CN114773955A - Water-based epoxy resin coating and preparation method thereof - Google Patents
Water-based epoxy resin coating and preparation method thereof Download PDFInfo
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- CN114773955A CN114773955A CN202210535276.4A CN202210535276A CN114773955A CN 114773955 A CN114773955 A CN 114773955A CN 202210535276 A CN202210535276 A CN 202210535276A CN 114773955 A CN114773955 A CN 114773955A
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention relates to a water-based epoxy resin coating, which comprises the following components: A) a main agent comprising an aqueous epoxy resin emulsion, the main agent further comprising wood fibers modified with a silane coupling agent; B) a curing agent, wherein the amount of component B) is from 5.0 to 25.0 wt. -%, preferably from 7.5 to 20.0 wt. -%, more preferably from 10.0 to 15.0 wt. -%, based on the weight of component a); also relates to a method for preparing the waterborne epoxy resin coating containing the silane coupling agent modification. The water-based epoxy resin coating can avoid the discharge of organic solvent, and has improved adhesive force to the carbon fiber composite material.
Description
Technical Field
The invention relates to a coating, in particular to a two-component epoxy coating, and especially relates to an epoxy resin coating containing silane modified wood fibers and a preparation method thereof.
Background
Carbon fiber is a special fiber composed of carbon elements, is compounded with resin, metal, ceramic, carbon and the like as a reinforcing material, is used for manufacturing advanced composite materials, and is widely applied to automobile parts. In order to further enhance the performance of these carbon fiber composite materials, the carbon fiber composite materials need to be further coated.
In the prior art, coatings for carbon fiber composite materials are all solvent-based coatings, and although the coatings have good adhesion on the carbon fiber composite materials, the coatings generally contain organic solvents, and the organic solvents can generate harmful gases in the coating process and pollute the environment after being discharged.
CN111117403A describes a colored filling primer for carbon fiber composite material, which contains 5-10 parts of xylene and 5-10 parts of butyl acetate, and these Volatile Organic Compounds (VOCs) can volatilize into the atmosphere during the coating process, causing environmental pollution.
CN107129731A describes a single-coating UV paint with colored nano-particles for carbon fiber and plastic surface, wherein the single-coating UV paint needs to be cured by irradiation with a special ultraviolet emitting device during the drying process, which limits the application.
Disclosure of Invention
In order to solve the problem that the carbon fiber coating pollutes the environment in the prior art, the invention provides the water-based epoxy resin coating, and in addition, in order to ensure that the coating has improved adhesive force to the carbon fiber composite material, the invention particularly provides the epoxy resin coating containing the wood fiber modified by the silane coupling agent.
The object of the present invention is achieved by providing an epoxy resin coating containing wood fibers modified with a silane coupling agent, the coating comprising the following components:
A) a main agent comprising an aqueous epoxy resin emulsion, the main agent further comprising wood fibers modified with a silane coupling agent;
B) a curing agent for the curing of a silicone rubber composition,
wherein the amount of component B) is from 5.0 to 25.0 wt. -%, preferably from 7.5 to 20.0 wt. -%, more preferably from 10.0 to 15.0 wt. -%, based on the weight of component a).
Optionally, wherein the component A) further comprises water, pigments and fillers and other additives besides pigments and fillers.
In another aspect, the present invention also provides a method for preparing the epoxy resin coating, comprising the steps of:
i) preparing a main agent, comprising:
a) reacting a silane coupling agent with the wood fibers; obtaining wood fiber modified by silane coupling agent;
b) mixing the wood fiber modified by the silane coupling agent with the waterborne epoxy emulsion to obtain a main agent;
ii) providing a curing agent;
wherein the amount of the curing agent is 5.0 to 25.0 wt%, preferably 7.5 to 20.0 wt%, more preferably 10.0 to 15.0 wt%, based on the weight of the main agent.
