CN106883716B - A kind of water-based paint compositions and preparation method thereof - Google Patents

A kind of water-based paint compositions and preparation method thereof Download PDF

Info

Publication number
CN106883716B
CN106883716B CN201710208586.4A CN201710208586A CN106883716B CN 106883716 B CN106883716 B CN 106883716B CN 201710208586 A CN201710208586 A CN 201710208586A CN 106883716 B CN106883716 B CN 106883716B
Authority
CN
China
Prior art keywords
water
based paint
paint compositions
clay
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710208586.4A
Other languages
Chinese (zh)
Other versions
CN106883716A (en
Inventor
熊绍泊
唐晌
李海荣
汪少锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NIPPON PAINT (GUANGZHOU) CO Ltd
Original Assignee
NIPPON PAINT (GUANGZHOU) CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NIPPON PAINT (GUANGZHOU) CO Ltd filed Critical NIPPON PAINT (GUANGZHOU) CO Ltd
Priority to CN201710208586.4A priority Critical patent/CN106883716B/en
Publication of CN106883716A publication Critical patent/CN106883716A/en
Application granted granted Critical
Publication of CN106883716B publication Critical patent/CN106883716B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • 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
    • C09D175/04—Polyurethanes
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • 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
    • 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
    • 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
    • C08K2201/011—Nanostructured additives
    • 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
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Plant Pathology (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention discloses a kind of water-based paint compositions, which includes: at least partly dendroid that is cationized of Amino End Group or hyperbranched polyol amine；Clay；Film forming matter includes at least one emulsion polymer；Wherein, the dendroid or hyperbranched polyol amine at least partly intercalation that at least partly Amino End Group is cationized enter in clay layer.The paint film that compatibility is good between the water-based paint compositions each component, is formed has higher gel content and improved machinery, barrier property, scrub performance and corrosion resistance.The invention also discloses the preparation methods of the water-based paint compositions.

