氰酸酯官能度的多官能聚异氰酸酯预聚体。
作为优选，所述聚异氰酸酯预聚体选自甲苯-2,4-二异氰酸酯(TDI)、二苯甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯(HDI，HMDI)、聚合的二苯甲烷二异氰酸酯(PMDI)、四甲基间苯二亚甲基二异氰酸酯(TMXDI)、异佛尔酮二异氰酸酯(IPDI)、4,4’-二环己基甲烷二异氰酸酯(H12MDI)中的一种或两种以上的组合物。
作为优选，所述聚醚胺为至少具有两个以上胺官能度的多官能聚醚胺，且分子量在200-5000g/mol。
作为优选，所述涂料中胺摩尔数与异氰酸酯摩尔数的比例为1-4。
作为优选，所述涂料具有根据DIN EN ISO 2813在60°下测得的大于或等于10且小于或等于70的光泽度值。
作为优选，所述涂料具有根据DIN EN ISO 2813在85°下测得的大于或等于10且小于或等于70的光度值。
作为优选，所述磨细的碳纤维的重量分数大于或等于7.5％且小于或等于15％。
作为优选，所述涂料还包括重量分数大于或等于2.5％且小于或等于10％的位阻胺树脂。
作为优选，所述涂料还包括脱气剂、分散剂、UV稳定剂、颜料、填料中的一种或两种以上的组合物。
作为优选，所述磨细的碳纤维具有大于或等于2.5μm且小于或等于10μm的平均纤维直径。
作为优选，所述涂料的溶剂含量小于或等于1％。
作为优选，以重量分数计，所述涂料中聚异氰酸酯的含量大于或等于30％且小于或等于50％，聚醚胺的含量大于或等于20％且小于或等于80％，扩链剂的含量大于或等于5％且小于或等于40％，磨细的碳纤维形式的消光剂的含量大于或等于5％且小于或等于10％的，其中各个成分也可以彼此以反应产物的形式存在。
作为优选，所述反应通过喷雾工艺进行。
本申请的另一方面提供一种用于生产无溶剂哑光聚脲涂料的零件套装，所述套装至少具有一个用于多官能聚异氰酸酯预聚体的容器，一个用于聚醚胺的容器以及混合和挤出装置，并且以上至少一个容器内具有大于或等于2.5重量％且小于或等于20重量％的磨细的碳纤维，纤维长度大于或等于50μm且小于或等于150μm。
与现有技术相比，本申请具有以下有益效果：
(1)本申请所提供的无溶剂哑光聚脲涂料，通过加入磨细的碳纤维作为消光剂，使得该涂料涂覆获得的涂层在具有优异的机械性能的同时，还具有非常无光泽的表面。
(2)本申请针对碳纤维提出了其作为消光剂的新的应用方式，克服了现有技术对碳纤维认识的局限性，并且获得了预料不到的哑光效果。
(3)本申请所提供的涂料没有添加溶剂，因此被认为不含溶剂。
(4)本申请通过调节聚异氰酸酯预聚体、聚醚胺的官能度或者各组分的占比，可延长反应的时间，使得涂料的手动施涂成为可能。
(5)本申请通过加入位阻胺树脂，有助于形成耐久的涂层，延长涂层的使用寿命。
(6)本申请提供的用于生产无溶剂哑光聚脲涂料的零件套装，能够在手动或机器设备的应用中提供高度可再现且可靠的哑光聚脲涂层。
具体实施方式
下面将对本申请具体实施例中的技术方案进行详细、完整的描述。显然，所描述的实施例仅仅是本发明总的技术方案的部分具体实施方式，而非全部的实施方式。基于本发明的总的构思，本领域普通技术人员所获得的所有其他实施例，都落于本发明保护的范围。
本申请实施方式提出的无溶剂哑光聚脲涂料，通过使至少以下组分反应而获得：
a)聚异氰酸酯预聚体；
b)聚醚胺；
c)主扩链剂；其中，