The water-based epoxy coating can avoid the problem of organic solvent emission, and meanwhile, the coating has improved adhesion to carbon fiber composite materials.
Detailed Description
In the present invention, unless otherwise stated, all operations are carried out at room temperature and normal pressure.
In one aspect, the present invention provides an epoxy resin coating containing wood fiber modified with a silane coupling agent, comprising the following components:
A) a main agent comprising an aqueous epoxy resin emulsion, the main agent further comprising wood fibers modified with a silane coupling agent;
B) a curing agent for the curing of a silicone rubber composition,
wherein the amount of component B) is from 5.0 to 25.0 wt. -%, preferably from 7.5 to 20.0 wt. -%, more preferably from 10.0 to 15.0 wt. -%, based on the weight of component a).
In the present invention, the aqueous epoxy resin is any water-dispersible epoxy resin that is dispersible in water or emulsifiable in water. The aqueous epoxy resin may be a self-emulsifying epoxy resin, or an emulsion or dispersion of one or more epoxy compounds with a surfactant (e.g., a nonionic or ionic surfactant) for emulsifying the epoxy compounds. The self-emulsifying epoxy resin may be mixed with water to form an aqueous dispersion. The self-emulsifying epoxy resin may be an adduct of an epoxy compound with a hydrophilic monomer or polymer containing at least one group selected from a carboxyl group, a hydroxyl group, a sulfonic acid group, an oxirane group, or an amino group, and in the present invention, examples of the aqueous epoxy resin are glycidyl ether type epoxy resins including, but not limited to, diglycidyl ethers of bisphenol a, diglycidyl ethers of bisphenol F, 1, 4-butanediol diglycidyl ether, diglycidyl ethers of 1, 6-hexanediol and glycidyl ether terephthalic acid, diglycidyl ethers of 1, 4-cyclohexanemethanol diglycidyl ether, diglycidyl ethers of 1, 3-cyclohexanemethanol diglycidyl ether, diglycidyl ethers of hexahydroterephthalic acid; and novolac resins and mixtures of two or three thereof. Examples of commercially available waterborne epoxy resins are OUDRASPERSE WB-6001, OUDRASPERSE WB 3001, OUDRASPERSE WB4001, available from Olin Corporation.
In one embodiment of the invention, the number average molecular weight of the epoxy resin is in the range 420-1,700 (e.g. 454 to 1,666), preferably 850 to 1,000, as determined according to GB/T21863-2008 (the molecular weight of the other polymeric species is also determined using this standard); an epoxy equivalent weight of 227 to 833, preferably 475 to 500, determined according to the method GB/T4612-2008; the solids content of the aqueous epoxy resin emulsion was 47%.
In the present invention, the silane coupling agent has a structure of the following general formula (I)
YSiX3 (I)
Wherein the content of the first and second substances,
y is a non-hydrolyzable group including C2-6Alkenyl, substituted or unsubstituted C1-6Alkyl or C1-6An alkoxy group; and
x is a hydrolyzable group including halogen, C1-6Alkoxy and acetoxy.
Preferably, Y is a terminal halogen, amino, mercapto, C containing at least one heteroatom selected from N, O or S3-6Heterocyclyl, (meth) acryloyloxy, isocyanato-substituted C1-6Alkyl or C1-6An alkoxy group.
More preferably, Y is C substituted with an isocyanate group1-6Alkyl, especially more preferably Y is C substituted with an isocyanate group1-C3An alkyl group.
More preferably, X is methoxy or ethoxy.
In a preferred embodiment of the present invention, the silane coupling agent is selected from the group consisting of 3-aminopropyltriethoxysilane (KH550), 3- (2, 3-glycidoxy) propyltrimethoxysilane (KH560), gamma- (methacryloyloxy) propyltrimethoxysilane (KH570) and vinyltrimethoxysilane (KH171), isocyanatoethylenetriethoxysilane, preferably isocyanatoethylenetriethoxysilane. An example of a commercially available silane coupling agent is A-Link 25 supplied by Meiji corporation, USA.