Description

A kind of water-based paint compositions and preparation method thereof
Technical field
The present invention relates to coating compositions.More particularly, to a kind of water-based paint compositions and preparation method thereof.
Background technique
Dendritic and dissaving polymer are all the highly branched high scores with nano-scale three-dimensional branched structure Son.It has been generally acknowledged that dendrimer structure is very regular, there is molecular vibrational temperature Mw/MnMolecular structure close or equal to 1, But synthesis step is usually comparatively laborious.Compare with dendritic, dissaving polymer is without so regular, molecular mass point Cloth is wider, usual 1.2 < Mw/Mn< 2.5, because having similar structure with Dendrimers, so performance also close to.But it is hyperbranched Synthetic method of polymers is simple, and one-step polymerization method synthesis generally can be used.Dendritic and dissaving polymer have class Spheroidal cramped construction has higher modified with functional group degree relative to linear polymeric, i.e. the degree of branching is very high；Fluid simultaneously The mechanics radius of gyration is small, and molecular entanglement is few, and substance viscosity is smaller with the increase variation of relative molecular mass.Usual dendroid The molecular weight of polymer and dissaving polymer is relatively large, thus volatility is very low, almost without smell, belongs to environment Friendly ep-type material.
Application of polymer-inorganic nanocomposite, especially nano composite polymer/laminated silicate material are to open in recent years The popular new material of hair, by the addition of inorganic material so that the machinery of polymer, calorifics, optics or physicochemical properties Enhance in a controlled manner.Different from traditional micron level composite material, polymer/silicate composite material referred herein It is to remove silicate nano layer sufficiently simultaneously by the bidimensional interfacial interaction between polymer and nano-dispersed silicate layer It is dispersed in polymeric matrix, to have the advantages that conventional composites materials are incomparable: 1. mass are lighter, because its is inorganic Object additive amount is low (organoclay, which mixes 0.5~5wt.%, so that polymer performance is obviously improved)；2. mechanical property is improved, The lamellar structure of nano-dispersed has humidification to polymer in two-dimensional directional；3. excellent gas barrier effect and certain Fire retarding effect；4. the transparency of material is not influenced, because the lamellar structure thickness of its dispersion is about 1nm, with visible light wave wavelength Quite, light wave can directly pass through；5. it is low in cost, it is easy to process.
Natural clay mineral is the important member of silicate family；It mainly include montmorillonite, kaolin, talcum, mica, mud Limestone, zeolite, hectorite etc..Wherein montmorillonite (Montmorillonite, MMT) is to belong to the referred to as laminar silicic acid of 2:1 Salt, as the term suggests there is layer structure.Its unit cell presss from both sides one layer of alumina octahedral by two layers of oxygen-octahedron and forms, tetrahedron It is connected with octahedron with common oxygen atom, forms about 0.96 nanometer thick, the standard two of the high-sequential of draw ratio about 100-1000 Chip is tieed up, about 8-10 chip constitutes an elementary particle, then constitutes montmorillonite particle by several elementary particles.Montmorillonite Two adjacent sheets between only connected by oxygen atomic layer and oxygen atomic layer, without chemical bond and hydrogen bond, only faint model moral Hua Li.There is the cations that can be replaced, including Mg between crystal layer2+, Ca2+, Na+, K+, Li+And H+Deng.
Up to the present, nano composite polymer/laminated silicate material is studied, polymer object mostly concentrates on Engineering plastics, such as polycarbonate, acrylonitrile-butadiene-styrene (ABS), polypropylene, polyethylene, polyurethane, nylon.Montmorillonite master Polymer is then mixed by melting mixing mode first by hydrophobic cetyl trimethylammonium bromide (CTAB) intercalation modifying In matrix.However compatibility of the montmorillonite of hydrophobically modified in aqueous coating system is bad, is difficult to remove and be easy coalescence, it is right The performance of coating paint film plays reaction.How more effectively to disperse clay in aqueous coating system improve clay with it is aqueous The compatibility of coating system, the performance for improving coating paint film is the problem to be solved in the present invention.
Summary of the invention
The first purpose of this invention is to provide a kind of water-based paint compositions, in the composition in clay and system Polymer matrix compatability is good, and clay can be removed effectively and is dispersed in polymeric matrix, and the water paint group The paint film that compatibility is good between conjunction object each component, is formed has higher gel content and improved machinery, barrier property, scrubbing resistance Performance and corrosion resistance.
Second object of the present invention is to provide a kind of preparation method of water-based paint compositions.
In order to achieve the above first purpose, the present invention adopts the following technical solutions:
A kind of water-based paint compositions, it includes:
At least partly dendroid that is cationized of Amino End Group or hyperbranched polyol amine；
Clay；
Film forming matter includes at least one emulsion polymer；
Wherein, at least partly Amino End Group is cationized dendroid or hyperbranched polyol amine at least partly intercalation into Enter in clay layer.
According to the preferred embodiment of the present invention, at least one official that can be reacted with amino is contained in the emulsion polymer It can roll into a ball, the functional group is selected from:
In the present invention, at least partly intercalation of the dendroid or hyperbranched polyol amine that are cationized of Amino End Group as clay Agent can be more effectively inserted between the crystal layer of clay, expand the interlamellar spacing of clay to reduce interlaminar action power.So that viscous Soil is more effectively removed and evenly dispersed in the paint film that water-based paint compositions are formed, improve paint film gel content, Improve mechanical performance, barrier property, scrub performance and corrosion resistance.At least partly branch that is cationized of Amino End Group Shape or hyperbranched polyol amine can be crosslinked with the emulsion polymer containing above-mentioned functional group to react, and can further improve The above-mentioned characteristic of paint film, such as mechanical performance and gel content.
According to the preferred embodiment of the present invention, the dendroid or hyperbranched that at least partly Amino End Group is cationized Polyamine is the PAMAM (polyamide-amide) that at least partly Amino End Group is cationized.In certain specific embodiments of the invention In, the weight average molecular weight of the PAMAM raw material of PAMAM that at least partly Amino End Group is cationized is greater than 500, preferably 500~ 6000.Preferably, the PAMAM is selected from the 0th generation, 1st generation, 2nd generation dendroid PAMAM.Wherein, 1st generation dendroid PAMAM Structure is shown below:
According to the preferred embodiment of the present invention, PAMAM may include but be not limited to as the type of Weihai Chen Yuan molecule new material Number for CYD-100A, CYD-110A, CYD-D014 etc. PAMAM.
According to the preferred embodiment of the present invention, the structure for the PAMAM that at least partly Amino End Group is cationized is PAMAM-N+R1R2R3, wherein R1, R2, R3 can be identical or be different containing hydrogen, hydrocarbon alkyl, alkenyl, alkynyl, Phenyl, aryl.
According to the preferred embodiment of the present invention, the PAMAM that at least partly Amino End Group is cationized is by PAMAM At least partly Amino End Group be cationized as ammonium salt.
According to the preferred embodiment of the present invention, the preparation side for the PAMAM that at least partly Amino End Group is cationized Method are as follows: reaction kettle, Yu Shui is added by mole equivalent proportion 49:1~1:1 in the Amino End Group functional group of PAMAM and cationic reagent In synthesis is sufficiently stirred, obtain the PAMAM that at least partly Amino End Group is cationized.It is highly preferred that one of the PAMAM or two A or three amido functional groups are cationized by cationic reagent, and the rush thickening power effect to clay played at this time is more It is good.
In above-mentioned preparation method, after synthetic reaction, it can optionally remove water or directly use.
According to the preferred embodiment of the present invention, the cationic reagent is halogenated hydrocarbons, the organic acid, nothing of C1~C16 One of machine acid is a variety of.Preferably, organic acid is selected from the phosphorus of the fatty acid of C1~C16, the sulfonic acid of C1~C16, C1~C16 Acid；It is highly preferred that the fatty acid of the C1~C16 is one of oxalic acid, fatty acid, acrylic acid or a variety of.According to the present invention Preferred embodiment, the halogenated hydrocarbons of the C1~C16 can be for such as iodomethane, bromoethane, the sulfonic acid of the C1~C16 can Phosphoric acid for such as methane sulfonic acid, ethylsulfonic acid etc., C1~C16 can be for such as methyl acid phosphate, n-hexyl phosphoric acid.Preferably, The inorganic acid is selected from one of hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid or a variety of.It is highly preferred that the cationic reagent is salt Acid, the PAMAM of the cationization obtained at this time to the removing dispersion for promoting clay and and emulsion polymer combination effect more It is good.
According to the preferred embodiment of the present invention, the monomer that the emulsion polymer uses includes at least in following monomer It is one or more: acetoacetoxyethyl methacrylate, tert-butyl acetoacetate, Diacetone Acrylamide, to provide The above-mentioned functional group that can be reacted with amino is capable of providing in emulsion polymer.