还包括作为消光剂的磨细的碳纤维，所述碳纤维的平均纤维长度大于或等于50μm且小于或等于150μm，重量分数大于或等于4.5％且小于或等于25％；主扩链剂选自二乙基甲苯二胺、4,4-亚甲基双(N-仲丁基-环己胺)、4,4-二氨基二苯甲烷、4,4-二氨基二环己基甲烷、3-[[3-[[(2-氰基乙基)氨基]甲基]-3,5,5-三甲基环己基]氨基]丙腈、N，N'-异丙基(3-氨基甲基-3,5,5-三甲基环己胺)和1，3-环己二甲胺中的一种或两种以上的组合物。
令人惊讶地发现是，由上述涂料涂覆得到的涂层，除了有特别提升的机 械性能之外，还具有非常无光泽的表面。碳纤维由于其高强度高模量的特点被广泛应用于制造增强材料，但在本申请中，克服了对碳纤维的这种认识的局限性，打破了传统的思维，提出了碳纤维作为消光剂的新的应用方式。由于添加了碳纤维，涂层的强度和弹性在很大程度上保持不变，并且可以独立于机械性能和制造动力学而在很宽的范围内调节表面的光反射率。由于添加了相对较大的碳纤维使所获得的聚脲涂料不被快速反应理论所束缚。同时碳纤维提供了较大的共轭π电子体系，该体系与此处使用的聚脲单体结合，可确保与光的特殊相互作用。另外，碳纤维本身在可见光范围内具有吸收能力，因此结合以上的相互作用，涂层着色为黑色。碳纤维的组成和空间配置这两条可能就是同时保持涂层的实际机械性能的同时还能达到消光效果的根源。这与来自技术现状的无光泽聚脲层相反，这些无光泽聚脲层是通过例如在增链剂中掺入或添加芳族组分而被染成黑色。
本申请涉及无溶剂哑光聚脲涂料。聚脲或聚脲素是指可通过异氰酸酯和胺的加聚获得的聚合物。该聚合物至少部分具有以下结构元素：
Figure PCTCN2020111784-appb-000001
因此在结构上属于氨基塑料。将以上实施方式提供的聚脲涂料通过注塑生产整体部件或部件的一部分，或者用该聚脲涂料涂覆部件表面的全部或仅一部分，制成聚脲模制体或模制体部分。本申请实施方式的聚脲模制体优选为“纯”聚脲模制体，即，根据聚脲开发协会(PDA)关于聚脲的协议组分中不含有带有羟基的成分。本申请的聚脲涂料是无光泽的，因此所制成的聚脲模制体或模制体部分具有不光滑的表面。可以使用标准方法(例如DIN EN ISO 2813，德国哑光判定标准)确定表面的光泽度。如涂层在60°的角度下 具有大于或等于5且小于或等于80的值，则可视为无光泽。如果涂层溶剂的含量小于或等于5质量％，则该涂层是判定为无溶剂的。在溶剂是水的情况下可以例如通过Karl Fischer确定溶剂的含量，或者在溶剂是有机溶剂的情况下，可以通过本领域技术人员熟知的HPLC方法确定溶剂的含量。
本申请涉及的涂料是通过至少使聚异氰酸酯预聚体和聚醚胺以及扩链剂反应而获得。这意味着涂料主要由聚脲组成，除扩链剂外聚脲还由两种主要成分组成，即硬化剂和树脂成分。使它们进行反应形成包括一种或多种本申请组分之间的共价键。树脂在美国组分被称为组分B，在欧洲被称为组分A。模制体可优选包括70重量％的聚脲，或大于80重量％的聚脲，或大于85重量％。此外，模制体可以具有其他常规添加剂，例如染料、催化剂、流变助剂和增粘剂/助黏剂(氨基官能的三烷氧基硅烷)、填料(硅酸盐)、扩链剂和干燥剂(例如分子筛)。
涂料建立在至少双官能的聚异氰酸酯预聚体充分反应形成的共价键连接的三维网络的基础上。双官能异氰酸酯由通式生成，
Figure PCTCN2020111784-appb-000002