In a preferred embodiment of the present invention, the wood fibers may BE selected from palm fibers, paper fibers, straw fibers, having a molecular structure of a homogeneous polymer formed by linear linkage of D-glucose residues through beta-1, 4 glycosidic bonds, and the commercially available wood fibers of the present invention are water-insoluble wood fibers ARBOCEL-BE600/30PU (40 μm in length) from JRS, Germany.
In the present invention, the silane coupling agent modified wood fiber has the following molecular structure: a part of hydroxyl on the surface of the wood fiber is reacted with a silane coupling agent to introduce silane on the wood fiber to form a wood fiber linear polymer.
In a preferred embodiment of the present invention, in the a) component of the epoxy resin coating of the present invention, the weight ratio of the silane coupling agent to the wood fiber is 0.01 to 0.2:1, preferably 0.05 to 0.15:1, more preferably 0.08 to 0.12: 1.
In one embodiment of the present invention, in the epoxy resin coating of the present invention, wherein in the a) component, the weight ratio of the silane coupling agent modified wood fiber to the epoxy resin emulsion is 0.005 to 0.15:1, preferably 0.009 to 0.09:1, more preferably 0.036 to 0.086:1, and most preferably 0.036 to 0.058: 1.
In one embodiment of the present invention, wherein in the epoxy resin coating of the present invention, wherein in the a) component, the silane coupling agent modified wood fiber accounts for 0.1 to 4.0 wt%, preferably 0.2 to 3.5 wt%, more preferably 0.5 to 3.0 wt%, further preferably 1.8 to 2.2 wt% of the a) component.
In one embodiment of the present invention, wherein in the epoxy resin coating of the present invention, wherein in the a) and B) components, the silane coupling agent modified wood fiber accounts for 0.35 to 3.5% by weight, preferably 0.40 to 3.0% by weight of the sum of the a) and B) components.
In a preferred embodiment of the present invention, component a), i.e. the main agent of the epoxy resin coating, comprises the following components, based on the total weight of the main agent:
the sum of the components is 100 wt%.
Wherein the pigment filler comprises pigment and inorganic filler, the pigment is selected from iron oxide red, titanium dioxide and iron oxide yellow, and the pigment is used in an amount of 5.0 to 15.0 weight percent based on the total weight of the main agent; the inorganic filler is selected from the group consisting of precipitated barium sulfate, talc, kaolin, titanium white, calcium carbonate, zinc phosphate, mica, and mixtures thereof, and is used in an amount of 5.0 to 30.0 wt% based on the total weight of the main agent.
Wherein the other additives except the pigment and the filler are selected from defoaming agents, wetting agents, dispersing agents and rheological additives.
As used herein, "defoamer" refers to a chemical additive that reduces and retards foam formation. The defoamer may be a silicone based defoamer, a mineral oil based defoamer, an ethylene oxide/propylene oxide based defoamer, a polyalkyl acrylate or a mixture thereof. Suitable commercially available defoamers include, for example, Tego Airex 902W and Tego Foamex 1488 polyether siloxane copolymer emulsions, all available from Tego; BYK-024 Silicone antifoam is available from BYK, or mixtures thereof. The defoamer is used in an amount of 0.2 to 0.5 wt.%, based on the total weight of the base.
As used herein, "wetting agent" refers to a chemical additive that reduces the surface tension of a coating composition, making the coating composition more easily spread or penetrate over the surface of a substrate. Suitable wetting agent surfactants include one or more mixtures of low molecular weight siloxane type surfactants (e.g., terminal polyether modified low molecular weight polysiloxanes), fluorocarbon type surfactants, acetylenic diols, in amounts of 0.2 to 0.3 weight percent wetting agent based on the total weight of the base.