According to the preferred embodiment of the present invention, the emulsion polymer, which is selected from, contains acetoacetoxyethyl One of ethyl ester, tert-butyl acetoacetate, Diacetone Acrylamide or a variety of acrylate copolymer emulsions, styrene-the third Olefin(e) acid ester copolymer emulsion, polyvinyl acetate emulsion, vinyl acetate-ethylene copolymer, vinyl acetate-acrylate copolymer emulsion or Vinyl acetate-tertiary ethylene carbonate copolymer emulsion.It is highly preferred that the emulsion polymer, which is selected from, contains methacrylic acid acetyl second The acrylate copolymer emulsion or benzene of one or more of acyloxy ethyl ester, tert-butyl acetoacetate, Diacetone Acrylamide Ethylene-acrylate copolymers lotion.At this point, there is better compatibility between the water-based paint compositions each component, and formed The gel content of paint film is higher, mechanical performance, barrier property, scrub performance and corrosion resistance are higher.For example, the lotion Polymer can be selected from the model PRIMAL of DOW ChemicalTMThe acrylate copolymer emulsion (following abbreviation SF240) of SF240, bar The interpolymer latex of polystyrene and acrylic ester (hereinafter referred to as lotion 9259) of the model NPE-9259 of De Fu company.
In water-based paint compositions in the present invention containing above-mentioned functional group emulsion polymer film forming after, it is described at least The dendroid or hyperbranched polyol amine that part Amino End Group is cationized can also at room temperature in the emulsion polymer can The reaction was continued for the functional group reacted with amino, to become a part of obtained paint film, further improves the machine of coating paint film Tool performance, film forming, corrosion resistance etc..
According to the preferred embodiment of the present invention, the cation exchange capacity of the clay is 30~160mmol/100g. The amount that clay includes exchangeable cations is called cation exchange capacity (CEC), and unit is mmol/100g clay, i.e., and every 100 MM number of gram clay cation.It is highly preferred that the cation exchange capacity of the clay is 80~120mmol/100g. Clay at this time is quite well to monomer or the intercalation of polymer.If the CEC value of clay is too high, i.e., interlayer cation compared with More, high Coulomb force makes clay layer combine tighter, is unfavorable for the insertion of organic molecule and the removing of clay layer.Phase Instead, if the CEC value of clay is too low, the organic cation exchanged up after organic decoration is not enough to that silicate plate is completely covered The compatibility of layer surface, obtained organic clay and polymeric matrix is bad, cannot guarantee that sufficient intercalation stripping.
According to the preferred embodiment of the present invention, the clay is selected from montmorillonite, marlstone, talcum, mica, fine snake Stone, zeolite, hectorite, fluorine hectorite, hectorite.More preferably montmorillonite, intercalation effect is obvious, conducive to clay Modified and improvement and coating polymer matrix compatibility, improves paint film mechanical performance, corrosion resistance, resistance to barrier property, anti-scratch Washing property etc..
According to the preferred embodiment of the present invention, 100 parts by weight meter of water-based paint compositions total amount, the film forming matter Additive amount is 5~50 parts.
According to the preferred embodiment of the present invention, 100 parts by weight meter of water-based paint compositions total amount, it is described at least partly to hold The additive amount of dendroid or hyperbranched polyol amine that amino is cationized is 0.1~5 part, and the additive amount of clay is 0.2~10 Part.It is highly preferred that the additive amount of dendroid or hyperbranched polyol amine that at least partly Amino End Group is cationized be 0.1~ 2 parts, the additive amount of clay is 0.2~5 part, and the paint film that gained water-based paint compositions are formed at this time has higher gel content With improved machinery, barrier property, scrub performance and corrosion resistance.
More preferable embodiment according to the present invention, when the water-based paint compositions match finished product paint, by by aqueous 100 parts by weight meter of coating composition total amount, the additive amount of the film forming matter are 20~45 parts.In specific embodiment party of the invention In formula, the film forming matter may also include but be not limited to 30~45 parts, 35~45 parts, 35~40 parts etc..
According to the preferred embodiment of the present invention, when the water-based paint compositions match obtained varnish, by by water paint 100 parts by weight meter of total composition, the additive amount of the film forming matter are 96~98 parts.It is highly preferred that at least portion described at this time The additive amount of the dendroid or hyperbranched polyol amine of dividing Amino End Group to be cationized is 0.1~0.5 part, and the additive amount of clay is 0.2~2 part, preferably 0.2~1 part, the performances such as mechanical performance, film forming, corrosion resistance of the varnish prepared at this time It is excellent.
Specific embodiment according to the present invention, the water-based paint compositions are the combination of single-component water-based building coating Object.
Specific embodiment according to the present invention, also comprising conventional coating additive in the water-based paint compositions.It applies Selection those skilled in the art of material auxiliary agent can operate according to actual needs.For example, when the water-based paint compositions are matched When finished product paint, it is preferable that also include water, inorganic filler, dispersing agent, wetting agent, defoaming in the water-based paint compositions Agent, thickener, coalescing agent, in-can preservative, it is several in mould inhibitor, pH adjusting agent.For example, working as the aqueous coating composition It also may include surfactant, coalescing agent, defoaming agent etc. in the water-based paint compositions when object matches obtained varnish.
Wherein, inorganic filler can reduce gloss of film, reduce cost.Exemplary inorganic filler include but is not limited to be talcum Powder, calcium carbonate etc..In terms of being 100 parts by weight by the total amount of water-based paint compositions, the additive amount of inorganic filler can be 10~20 parts.
Pigments and fillers can be dispersed in dispersing agent.Exemplary dispersing agent include but is not limited to be sodium polycarboxylate salt dispersing agent.With water Property coating composition total amount be 100 parts by weight meters, dispersing agent additive amount can be 0.5~0.8 part.
Wetting agent and coalescing agent can reduce film-forming temperature, promote film forming.With the total amount of water-based paint compositions for 100 weights Part meter is measured, additive amount can be 1~2 part.
Defoaming agent can play the role of defoaming.Exemplary defoaming agent include but is not limited to be organosilicon or mineral substance defoaming Agent.By the total amount of water-based paint compositions be 100 parts by weight in terms of, additive amount can be 0.2~0.5 part.
Thickener can be PU thickener and/or HEC thickener, be used for regulation system viscosity.With water-based paint compositions Total amount is 100 parts by weight meters, and PU thickener additive amount can be 0~2 part；HEC thickener additive amount can be 0.1~0.4 part.
In-can preservative is not interfered for system in protective pot by bacterium, can be CMIT/MIT.With water-based paint compositions Total amount be 100 parts by weight meters, additive amount can be 0.1~0.2 part.
Mould inhibitor is for protecting film not by the erosion of mould.By the total amount of water-based paint compositions be 100 parts by weight in terms of, Its additive amount can be 1~2 part.
PH adjusting agent is used for regulation and control system pH.By the total amount of water-based paint compositions be 100 parts by weight in terms of, Additive amount can be 0.05~0.2 part.
Water is decentralized medium, and dispersion and premix raw material adjust viscosity.With the total amount of water-based paint compositions for 100 weight Part meter, additive amount can be 10~35 parts.
Antifreeze can also be contained in water-based paint compositions of the invention, for improving coating system freezing stability.With water Property coating composition total amount be 100 parts by weight meters, additive amount can be 0.5~2 part.
Pigment can also be contained in water-based paint compositions of the invention, play the role of covering, such as titanium dioxide.With aqueous painting The total amount of feed composition is 100 parts by weight meters, and additive amount can be 10~25 parts.
To reach above-mentioned second purpose, the present invention provides the preparation method of above-mentioned water-based paint compositions, this method packet Include following steps: dendroid or hyperbranched polyol amine that at least partly Amino End Group is cationized and clay after mixing, It adds in the raw material comprising film forming matter and water-based paint compositions is prepared.
In the present invention, mixed by dendroid or hyperbranched polyol amine that at least partly Amino End Group is cationized with clay After conjunction, realizes and dendroid or hyperbranched polyol amine at least partly intercalation that at least partly Amino End Group is cationized are entered into clay In lamella.
According to the preferred embodiment of the present invention, the step of preparation method can are as follows: will at least partly Amino End Group it is positive The dendroid or hyperbranched polyol amine of ionization are dissolved in the aqueous solution of clay, after mixing, by centrifuged precipitating Object is added in the raw material comprising film forming matter.
According to the preferred embodiment of the present invention, the preparation method includes the following steps:
1) water, clay, at least partly dendroid or hyperbranched more that is cationized of Amino End Group are successively added into container First amine, and be uniformly mixed, obtain mixture A；
2) mixture A is uniformly mixed again with other raw materials, obtains water-based paint compositions.
More preferable embodiment according to the present invention, the preparation method include the following steps:
1) water, clay, at least partly dendroid or hyperbranched more that is cationized of Amino End Group are successively added into container First amine, and be uniformly mixed, obtain mixture A；
2) water, part thickener, pH adjusting agent, dispersing agent, defoaming agent, mixture A and inorganic are successively added into container Filler, and be uniformly mixed, obtain mixture B；