其中R表示芳族、脂肪族或混合烃结构。可能的双官能聚异氰酸酯预聚体是例如甲苯-2,4-二异氰酸酯(TDI)、二苯甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯(HDI，HMDI)、聚合的二苯甲烷二异氰酸酯(PMDI)、四甲基间苯二亚甲基二异氰酸酯(TMXDI)、异佛尔酮二异氰酸酯(IPDI)、4,4’-二环己基甲烷二异氰酸酯(H12MDI)，也可以是以上异氰酸酯的混合物。在实施例方法步骤a)中制备的混合物的定量比和异氰酸酯的量可以方便地基于来自方法步骤a)的预混合物的官能度和异氰酸酯官能度来确定。官能团可以通过纯粹数学确定。相应地，每摩尔胺使用一摩尔的异氰酸酯官能度。但是，混合比也不能是化学计量的。可以将混合比设置为1-4(以胺摩尔数/异氰酸酯摩尔数计算)。
聚醚胺是其中伯胺基团存在于聚醚主链末端的聚合物。聚醚主链通常由环氧丙烷，环氧乙烷或混合的环氧乙烷/环氧丙烷结构单元形成。所使用的 聚醚胺可以以单分散形式存在，具有固定的分子量或具有或多或少的宽分子量分布。潜在存在的侧链也可被其他伯胺基团占据，因此存在具有两个以上胺官能度的多官能聚醚胺。双官能聚醚胺可以使用例如以下结构式表示：
Figure PCTCN2020111784-appb-000003
使用的聚醚胺的分子量在200至5000g/mol之间。聚醚胺的官能度可以优选为2至4，特别优选为2至3。此时也可以向混合物中添加其他仲聚醚胺。这可以延长示例处理步骤b)中的反应速率。
事实证明，本申请实施方式所采用的主扩链剂特别适用于获得在机械和光学上表现优异的涂料。主扩链剂选自二乙基甲苯二胺、4,4-亚甲基双(N-仲丁基-环己胺)、4,4-二氨基二苯甲烷、4,4-二氨基二环己基甲烷、3-[[3-[[(2-氰基乙基)氨基]甲基]-3,5,5-三甲基环己基]氨基]丙腈、N，N'-异丙基(3-氨基甲基-3,5,5-三甲基环己胺)和1，3-环己二甲胺中的一种或两种以上的组合物。这些扩链剂可有助于获得具有特别合适的光学性能的涂料。
为了获得无光泽涂料，该涂料包含平均纤维长度大于或等于50μm并且小于或等于150μm，且重量分数大于或等于4.5％且小于或等于25％的磨细的碳纤维作为消光剂。已经证明该比例的碳纤维特别适合于获得特别柔性和稳定的涂层。可以生产出非常哑光的涂层而不会过度损害聚脲的机械性能。碳纤维的平均纤维长度可以例如通过涂层的部分的显微图像确定。重量分数也可以使用纤维和聚脲的密度通过显微镜确定。
在涂料的优选实施方案中，涂料具有根据DIN EN ISO 2813在60°下测得的光泽度值，该光泽度值大于或等于10且小于或等于70。本实施方式的涂料可以具有特别无光泽的光学性质，同时保留所需的机械性质。
在涂料的另一个实施方案中，涂料根据DIN EN ISO 2813在85°下测得的光泽度值大于或等于10且小于或等于70。本实施方式的涂料为采用普通 喷涂方式(非喷雾工艺)获得，可以特别地具有保持所需的机械性能的同时，获得无光泽的光学性能。
在涂料的另一个实施方案中，涂料根据DIN EN ISO 2813在85°下测得的光泽度值小于或等于10。本实施方式的涂料为采用喷雾工艺获得，可以特别地具有保持所需的机械性能的同时，获得更优的无光泽的光学性能。
作为优选的实施方式，磨细的碳纤维的重量分数可以大于或等于7.5％且小于或等于15％。已证明该比例的碳纤维特别适合于保持所需的机械性能的同时获得特别的无光泽涂层。进一步的优选范围可以在大于或等于8.5％且小于或等于12.5％之间，并且进一步大于或等于9.0％且小于或等于11％。
在另一个优选实施方式中，涂料还可以包含重量分数大于或等于2.5％且小于或等于10％的位阻胺树脂。位阻胺树脂也称为HALS(受阻胺光稳定剂)，例如可属于液体或固体哌啶衍生物。这些物质有助于形成特别耐久的涂层，光学性能在使用寿命期间几乎不会改变。