Suitable dispersants include one or more of anionic (e.g., sodium oleate, carboxylates, sulfonates, etc.), cationic (e.g., octadecenylamine acetate, alkyl quaternary ammonium salts, aminopropylamine dioleate, quaternary ammonium salts, polyaminoamide phosphates), nonionic (e.g., fatty acid ethylene oxide adducts, polyethylene glycol polyols, polyvinylamine derivatives), electroneutral (e.g., oleyl oleate), polymeric (e.g., multiintracomplex polyol-polyethyleneimine block copolymers, reactants of polycaprolactone with triethylenetetramine, acrylate polymers, polyacrylates), and are used in amounts of 1.0 to 1.5 wt.%, based on the total weight of the base compound.
Suitable rheological aids include bentonite, attapulgite, aluminum silicate; celluloses such as methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose; polyacrylates such as polyacrylates, homopolymers of acrylic and methacrylic acids, and the like; polyurethane rheology auxiliaries, suitable commercially available rheology auxiliaries are for example rheovisis PU 1190 from BASF, germany. The rheology auxiliaries are used in amounts of 0.3 to 0.5% by weight, based on the total weight of the base.
The coating of the present invention also includes component B) a curing agent to cure the coating composition. Curing agents known to be suitable for curing epoxy resins may be employed including amine-based curing agents, anhydride-based curing agents, synthetic resin-based curing agents (e.g., phenolic resins, polyamide resins, amino resins formed by the reaction of urea and melamine with aldehydes). Among them, amine-based curing agents are preferred, such as:
aliphatic amines, such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 2, 4-trimethylhexamethylenediamine, 2,4, 4-trimethylhexamethylenediamine, 1, 6-hexamethylenediamine, 1-ethyl-1, 3-propanediamine, bis (3-aminopropyl) piperazine, N-aminoethylpiperazine, N-bis (3-aminopropyl) ethylenediamine;
cycloaliphatic amines, such as 1, 2-diaminocyclohexane, 1, 4-diamino-3, 6-diethylcyclohexane, 1, 2-diamino-4-ethylcyclohexane, 1, 4-diamino-3, 6-diethylcyclohexane, 1-cyclohexyl-3, 4-diaminocyclohexane, isophorone-diamine, norbornanediamine, 4 '-diaminodicyclohexylmethane, 4' -diaminodicyclohexylpropane, 2-bis (4-aminocyclohexyl) propane, 3 '-dimethyl-4, 4' -diaminodicyclohexylmethane, 3-amino-1-cyclohexane-aminopropane, 1, 3-and 1, 4-bis (aminomethyl) cyclohexane;
aromatic amines such as 2, 4-toluenediamine, 2, 6-toluenediamine, m-xylylenediamine, p-xylylenediamine;
polyetheramines such as polyoxypropylene diamine;
polyamidoamines.
Commercially available curing agents may be used, including EPI-CURE8535, 8536, 8537, 8290 and 8292 curing agents available from Hexion; anquamine 401 and Epilink381 curatives from air products; beckobox EH659W, EH623W, and VEH2133W curatives available from Allnex; EPOTUF 37-680 and 37-681 curing agents available from Reichhold, OUDRACURE WB 8001 curing agent available from Olin Corporation.
Component B) is used in amounts of from 5.0 to 25.0% by weight, preferably from 7.5 to 20.0% by weight, more preferably from 10.0 to 15.0% by weight, based on the weight of component a).
The epoxy resin coating is divided into A) a main agent and B) a curing agent, and the main agent and the curing agent are respectively contained in different containers before actual use; in use, the two components are mixed and applied to the desired location or material.
In still another aspect of the present invention, there is provided a method for preparing the above epoxy resin paint, comprising the steps of:
i) preparing a main agent, which comprises:
a) reacting a silane coupling agent with wood fibers; obtaining the wood fiber modified by the silane coupling agent;
b) mixing the wood fiber modified by the silane coupling agent with the waterborne epoxy resin emulsion to obtain a main agent;
ii) providing a curing agent;
wherein the amount of component B) is from 5.0 to 25.0 wt. -%, preferably from 7.5 to 20.0 wt. -%, more preferably from 10.0 to 15.0 wt. -%, based on the weight of component a).