3) into mixture, B sequentially adds film forming matter, coalescing agent, in-can preservative, mould inhibitor, remainder again Thickener, water are uniformly mixed, obtain water-based paint compositions.
Unless otherwise specified, the present invention in it is raw materials used can be by commercially available commercially available.
Beneficial effects of the present invention are as follows:
In water-based paint compositions of the invention, at least partly dendroid that is cationized of Amino End Group or hyperbranched polyol After amine carries out intercalation modifying to clay as intercalator, overcomes high molecular weight polymers and act on unconspicuous ask to clay intercalated Topic.The compatibility for improving clay Yu water paint polymeric matrix, is dispersed in clay in polymeric matrix；Further By being cooperated with specific emulsion polymer so that obtained paint film have higher gel content and improved machinery, Barrier property, scrub performance and corrosion resistance.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 shows the gel content figure of product paint film in embodiment 31.
Fig. 2 shows the pendulum-rocker hardness figures of product paint film in embodiment 32.
The elongation strain test curve of product paint film in embodiment 33 is shown respectively in Fig. 3 A, 3B, 3C.
Fig. 4 shows the corrosion resistance result of 34 product paint film of embodiment.
Fig. 5 shows the scrubbing resistance test result of 36 product paint film of embodiment.
Fig. 6 shows product XRD diagram in embodiment 46.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings It is bright.Similar component is indicated in attached drawing with identical appended drawing reference.It will be appreciated by those skilled in the art that institute is specific below The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
Raw material:
1.PAMAM (polyamide-amide): it is provided by Weihai Chen Yuan molecule new material Co., Ltd, the basic ginseng of PAMAM sample Number is as shown in table 1 below.
The basic parameter of table 1.PAMAM sample
2.PRIMALTMSF240 contains the acrylate copolymer emulsion of acetoacetoxyethyl methacrylate (AAEM) (hereinafter referred to as lotion SF240) is provided by Dow Chemical；(the following letter of NPE-9259 interpolymer latex of polystyrene and acrylic ester Claim lotion 9259) it is provided by Ahmedabad richness company.
3. literalness sodium montmorillonite (MMT, 99.8%, CEC=104mmol/100g)) from Bonding Chemical (USA) it buys.
4. remaining required raw material is also commercially available by commercially available.
Performance test methods:
1. gel content determining:
Emulsion paint is applied on a glass, is removed after crosslinking curing within room temperature seven days, weighs 0.5~1 gram of paint film therein.With Filter paper package, claims to obtain weight (Wx).It is placed in the container containing 200 milliliters of acetone solvents, with the speed of 500rpm in room temperature Lower magnetic agitation 24 hours.Filter paper and content are taken out and dried 30 minutes in air, is then placed in an oven 110 DEG C dry 30 minutes.Weighing (Wy) is taken out, gel content can be calculated by following formula:
Gel content (%)=(Wy/Wx) × 100
2. persoz puts experiment of hardness:
It is tested according to 53157 method persoz pendulum-rocker hardness of ISO1522/ASTM D4366/DIN.
3. scrubbing resistance is tested:
Emulsion paint sample is coated in byko-chart series of tests paper jam (#PB-5015), and is tested solid at room temperature before Change 7 days.It is placed in scrubbing resistance tester.Brush head uses the scouring pad (not using the brush head of ASTM standard) of 3M company.1000 After the secondary scouring period, the abrasion condition of paint film is observed and recorded.
4. passing through the elongation strain of dynamic mechanical analysis latex film:
Constant temperature (30 DEG C) are carried out to the paint film after solidification using dynamic mechanical analyzer DMA Q800 (TA Instrument) Elongation strain test.Pretightning force is 0.001 newton, and initial length is 5 millimeters, and extensibility holding per minute 10% is until 200%.
5. accelerated corrosion is tested
Coating cutter is fully cured standardized on panel on the sheet tin through polishing, to 7 days in varnish sample film " X " and coating is passed through downwards until substrate.Then plate is fixed with clip, it is molten that 5% (weight percent) NaCl is immersed in lower half Liquid.Panel is taken out after 72 hours, is dried, the corrosion condition of paint film plate is observed and recorded.
6.X optical diffraction (XRD) analysis.
Use German Brooker D8 Series X-ray diffractometer；Radiographic source is Cu-K αScanning angle is 2.5 To 33.2 °；Step-length is 0.02 ° (2 θ).
Embodiment 1
The intercalation modifying of nano montmorillonite is named as 100A-MMT. for 35 grams of CYD-100A and is dissolved in 65 grams of deionized water water In, it obtains mother liquor and is named as 100A.10 grams of montmorillonites and 300 grams of deionized waters are added in 500 milliliters of round-bottomed bottles, heating It is sufficiently stirred 30 minutes to 60 DEG C, 10 grams of 100A mother liquors is then added dropwise.Continue stirring 5 hours after being added dropwise, is then cooled to Room temperature is transferred to centrifuge tube and is centrifuged 20 minutes, removes supernatant.Deionized water washing is added toward sediment, is centrifuged, 5 times repeatedly, Vacuum oven is placed in remove water to obtain product.
Embodiment 2
The intercalation modifying of nano montmorillonite, be named as 100A-1HCl-MMT. by 35 grams of CYD-100A be dissolved in 58.3 grams go from In sub- water water, 6.7 grams of hydrochloric acid (37%) are added dropwise and are sufficiently stirred 30 minutes, obtained mother liquor and be named as 100A-1HCl. general 10 grams of montmorillonites and 300 grams of deionized waters are added in 500 milliliters of round-bottomed bottles, are heated to 60 degrees Celsius and are sufficiently stirred 30 points Then 10 grams of 100A-1HCl mother liquors are added dropwise in clock.Continue after being added dropwise stirring 5 hours, be then cooled to room temperature, be transferred to from Heart pipe is centrifuged 20 minutes, removes supernatant.Deionized water washing is added toward sediment, centrifugation 5 times repeatedly, is placed in vacuum drying Case removes water to obtain product.
Embodiment 3
The intercalation modifying of nano montmorillonite, is named as 100A-2HCl-MMT.By 35 grams of CYD-100A be dissolved in 51.7 grams go from In sub- water water, 13.3 grams of hydrochloric acid (37%) are added dropwise and are sufficiently stirred 30 minutes, mother liquor is obtained and is named as 100A-2HCl. 10 grams of montmorillonites and 300 grams of deionized waters are added in 500 milliliters of round-bottomed bottles, 60 DEG C is heated to and is sufficiently stirred 30 minutes, Then 10 grams of 100A-2HCl mother liquors are added dropwise.Continue stirring 5 hours after being added dropwise, is then cooled to room temperature, is transferred to centrifuge tube Centrifugation 20 minutes removes supernatant.Deionized water washing is added toward sediment, centrifugation 5 times repeatedly, is placed in vacuum oven and removes Water obtains product.
Embodiment 4
The intercalation modifying of nano montmorillonite, is named as 110A-MMT.35 grams of CYD-110A are dissolved in 65 grams of deionized water water In, it obtains mother liquor and is named as 110A.10 grams of montmorillonites and 300 grams of deionized waters are added in 500 milliliters of round-bottomed bottles, heating It is sufficiently stirred 30 minutes to 60 DEG C, 10 grams of 110A mother liquors is then added dropwise.Continue stirring 5 hours after being added dropwise, is then cooled to Room temperature is transferred to centrifuge tube and is centrifuged 20 minutes, removes supernatant.Deionized water washing is added toward sediment, is centrifuged, 5 times repeatedly, Vacuum oven is placed in remove water to obtain product.
Embodiment 5
The intercalation modifying of nano montmorillonite, is named as 110A-1HCl-MMT.By 35 grams of CYD-110A be dissolved in 62.0 grams go from In sub- water water, 3.0 grams of hydrochloric acid (37%) are added dropwise and are sufficiently stirred 30 minutes, mother liquor is obtained and is named as 110A-1HCl.It will 10 grams of montmorillonites and 300 grams of deionized waters are added in 500 milliliters of round-bottomed bottles, are heated to 60 DEG C and are sufficiently stirred 30 minutes, so 10 grams of 110A-1HCl mother liquors are added dropwise afterwards.Continue after being added dropwise stirring 5 hours, be then cooled to room temperature, be transferred to centrifuge tube from The heart 20 minutes, remove supernatant.Deionized water washing is added toward sediment, centrifugation 5 times repeatedly, is placed in vacuum oven water removal Obtain product.
Embodiment 6
The intercalation modifying of nano montmorillonite, is named as 100A-2HCl-MMT.By 35 grams of CYD-110A be dissolved in 59.0 grams go from In sub- water water, 6.0 grams of hydrochloric acid (37%) are added dropwise and are sufficiently stirred 30 minutes, mother liquor is obtained and is named as 100A-2HCl.It will 10 grams of montmorillonites and 300 grams of deionized waters are added in 500 milliliters of round-bottomed bottles, are heated to 60 DEG C and are sufficiently stirred 30 minutes, so 10 grams of 100A-2HCl mother liquors are added dropwise afterwards.Continue after being added dropwise stirring 5 hours, be then cooled to room temperature, be transferred to centrifuge tube from The heart 20 minutes, remove supernatant.Deionized water washing is added toward sediment, centrifugation 5 times repeatedly, is placed in vacuum oven water removal Obtain product.
Embodiment 7
The intercalation modifying of nano montmorillonite, is named as D014-MMT.35 grams of CYD-D014 are dissolved in 65 grams of deionized water water In, it obtains mother liquor and is named as D014.10 grams of montmorillonites and 300 grams of deionized waters are added in 500 milliliters of round-bottomed bottles, heating It is sufficiently stirred 30 minutes to 60 DEG C, 10 grams of D014 mother liquors is then added dropwise.Continue stirring 5 hours after being added dropwise, is then cooled to Room temperature is transferred to centrifuge tube and is centrifuged 20 minutes, removes supernatant.Deionized water washing is added toward sediment, is centrifuged, 5 times repeatedly, Vacuum oven is placed in remove water to obtain product.
Embodiment 8