位阻胺树脂可以具有以下示例结构，其中R可以相互独立地设定以调节在所用的聚脲体系中的溶解度。
Figure PCTCN2020111784-appb-000004
作为可选的实施方式，所述涂料还包含脱气剂、分散剂、紫外线稳定剂、颜料、填料中的至少一种或两种以上的组合。这组另外的添加剂可优选用于微调涂层的光学和机械性能。
在涂料的另一个优选的实施方案中，磨细的碳纤维的平均纤维直径可以大于或等于2.5μm并且小于或等于10μm。已经证明这些碳纤维特别适合于获得特别无光泽的聚脲涂料。只需少量，就可以获得机械性能超过无添加版本的无光泽涂料。磨细的纤维的平均直径可以例如通过显微镜在层截面上确 定。
在涂料的另一个优选实施方案中，涂料可以具有含量小于或等于1％的溶剂。本申请涉及的涂料可以具有非常低的溶剂比例。因此这些涂料在实际上可被认为不含溶剂。
在涂料优选层面的情况下，以重量分数计，所述涂料中聚异氰酸酯的含量大于或等于30％且小于或等于50％，聚醚胺的含量大于或等于20％且小于或等于80％；扩链剂的含量大于或等于5％且小于或等于40％；磨细的碳纤维形式的消光剂的含量大于或等于5％且小于或等于10％，其中各个成分也可以是以其反应产物的形式存在，即，可根据需要分阶段进行反应。各个组成部分的总和总计为100％。如果除以上外的助剂，则上述成分的总和和另外的添加剂的总和合计可以达到100重量％。涂料的这种组成已被证明是非常灵活的并且能产生足够的无光泽效果。另外，上述组合物保证了足够的应用期，因此即使是手工施涂也可以保证可再现的机械性能。
在涂料的一个优选实施方案中，该反应可以通过喷雾法实施，例如雾面喷涂。已经发现使用雾面喷涂法制造本申请涉及的涂料是特别有利的。该方法使各个组分之间特别成功的有效地反应，从而可以在最外层获得特别无光泽的层。不受理论的束缚，这种特定的表面粗糙度可以归因于由根据本申请的组分以及特定的应用技术的组合。
本申请实施方式的另一方面还涉及用于生产无溶剂哑光聚脲涂料的零件套装，至少具有一个用于多官能聚异氰酸酯预聚体的容器，一个用于聚醚胺的容器以及混合和挤出装置，并且以上至少一个容器内具有大于或等于2.5重量％且小于或等于20重量％的磨细的碳纤维，纤维长度大于或等于50μm且小于或等于150微米。
在以上实施方式提供的零件套装中，两个容器内混合物的粘度不同或相近，将碳纤维盛放入具有粘度较小的混合物的容器中，或如粘度相近，可将两个容器内都放入碳纤维。
该套装能够在手动或机器设备应用中提供高度可再现且可靠的哑光聚脲涂料。另外本申请涉及的针对涂料的保护也同样针对于实施该应用的零件套装。
实施例1
1.处理步骤a)
在室温下通过机械搅拌产生69重量％的聚醚胺(Huntsman Jeffamine D2000)和21重量％的二乙基甲苯二胺(Lonzacure DETDA 80)和10重量％的碳纤维颗粒的混合物。纤维颗粒的平均纤维长度为75至85μm，密度为1.7至1.9g/cm 3，直径为6至8μm。纤维的机械性能优选为2.5至4GPa的拉伸强度，150至250GPa的E模量和1-2％的断裂伸长率。选择这些区域内的纤维可以获得良好的机械和光学性能。混合直至获得均匀的预混物。
2.处理步骤b)
将来自处理步骤a)的反应预混物置于容器中。另一个容器中装有聚异氰酸酯预聚体(Huntsman Suprasec 2054)。将反应预混物和聚异氰酸酯预聚体用喷雾器，例如Graco反应器，喷涂到工件上以获得表面涂层。通过快速移动喷枪来产生雾气，从而导致在基材上形成粗糙的表面。来自处理步骤a)的预混物与本步骤的聚异氰酸酯预聚体的混合比为1：1。