In the method of the present invention for producing the above epoxy resin coating, the aforementioned description about each component of the coating is equally applicable, and the description is not necessarily repeated here.
In step a), the solvent used for dissolving the silane coupling agent is preferably an ester solvent or a ketone solvent, including ethyl acetate, butyl acetate, acetone, butanone, and preferably ethyl acetate. The silane coupling agent is dissolved in ethyl acetate, and then the wood fiber is soaked in the solution of the silane coupling agent, so that the wood fiber modified by the silane coupling agent can be obtained. Preferably, the solvent is removed, for example by evaporation (in particular vacuum evaporation).
The aqueous epoxy resin emulsion is preferably formed by dissolving the epoxy resin in water, and optionally using an emulsifier.
The silane coupling agent modified wood fiber is mixed with the aqueous epoxy resin emulsion to obtain a main agent, wherein an organic solvent is preferably not included.
In the step of providing the curing agent, it may be synthesized using a known method, or a commercially available curing agent, preferably an amine-based curing agent, as described above, may be used.
According to the method, the epoxy resin coating obtained in the step i) and the curing agent obtained in the step ii) are respectively contained in different containers before actual use; in use, the two components are mixed and applied to the desired location or material.
The invention also provides the use of the epoxy resin coating and the epoxy resin coating prepared according to the method for carbon fiber composite materials, in particular for preparing automobile coatings and anticorrosive coatings.
It is noted that within this specification, the various features, parameters, conditions and combinations thereof described for the waterborne epoxy resin coating product apply to the method of preparation and use thereof.
The invention is further described by the following examples, but is not limited thereto.
Examples
The raw materials used are as follows:
the test method used was:
number average molecular weight: determined according to GB/T21863-
Fineness: determined according to GB 1724-1979
Adhesion force: determination according to GB/T5210-
Example 1
Step 1: preparation of silane coupling agent modified Wood fiber
1.0g of the silane coupling agent A-Link 25 was dissolved in 9.0g of an ethyl acetate solvent, and mixed at a weight ratio of 1:9 to prepare a 10% ethyl acetate solution (10.0g) of the silane coupling agent A-Link 25.
10.0g of wood fiber ARBOCEL-BE600/30PU is soaked in the prepared silane coupling agent solution (10.0g) according to the mass ratio of 1:1, the mixture is kept stand in a closed environment at 25 ℃ for more than 24 hours, so that isocyanate groups and hydroxyl groups are fully reacted, and ethyl acetate is distilled and desolventized at 80 ℃ (the condensed and recovered ethyl acetate solvent can BE collected and recycled), so that 11.0g of wood fiber chemically modified by the silane coupling agent can BE obtained.
Step 2: preparing the main agent
a) 17.5g of water were added to the flask and stirring was started at 500r/min, followed by 0.3g of defoamer (FoamStar SI 2293 from BASF, germany), 0.2g of wetting agent (Hydropalat WE 3322 from BASF, germany), 1.1g of dispersant (Dispex Ultra PA 4550 from BYK, germany), 0.5g of silane-modified wood fibre (homemade, as described above), 10.0g of iron oxide red (BAYFERROX 4100 from lang, germany), 25.0g of precipitated barium sulphate (available from south africa, shanxi) and stirring for 5 min;
b) increasing the rotation speed to 800r/min, adding 45.0g of water-based epoxy resin (OUDRASPErse WB 6001 available from Olin in USA), dispersing at 2000r/min for 20min, and grinding to fineness of less than or equal to 30 μm;
c) the rotation speed was adjusted to 800r/min, 0.4g of a rheology auxiliary (Rheovis PU 1190 from BASF, Germany) was added, stirred for 20min and filtered. And standing for 24h for paint preparation.