The intercalation modifying of nano montmorillonite, is named as D014-1HCl-MMT.By 35 grams of CYD-D014 be dissolved in 62.2 grams go from In sub- water water, 2.8 grams of hydrochloric acid (37%) are added dropwise and are sufficiently stirred 30 minutes, mother liquor is obtained and is named as D014-1HCl.It will 10 grams of montmorillonites and 300 grams of deionized waters are added in 500 milliliters of round-bottomed bottles, are heated to 60 DEG C and are sufficiently stirred 30 minutes, so 10 grams of D014-1HCl mother liquors are added dropwise afterwards.Continue after being added dropwise stirring 5 hours, be then cooled to room temperature, be transferred to centrifuge tube from The heart 20 minutes, remove supernatant.Deionized water washing is added toward sediment, centrifugation 5 times repeatedly, is placed in vacuum oven water removal Obtain product.
Embodiment 9
The intercalation modifying of nano montmorillonite, is named as D014-2HCl-MMT.By 35 grams of CYD-D014 be dissolved in 59.4 grams go from In sub- water water, 5.6 grams of hydrochloric acid (37%) are added dropwise and are sufficiently stirred 30 minutes, mother liquor is obtained and is named as D014-2HCl.It will 10 grams of montmorillonites and 300 grams of deionized waters are added in 500 milliliters of round-bottomed bottles, are heated to 60 DEG C and are sufficiently stirred 30 minutes, so 10 grams of D014-2HCl mother liquors are added dropwise afterwards.Continue after being added dropwise stirring 5 hours, be then cooled to room temperature, be transferred to centrifuge tube from The heart 20 minutes, remove supernatant.Deionized water washing is added toward sediment, centrifugation 5 times repeatedly, is placed in vacuum oven water removal Obtain product.
Embodiment 10
Montmorillonite and other auxiliary agents are added in lotion SF240, varnish is made into according to table 2.
Table 2
Embodiment 11
Montmorillonite and other auxiliary agents are added in lotion SF240, varnish is made into according to table 3.
Table 3
Embodiment 12
In lotion SF240 be added intercalation modifying montmorillonite (100A-MMT, the i.e. product of embodiment 1) and other help Agent is made into varnish according to table 4.
Table 4
Embodiment 13
In lotion SF240 be added intercalation modifying montmorillonite (100A-MMT, the i.e. product of embodiment 1) and other help Agent is made into varnish according to table 5.
Table 5
Embodiment 14
In lotion SF240 be added intercalation modifying montmorillonite (100A-1HCl-MMT, the i.e. product of embodiment 2) and its His auxiliary agent, is made into varnish according to table 6.
Table 6
Embodiment 15
In lotion SF240 be added intercalation modifying montmorillonite (100A-1HCl-MMT, the i.e. product of embodiment 2) and its His auxiliary agent, is made into varnish according to table 7.
Table 7
Embodiment 16
In lotion SF240 be added intercalation modifying montmorillonite (100A-2HCl-MMT, the i.e. product of embodiment 3) and its His auxiliary agent, is made into varnish according to table 8.
Table 8
Embodiment 17
In lotion SF240 be added intercalation modifying montmorillonite (100A-2HCl-MMT, the i.e. product of embodiment 3) and its His auxiliary agent, is made into varnish according to table 9.
Table 9
Embodiment 18
In lotion SF240 be added intercalation modifying montmorillonite (110A-MMT, the i.e. product of embodiment 4) and other help Agent is made into varnish according to table 10.
Table 10
Embodiment 19
In lotion SF240 be added intercalation modifying montmorillonite (110A-MMT, the i.e. product of embodiment 4) and other help Agent is made into varnish according to table 11.
Table 11
Embodiment 20
In lotion SF240 be added intercalation modifying montmorillonite (110A-1HCl-MMT, the i.e. product of embodiment 5) and its His auxiliary agent, is made into varnish according to table 12.
Table 12
Embodiment 21
In lotion SF240 be added intercalation modifying montmorillonite (110A-1HCl-MMT, the i.e. product of embodiment 5) and its His auxiliary agent, is made into varnish according to table 13.
Table 13
Embodiment 22
In lotion SF240 be added intercalation modifying montmorillonite (110A-2HCl-MMT, the i.e. product of embodiment 6) and its His auxiliary agent, is made into varnish according to table 14.
Table 14
Embodiment 23
In lotion SF240 be added intercalation modifying montmorillonite (110A-2HCl-MMT, the i.e. product of embodiment 6) and its His auxiliary agent, is made into varnish according to table 15.
Table 15
Embodiment 24
In lotion SF240 be added intercalation modifying montmorillonite (D014-MMT, the i.e. product of embodiment 7) and other help Agent is made into varnish according to table 16.
Table 16
Embodiment 25
In lotion SF240 be added intercalation modifying montmorillonite (D014-MMT, the i.e. product of embodiment 7) and other help Agent is made into varnish according to table 17.
Table 17
Embodiment 26
In lotion SF240 be added intercalation modifying montmorillonite (D014-1HCl-MMT, the i.e. product of embodiment 8) and its His auxiliary agent, is made into varnish according to table 18.
Table 18
Embodiment 27
In lotion SF240 be added intercalation modifying montmorillonite (D014-1HCl-MMT, the i.e. product of embodiment 8) and its His auxiliary agent, is made into varnish according to table 19.
Table 19
Embodiment 28
In lotion SF240 be added intercalation modifying montmorillonite (D014-2HCl-MMT, the i.e. product of embodiment 9) and its His auxiliary agent, is made into varnish according to table 20.
Table 20
Embodiment 29
In lotion SF240 be added intercalation modifying montmorillonite (D014-2HCl-MMT, the i.e. product of embodiment 9) and its His auxiliary agent, is made into varnish according to table 21.
Table 21
Embodiment 30
As reference, other auxiliary agents are added in SF240 lotion, varnish is made into according to table 22.
Table 22
Embodiment 31
By the sample of embodiment 10-30 film on a glass, paint film peel test gel is contained after room temperature curing in 7 days Amount, is as a result listed in table 23 and draws histogram in favor of intuitively comparing (Fig. 1).As can be seen from the table, as the embodiment of reference 30 gel content is minimum (77.52%), and the gel content that its paint film after a small amount of clay is added increases, and is added 1% montmorillonite is always higher than 0.5% gel content, and reason has two o'clock: barriering effect of 1. montmorillonites after paint film dispersion；2. Additional clay quality, this is because clay do not dissolve in for test acetone solvent, thus can be attached to gel test after In residual mass.After adding the modified montmorillonite of the PAMAM without cationization modification, gel content, which has, further to be mentioned Height, this point can be found out from embodiment 12-13,18-19,24-25 and the comparing result of embodiment 10-11.On the other hand It is being added after the modified montmorillonite of the PAMAM of cationization modification from can be seen that in remaining embodiment, gel content has Obviously improve；Further, thus it is speculated that may be smaller due to the small molecule of the CYD-100A in zero generation, relative to CYD- 110A or CYD-D014 is easier between the crystal layer for being inserted into montmorillonite and obtains in paint film more effectively removing dispersion, formed compared with Continuous phase reaches barriering effect, therefore the gel content measured is higher.The above results show that the PAMAM of cationization can be more It is effectively peeled off montmorillonite in a polymer matrix evenly dispersed, action principle is possibly via montmorillonite crystal layer Between exchangeable cations (Mg2+, Ca2+, Na+, K+, Li+And H+Deng) carry out the mode that exchanges of cation with ionization PAMAM and make PAMAM is inserted into crystal layer gap, expands interlamellar spacing to reduce interlaminar action power.Simultaneously because containing second in lotion SF240 Ethyl acetoacetic acid functional group, can occur chemical reaction with amino and generate crosslinking, improve crosslink density, have one to gel content is improved It is fixed to help.
23. gel content test result of table
Embodiment 32
By embodiment 10-30 sample film on a glass, the pendulum-rocker hardness of paint film, knot are tested after room temperature curing in 7 days Fruit is listed in table 24 and draws histogram in favor of intuitively comparing (Fig. 2).The film of the embodiment 30 (reference) of no added montmorillonite is hard Degree is minimum in all test paint films；And as expected, by the way that unmodified montmorillonite is added, so that embodiment 10 and 11 Hardness of paint film is improved, and is incremented by as additional amount increases.However we have found that unmodified montmorillonite is added, paint film Transparency and gloss are all declined relative to referring to embodiment 30, this shows that montmorillonite is not fine and is evenly dispersed in high score Subbase body.The hardness of paint film of embodiment 12-13,18-19,24-25 have further raising, this may be due to PAMAM pairs The special adsorption of montmorillonite, so that it is in paint stripping dispersed phase to preferable.On the other hand, the knot of remaining embodiment film Fruit clearly shows, is adding after the modified montmorillonite of the PAMAM of cationization modification, the hardness of paint film, which has, significantly to be mentioned Height significantly improves it has been found that the smooth and transparency of paint film has also relative to embodiment 10 and 11, this is illustrated through changing Property montmorillonite obtained in paint film matrix it is effective removing with it is evenly dispersed.It should be pointed out that the illiteracy of intercalation modifying is de- Soil should not be added excessively, because it can dramatically increase the viscosity of lotion and change its rheological behaviour, in varnish, more appropriate is inserted The additive amount of the modified montmorillonite of layer should control 0.2~2wt% in varnish raw material total amount.
24. pendulum-rocker hardness test result of table
Embodiment 33