实施例2
1.处理步骤a)
在室温下通过机械搅拌产生51.5重量％的聚醚胺(24.5重量％的Huntsman Jeffamine D2000+19重量％的Huntsman JeffamineD400+7.5重量％的Huntsman JeffamineT5000+0.5重量％助粘剂)和39.5重量％的扩链剂(7.9重量％Lonzacure DETDA 80+31.6重量％Jefflink754)和9重量％的碳纤维颗粒的混合物。纤维颗粒的平均纤维长度为50μm，密度为1.7至1.9g/cm 3，直径为6至8μm。纤维的机械性能优选为2.5至4GPa的拉 伸强度，150至250GPa的E模量和1-2％的断裂伸长率。选择这些区域内的纤维可以获得良好的机械和光学性能。混合直至获得均匀的预混物。
2.处理步骤b)
将来自处理步骤a)的反应预混物置于容器中。另一个容器中装有聚异氰酸酯预聚体(Huntsman Suprasec 2067)。将反应预混物和聚异氰酸酯预聚体用喷雾器，例如Graco反应器，喷涂到工件上以获得表面涂层。通过快速移动喷枪来产生雾气，从而导致在基材上形成粗糙的表面。来自处理步骤a)的预混物与本步骤的聚异氰酸酯预聚体的混合比为1：1。
实施例3
1.处理步骤a)
在室温下通过机械搅拌产生51.5重量％的聚醚胺(24.5重量％的Huntsman Jeffamine D2000+19重量％的Huntsman JeffamineD400+7.5重量％的Huntsman Jeffamine T5000+0.5重量％助粘剂)和39.5重量％的扩链剂(7.9重量％Lonzacure DETDA 80+31.6重量％Jefflink754)和9重量％的碳纤维颗粒的混合物。纤维颗粒的平均纤维长度为150μm，密度为1.7至1.9g/cm 3，直径为6至8μm。纤维的机械性能优选为2.5至4GPa的拉伸强度，150至250GPa的E模量和1-2％的断裂伸长率。选择这些区域内的纤维可以获得良好的机械和光学性能。混合直至获得均匀的预混物。
2.处理步骤b)
将来自处理步骤a)的反应预混物置于容器中。另一个容器中装有聚异氰酸酯预聚体(Huntsman Suprasec 2067)。将反应预混物和聚异氰酸酯预聚体用喷雾器，例如Graco反应器，喷涂到工件上以获得表面涂层。通过快速移动喷枪来产生雾气，从而导致在基材上形成粗糙的表面。来自处理步骤a)的预混物与聚异氰酸酯预聚体混合比为1：1。
对比例1
与实施例1相比，除不添加碳纤维外，其余相同。
对比例2
与实施例2和实施例3相比，除不添加碳纤维外，其余相同。
性能测试
1、根据DIN EN ISO 2813测量各实施例采用雾化喷涂形成的漆膜表面在85°时的消光度，以及，不采用雾化方式的情况下喷涂产生的漆膜表面在60°时的光泽度。
2、根据DIN EN ISO 2813测量各对比例不采用雾化方式喷涂形成的漆膜表面在85°时和60°时的光泽度。
3、测量各实施例和对比例中喷涂形成的涂层的拉伸强度和断裂伸长率。
性能测试结果如表1所示。
表1性能对比表
Figure PCTCN2020111784-appb-000005
从表1可以看出，与不添加碳纤维的对比例相比，本申请实施例所提供的涂料喷涂形成的涂层，其光泽度值很低，具有非常无光泽的表面，而且同时可以保持与现有涂层相近的机械性能(参见实施例2)，甚至具有比现有涂层更优的机械性能(参见实施例1、实施例3)。

Claims (15)

  1. 无溶剂哑光聚脲涂料，通过使至少以下组分反应而获得：