And step 3: providing a curing agent
The rotation speed was adjusted to 800r/min, and 2.5g of water and 10.0g of amine-based curing agent resin (OUDRACURE WB 8001 available from Olin, USA) were added to the flask and dispersed for 3 min.
And 4, step 4: mixing the main agent and the curing agent
Preparing the main agent and the curing agent into paint according to the mass ratio of 8:1, mechanically stirring for 2min, adding deionized water to dilute until the solid content is 10-15 wt%, and performing coating preparation by adopting air spraying.
Examples 2 to 6
The preparation method was similar to example 1 except that in examples 2 to 6, wood fibers modified with silane coupling agent in different amounts from example 1 were used, the amount of the silane coupling agent modified wood fibers used in examples 2 to 6 is shown in table 1, and further the total amount of the reagents was balanced with deionized water so that the total amount of the main agent was 100 g.
Comparative example 1
The preparation method was similar to example 1 except that in comparative example 1, the silane coupling agent-modified wood fiber was not added, and the total amount of the main agent was equilibrated with deionized water so that the total amount of the main agent was 100 g.
Testing
The aqueous epoxy coating is prepared by adopting the scheme, is sprayed on a carbon fiber composite substrate for construction, and is maintained for 7 days, and the adhesive force of the coating on the carbon fiber composite is tested by adopting a pull-off method of the American DeFelsko company with the model number of Posi Test AT-A according to the stipulation of the Standard Test method for measuring the pull-off strength of the coating by using a portable adhesion tester according to ASTM D4541-17, wherein the specific Test method comprises the following steps: bonding a cylindrical aluminum ingot with the size of 20mm to the surface of the coating by using a portable adhesion tester and epoxy resin type AB structural adhesive of the Lei-Li-group Limited company; after the structural adhesive is cured, applying tensile stress to the aluminum ingot along the direction vertical to the plane of the substrate by using an adhesion tester until the coating is damaged; the results of the experiment are expressed in terms of the tensile force that breaks the interface between the coating and the substrate or the coating itself. The adhesion test results of the water-based epoxy coating with different addition amounts of silane coupling agent chemically modified wood fiber XFMMS on the carbon fiber composite material are shown in Table 1.
Table 1 amount of silane coupling agent chemically modified wood fiber XFMS and adhesion test results
When the use amount of the silane coupling agent chemically modified wood fiber XFMMS reaches 2.0 percent (based on the total weight of the main agent), the best effect on the adhesion improvement is achieved, the adhesion reaches 5.22MPa, and compared with the comparative example 1, the adhesion is increased by 67.3 percent. And then, along with the increase of the dosage of the silane coupling agent chemically modified wood fiber XFMMS, the adhesion force improvement effect is not obvious and tends to be stable gradually.
When the dosage of the silane coupling agent chemically modified wood fiber is 2.0%, the epoxy coating and the surface of the carbon fiber composite material substrate tend to be distributed and saturated, and the optimal addition amount for improving the adhesive force is achieved.
Claims (10)
1. A two-component water-based epoxy resin coating comprises the following components:
A) a main agent comprising an aqueous epoxy resin emulsion, the main agent further comprising wood fibers modified with a silane coupling agent;
B) a curing agent for a curable composition comprising a curable resin,
wherein the amount of component B) is from 5.0 to 25.0 wt. -%, preferably from 7.5 to 20.0 wt. -%, more preferably from 10.0 to 15.0 wt. -%, based on the weight of component a).
2. The epoxy resin coating of claim 1, wherein in component a), the weight ratio of the silane coupling agent to wood fiber is 0.01-0.2:1, preferably 0.05-0.15:1, more preferably 0.08-0.12: 1.