The varnish sample of embodiment 10-30 is used into 250 microns of coating device films on a glass.After room temperature curing in 7 days, Paint film is removed from glass, carries out elongation strain test, as a result sees Fig. 3 A-3C, while in 100% and 150% extensibility Under stress data be listed in table 25.The trend that elongation strain result is substantially consistent with pendulum-rocker hardness；That is, adding Add after the modified montmorillonite of the PAMAM of cationization modification, paint film strength has obvious raising, the CYD-100A in zero generation CYD-110A or hyperbranched CYD-D014 relative to the first generation are easier between the crystal layer for being inserted into montmorillonite, thus in resin Extent of exfoliation is higher in matrix, and dispersion more evenly, reaches higher paint film intensity.It is otherwise noted that CYD-100A system It arranges the slope of curve of (embodiment 12,13,16,17) and maintains that almost the same (Fig. 3 A, i.e., 4 parallel in entire range of stretch class Curve), and CYD-110A's serial (embodiment 18,19,22,23) and CYD-D014 serial (embodiment 24,25,28,29) In curve (respectively Fig. 3 B and Fig. 3 C), it is being added to the modified montmorillonite of the PAMAM through cationization modification, paint film is (real Apply example 22,23,28,29) the slope of stress strain curve not obviously to be cationized greater than those the embodiment (embodiment of modification 18,19,24,25).This discovery equally illustrates influence of the PAMAM molecular size to the special adsorption of montmorillonite, i.e. molecule is got over Greatly, it acts on weaker；However PAMAM is cationized and is swapped with the cation in montmorillonite crystal layer, then facilitate to overcome This is difficult.
Stress data of the table 25. under 100% and 150% extensibility
Embodiment 34
Representational some varnish sample films are chosen in embodiment 10-30 on the sheet tin through polishing, it is complete to 7 days All solidstate carries out accelerated corrosion tests, is then photographed to record the degree of wear of film (see Fig. 4).Experimental result understands table Bright, the corrosion resistance of reference paint film (embodiment 30) of no added montmorillonite is poor, and is added to cover through PAMAM intercalation modifying and take off The corrosion resistance of the paint film sample (embodiment 13,19,25) of soil then has obvious raising.In addition, in addition through cation After the modified montmorillonite of PAMAM for changing modification, the corrosion resistance of paint film obtained further enhancing (embodiment 15,17, 21,23,27,29)., the results show that using the PAMAM of cationization modification as the intercalator of montmorillonite, energy is finer for these Montmorillonite-based nano lamella is evenly dispersed in polymeric matrix, forms finer and close physical barriers, so that enhancing is to corrosion Blocking effect.
Embodiment 35
A kind of finished product paint is prepared, and is named as Paint-X.The specific method is as follows: according to the formula of table 26, will first go from Sub- water 1 is added in dispersion tank, control800-1000 revs/min of revolving speed, then successively increase raw material 2-8:HEC Thick dose, pH adjusting agent, sodium polycarboxylate salt dispersing agent, organic silicon defoaming agent, titanium dioxide, talcum powder, kaolin addition dispersion It in tank, when addition, controls every kind of raw material and is added time interval 2~3 minutes, to guarantee that mixing is abundant；Revolving speed is increased to 1500- 1800 revs/min, continue dispersion 15~after twenty minutes, reduce revolving speed to 500-800 revs/min, sequentially add raw material 9-13: Acrylic emulsion, coalescing agent, in-can preservative, mould inhibitor, PU thickener, deionized water.When addition, every kind of raw material of control adds Angle of incidence interval 2~3 minutes, to guarantee that sufficiently, finished product paint Paint-X is prepared in mixing.
The compositing formula of 26. finished product paint Paint-X of table
Serial number Primary raw material title Wt%
1 Deionized water 15
2 HEC thickener 0.4
3 PH adjusting agent AMP95 0.1
4 Sodium polycarboxylate salt dispersing agent 0.8
5 Organic silicon defoaming agent 0.5
6 Titanium dioxide 21
7 Talcum powder 5
8 Kaolin 5
9 Acrylic emulsion (SF240) 36.5
10 Coalescing agent (Eastman OE300) 1.5
11 In-can preservative (Lanxess Preventol D7) 0.2
12 Mould inhibitor (Lanxess Biox AM 139) 2
13 PU thickener 2
14 Deionized water 10
In total 100
Embodiment 36
Modification clay product in embodiment 1-9 is added separately in Paint-X with 1% ratio (mass percent), Obtained 9 emulsion paint samples are coated on three byko-chart series of tests paper jams for three groups according to PAMAM type point respectively (PB-5015) on, scrubbing resistance test is carried out after film solidifies 7 days at room temperature, then the degree of wear of film is clapped According to record (see Fig. 5).Experimental result reconfirms that the PAMAM of cationization helps to further increase to cover as intercalator to be taken off Soil disperses in formulation for coating material, to improve the mechanical strength (embodiment 2,3,5,6,8,9) of coating；With without cationization PAMAM makees intercalator (embodiment Isosorbide-5-Nitrae, 7), and the scrub resistance of paint film is relatively poor.In order to reaffirm experimental result, and subtract Few instrument error, will obtain the sample of best result, i.e. embodiment 3,6,9 in each group, be coated on same test paper jam but not Previous position (for example, previous right side in C in Fig. 6 of embodiment 9, in present Fig. 6 on the left of D) is same as to carry out repeating test.Its It as a result is repeatable and satisfactory as shown in D in Fig. 6.Meanwhile we also studied influence of the additive amount to scrub resistance； The E from Fig. 6 as it can be seen that no added montmorillonite reference paint film scrub resistance it is minimum, add 0.5% (mass percent) implementation Scrub performance improves after the product of example 7；Then there is obvious raising after additive amount is increased to 1%.
Embodiment 37
In dispersions of polyurethanesThe montmorillonite of intercalation modifying is added in UH 2593/1 (creating purchased from Cohan) (100A-2HCl-MMT, the i.e. product of embodiment 3) and other auxiliary agents, are made into varnish according to table 27.
Table 27
Embodiment 38
In dispersions of polyurethanesThe montmorillonite of intercalation modifying is added in UH 2593/1 (creating purchased from Cohan) (100A-2HCl-MMT, the i.e. product of embodiment 3) and other auxiliary agents, are made into varnish according to table 28.
Table 28
Embodiment 39
It, will be in dispersions of polyurethanes as referenceOther auxiliary agents are added in UH 2593/1, are matched according to table 29 At varnish.
Table 29
By embodiment 37-39 sample film on a glass, the gloss of paint film is tested after room temperature curing in 7 days, swing rod is hard Degree, gel content and weatherability test, are as a result listed in table 30.Further, we study what the PAMAM through being cationized was modified Effect of the montmorillonite in dispersions of polyurethanes, result can be seen from table,UH 2593/1 itself has very High glossiness, after the modified montmorillonite of addition, the glossiness decline of paint film is larger, becomes semi-gloss from bloom；It can be pre- If the glossiness that meter continuously adds montmorillonite its paint film will be further compromised.As can be seen from the table, after intercalation modifying being added After MMT, the gel content and pendulum-rocker hardness of paint film also have a degree of improvement.
Table 30
Embodiment 40
Other auxiliary agents are added in lotion 9259, varnish is made into according to table 31.
Table 31
Embodiment 41
Montmorillonite and other auxiliary agents are added in lotion 9259, varnish is made into according to table 32.
Table 32
Embodiment 42
In lotion 9259 be added intercalation modifying montmorillonite (100A-2HCl-MMT, the i.e. product of embodiment 3) and other Auxiliary agent is made into varnish according to table 33.
Table 33
Embodiment 43
In lotion 9259 be added intercalation modifying montmorillonite (110A-2HCl-MMT, the i.e. product of embodiment 6) and other Auxiliary agent is made into varnish according to table 34.
Table 34
Embodiment 44
In lotion 9259 be added intercalation modifying montmorillonite (D014-2HCl-MMT, the i.e. product of embodiment 9) and other Auxiliary agent is made into varnish according to table 35.
Table 35
By the sample of embodiment 40-44 film on a glass, pendulum-rocker hardness is tested after room temperature curing in 7 days, then will Paint film peel test gel content, is as a result listed in table 36.As can be seen from the table, it is especially cationized in addition montmorillonite After PAMAM modified montmorillonite, hardness and gel content have obvious promotion, but glossiness decline is obvious.Trend with it is aforementioned Embodiment is consistent.
Table 36
Embodiment 45
By 15,21 and 27 sample of embodiment film on a glass, film is shelled from glass plate after room temperature curing in 7 days Under, it is fixed on the sample stage of XRD and is tested with double-sided adhesive, while measuring literalness montmorillonite and embodiment 2,5, The powder X-ray RD of 8 montmorillonite obtains result and sees Fig. 6 and table 37.As can be known from the results, through its piece interlayer of the montmorillonite of PAMAM modification Away from being significantly increased compared to literalness montmorillonite, it was demonstrated that (the XRD result difference of embodiment 2,5,8 is or not its intercalation effect Greatly, chart only provides the result of embodiment 2)；And after paint film being made in the montmorillonite addition lotion after modification, due to high score The intercalation of subchain makes interlamellar spacing further expansion, it was demonstrated that uses the PAMAM of cationization as the intercalator of montmorillonite, can make Montmorillonite-based nano lamella is more dispersible in polymer matrix body.
Table 37
Embodiment 46
Embodiment 3 is repeated, difference is, montmorillonite is changed to the talcum of equivalent, remaining condition is constant, and preparation obtains intercalation Modified talcum is named as 100A-2HCl- talcum；Prepare varnish as described in Example 17 again, difference is, by 100A- 2HCl-MMT changes the 100A-2HCl- talcum of equivalent into, remaining condition is constant, obtains varnish.According still further to the side of embodiment 31~35 Method is tested for the property varnish.Known to test result: gained varnish gel content is 88.26%, pendulum-rocker hardness is 141 times, Stress value 1.37MPa under 100% extensibility, the stress value under 150% extensibility are 1.75MPa.
Comparative example 1
Embodiment 17 is repeated, difference is, changes lotion SF240 into conventional acrylic emulsion (Acronal 7079, purchase From BASF), remaining condition is constant, and preparation obtains varnish.Again by gained varnish according to embodiment 31~35 method respectively into Row test, test result is it is found that gained varnish gel content is 83.24%, pendulum-rocker hardness is 107 times, under 100% extensibility Stress value 0.89MPa, the stress value under 150% extensibility are 1.12MPa.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.