    a)聚异氰酸酯预聚体；
    b)聚醚胺；
    c)主扩链剂；其特征在于：
    所述涂料还包括作为消光剂的磨细的碳纤维，所述碳纤维的平均纤维长度大于或等于50μm且小于或等于150μm，重量分数大于或等于4.5％且小于或等于25％，并且所述主扩链剂选自二乙基甲苯二胺、4,4-亚甲基双(N-仲丁基-环己胺)、4,4-二氨基二苯甲烷、4,4-二氨基二环己基甲烷、3-[[3-[[(2-氰基乙基)氨基]甲基]-3,5,5-三甲基环己基]氨基]丙腈和1，3-环己二甲胺中的一种或两种以上的组合物。
  2. 根据权利要求1所述的涂料，其特征在于，所述聚异氰酸酯预聚体为至少具有两个以上异氰酸酯官能度的多官能聚异氰酸酯预聚体。
  3. 根据权利要求2所述的涂料，其特征在于，所述聚异氰酸酯预聚体选自甲苯-2,4-二异氰酸酯(TDI)、二苯甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯(HDI，HMDI)、聚合的二苯甲烷二异氰酸酯(PMDI)、四甲基间苯二亚甲基二异氰酸酯(TMXDI)、异佛尔酮二异氰酸酯(IPDI)、4,4’-二环己基甲烷二异氰酸酯(H12MDI)中的一种或两种以上的组合物。
  4. 根据权利要求1所述的涂料，其特征在于，所述聚醚胺为至少具有两个以上胺官能度的多官能聚醚胺，且分子量在200-5000g/mol。
  5. 根据权利要求1-4任一项所述的涂料，其特征在于，所述涂料中胺摩尔数与异氰酸酯摩尔数的比例为1-4。
  6. 根据权利要求1所述的涂料，其特征在于，所述涂料具有根据DIN EN ISO 2813在60°下测得的大于或等于10且小于或等于70的光泽度值。
  7. 根据权利要求1或6所述的涂料，其特征在于，所述涂料具有根据DIN  EN ISO 2813在85°下测得的大于或等于10且小于或等于70的光度值。
  8. 根据权利要求1所述的涂料，其特征在于，所述磨细的碳纤维的重量分数大于或等于7.5％且小于或等于15％。
  9. 根据权利要求1所述的涂料，其特征在于，所述涂料还包括重量分数大于或等于2.5％且小于或等于10％的位阻胺树脂。
  10. 根据权利要求1或9所述的涂料，其特征在于，所述涂料还包括脱气剂、分散剂、UV稳定剂、颜料、填料中的一种或两种以上的组合物。
  11. 根据权利要求1所述的涂料，其特征在于，所述磨细的碳纤维具有大于或等于2.5μm且小于或等于10μm的平均纤维直径。
  12. 根据权利要求1所述的涂料，其特征在于，所述涂料的溶剂含量小于或等于1％。
  13. 根据权利要求1所述的涂料，其特征在于，以重量分数计，所述涂料中聚异氰酸酯的含量大于或等于30％且小于或等于50％，聚醚胺的含量大于或等于20％且小于或等于80％，扩链剂的含量大于或等于5％且小于或等于40％，磨细的碳纤维形式的消光剂的含量大于或等于5％且小于或等于10％的，其中各个成分也可以彼此以反应产物的形式存在。
  14. 根据权利要求1所述的涂料，其特征在于，所述反应通过喷雾工艺进行。
  15. 用于生产无溶剂哑光聚脲涂料的零件套装，其特征在于，至少具有一个用于多官能聚异氰酸酯预聚体的容器，一个用于聚醚胺的容器以及混合和挤出装置，并且以上至少一个容器内具有大于或等于2.5重量％且小于或等于20重量％的磨细的碳纤维，纤维长度大于或等于50μm且小于或等于150μm。
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