3. The epoxy resin coating according to claim 1 or 2, wherein in the a) component, the weight ratio of the silane coupling agent-modified wood fiber to the epoxy resin is from 0.005 to 0.15:1, preferably 0.009-0.09:1, more preferably 0.036-0.086:1, most preferably 0.036-0.058: 1; the silane coupling agent-modified wood fiber accounts for 0.1 to 4.0% by weight, preferably 0.2 to 3.5% by weight, more preferably 0.5 to 3.0% by weight, further preferably 1.8 to 2.2% by weight of the component A).
4. The epoxy resin coating according to claim 1 or 2, wherein in the A) and B) components, the silane coupling agent modified wood fiber accounts for 0.35 to 3.5 wt%, preferably 0.40 to 3.0 wt%, of the sum of the A) and B) components.
5. The epoxy resin paint according to claim 1 or 2, wherein the epoxy resin emulsion is a glycidyl ether based epoxy resin, a phenolic novolac resin, preferably a glycidyl ether based epoxy resin, the epoxy resin has a number average molecular weight in the range of 450-.
6. The epoxy coating of claim 1 or 2, wherein the silane coupling agent is selected from the group consisting of 3-aminopropyltriethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane and vinyltrimethoxysilane, isocyanatoethylenetriethoxysilane, preferably isocyanatoethylenetriethoxysilane.
7. The epoxy resin coating according to claim 1 or 2, wherein the main agent comprises the following components, based on the total weight of the main agent:
the sum of the components is 100 wt.%.
8. The epoxy resin coating according to claim 1 or 2, wherein the B) curing agent is an amine curing agent selected from aliphatic amines, cycloaliphatic amines, aromatic amines, polyetheramines, polyamidoamines, preferably aliphatic amines, and the amine curing agent resin has an amine value of 100-400mg KOH/g, preferably 160-180mg KOH/g, determined according to DIN 16945/5.6.
9. A process for preparing the epoxy resin coating of any one of claims 1 to 8, comprising the steps of:
i) preparing a main agent, which comprises:
a) reacting a silane coupling agent with wood fibers to obtain modified wood fibers;
b) mixing the wood fiber modified by the silane coupling agent with the water-based epoxy emulsion to obtain a main agent;
ii) providing a curing agent;
wherein the amount of component B) is from 5.0 to 25.0 wt. -%, preferably from 7.5 to 20.0 wt. -%, more preferably from 10.0 to 15.0 wt. -%, based on the weight of component a).
10. Use of an epoxy resin coating according to any one of claims 1 to 8 and an epoxy resin coating prepared according to the process of claim 9 for carbon fiber composites.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116535940A (en) * | 2023-06-12 | 2023-08-04 | 深圳市昊日兴科技有限公司 | Wear-resistant and conductive coordinated metal substrate coating and method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112457740A (en) * | 2020-10-29 | 2021-03-09 | 内蒙古农业大学 | Coupling agent modified nano-cellulose grafted epoxy resin composite water-based paint and preparation method thereof |
| CN114316738A (en) * | 2021-12-30 | 2022-04-12 | 湖南宏泰新材料有限公司 | Epoxy transparent primer coating for water-based carbon fiber substrate fishing rod |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112457740A (en) * | 2020-10-29 | 2021-03-09 | 内蒙古农业大学 | Coupling agent modified nano-cellulose grafted epoxy resin composite water-based paint and preparation method thereof |
| CN114316738A (en) * | 2021-12-30 | 2022-04-12 | 湖南宏泰新材料有限公司 | Epoxy transparent primer coating for water-based carbon fiber substrate fishing rod |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116535940A (en) * | 2023-06-12 | 2023-08-04 | 深圳市昊日兴科技有限公司 | Wear-resistant and conductive coordinated metal substrate coating and method thereof |
| CN116535940B (en) * | 2023-06-12 | 2023-10-13 | 深圳市昊日兴科技有限公司 | Wear-resistant and conductive coordinated metal substrate coating and method thereof |
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