Claims (13)

1. a kind of water-based paint compositions, which is characterized in that it includes:
At least partly the dendroid that is cationized of Amino End Group or hyperbranched polyol amine, at least partly Amino End Group are cationic The dendroid or hyperbranched polyol amine of change are the PAMAM that at least partly Amino End Group is cationized；
Clay, the cation exchange capacity of the clay are 30~160mmol/100g；
Film forming matter includes at least one emulsion polymer；
Wherein, the dendroid or hyperbranched polyol amine that at least partly Amino End Group is cationized at least partly intercalation enter viscous In native lamella；
Contain at least one functional group that can be reacted with amino in the emulsion polymer, the functional group is selected from:
Wherein, based on 100 parts by weight of water-based paint compositions total amount, the additive amount of the film forming matter is 5~50 parts；It is described extremely The additive amount of dendroid or hyperbranched polyol amine that small part Amino End Group is cationized is 0.1~5 part, and the additive amount of clay is 0.2~10 part.
2. water-based paint compositions according to claim 1, it is characterised in that；At least partly Amino End Group is cationic The PAMAM's the preparation method comprises the following steps: the Amino End Group functional group of PAMAM and cationic reagent are pressed mole equivalent proportion 49:1~1 of change: 1 is added reaction kettle, and Yu Shuizhong is sufficiently stirred synthesis, obtains the PAMAM that at least partly Amino End Group is cationized.
3. water-based paint compositions according to claim 2, which is characterized in that the weight average molecular weight of the PAMAM is greater than 500；The cationic reagent is one of halogenated hydrocarbons, organic acid, inorganic acid of C1~C16 or a variety of.
4. water-based paint compositions according to claim 2, which is characterized in that the weight average molecular weight of the PAMAM is 500 ~6000.
5. water-based paint compositions according to claim 3, which is characterized in that the organic acid be selected from oxalic acid, fatty acid, One of acrylic acid is a variety of.
6. water-based paint compositions according to claim 3, which is characterized in that the inorganic acid is selected from hydrochloric acid, carbonic acid, sulphur One of acid, phosphoric acid are a variety of.
7. water-based paint compositions according to claim 1, which is characterized in that the emulsion polymer, which is selected from, contains methyl One of acrylic acid acetoacetoxyethyl, tert-butyl acetoacetate, Diacetone Acrylamide or a variety of acrylate Copolymer emulsion, interpolymer latex of polystyrene and acrylic ester, polyvinyl acetate emulsion, vinyl acetate-ethylene copolymer, acetic acid second Alkene-acrylate copolymer emulsion or vinyl acetate-tertiary ethylene carbonate copolymer emulsion.
8. water-based paint compositions according to claim 1 or claim 7, which is characterized in that the emulsion polymer is selected from Tao Shi The model PRIMAL of chemistryTMThe benzene second of the acrylate copolymer emulsion of SF240, the model NPE-9259 of Ahmedabad richness company Alkene-acrylate copolymer emulsion.
9. water-based paint compositions according to claim 1, which is characterized in that the cation exchange capacity of the clay is 80~120mmol/100g.
10. water-based paint compositions according to claim 1, which is characterized in that the clay is selected from montmorillonite, plaster Stone, talcum, mica, choysotile, zeolite, hectorite, fluorine hectorite, hectorite.
11. water-based paint compositions according to claim 1, which is characterized in that the additive amount of the film forming matter is 20 ~45 parts.
12. water-based paint compositions according to claim 1, which is characterized in that the water-based paint compositions are single group Part aqueous architectural coating composition；It also include water, inorganic filler, dispersing agent, wetting agent, defoaming in the water-based paint compositions Agent, thickener, coalescing agent, in-can preservative, mould inhibitor and pH adjusting agent.
13. such as the preparation method of the described in any item water-based paint compositions of claim 1~12, which is characterized in that including such as Lower step: dendroid or hyperbranched polyol amine that at least partly Amino End Group is cationized and clay after mixing, then plus Enter in the raw material comprising film forming matter and water-based paint compositions are prepared.
CN201710208586.4A 2017-03-31 2017-03-31 A kind of water-based paint compositions and preparation method thereof Active CN106883716B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710208586.4A CN106883716B (en) 2017-03-31 2017-03-31 A kind of water-based paint compositions and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710208586.4A CN106883716B (en) 2017-03-31 2017-03-31 A kind of water-based paint compositions and preparation method thereof

Publications (2)

Publication Number Publication Date
CN106883716A CN106883716A (en) 2017-06-23
CN106883716B true CN106883716B (en) 2019-08-02

Family

ID=59181611

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710208586.4A Active CN106883716B (en) 2017-03-31 2017-03-31 A kind of water-based paint compositions and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106883716B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018004234A1 (en) * 2018-05-25 2019-11-28 Ask Chemicals Gmbh Sizing composition, method of coating a mold and use of the sizing composition to coat a mold
EP3741814A1 (en) * 2019-05-24 2020-11-25 Jotun A/S Composition

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101120047A (en) * 2004-12-02 2008-02-06 克里奥瓦克公司 Intercalated layered silicates
CN104710652A (en) * 2015-03-27 2015-06-17 上海工程技术大学 Dendritic modified montmorillonite flame retardant and preparation method thereof
CN105107477A (en) * 2015-08-26 2015-12-02 河南科技大学 Hyperbranched polymer/clay mineral hybrid material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101120047A (en) * 2004-12-02 2008-02-06 克里奥瓦克公司 Intercalated layered silicates
CN104710652A (en) * 2015-03-27 2015-06-17 上海工程技术大学 Dendritic modified montmorillonite flame retardant and preparation method thereof
CN105107477A (en) * 2015-08-26 2015-12-02 河南科技大学 Hyperbranched polymer/clay mineral hybrid material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
树枝状大分子PAMAM合成及对蒙脱土插层改性和应用研究;陈枫等;《高分子通报》;20101031(第10期);第70-71页

Also Published As

Publication number Publication date
CN106883716A (en) 2017-06-23

Similar Documents

Publication Publication Date Title
CN101356205B (en) Method of producing an impact-resistant thermoplastic resin
CA2792151C (en) Hybrid organic-inorganic nanocomposites
RU2447109C2 (en) Using comb-shaped polymer, containing at least one grafted polyalkylene oxide group, as mineral filler compatibility agent in chlorinated thermoplastic materials
Zhu et al. Effect of flexibility of grafted polymer on the morphology and property of nanosilica/PVC composites
EP2675850B1 (en) Modified composite particles
BRPI0502540B1 (en) opacifying particle, method for forming it, and coating and plastic compositions
KR101147855B1 (en) Manufacturing method of globular hybrid particles having the structure of silica core polymer shell
JP6545407B2 (en) Resin composition, molded article, laminate, gas barrier material, coating material and adhesive
Wang et al. Synthesis, morphology and rheology of core-shell silicone acrylic emulsion stabilized with polymerisable surfactant.
CN106883716B (en) A kind of water-based paint compositions and preparation method thereof
AU2014290450A1 (en) Polymer-encapsulated pigment particle
BR112015005680B1 (en) AQUEOUS COATING COMPOSITION, METHOD FOR PROVIDING A COATING, AND, COATING
US10487240B2 (en) Silicone based emulsion, method for making same, and waterborne co-binder resin compositions comprising such emulsions
BR0302747B1 (en) aqueous dispersion of silica, process for the preparation of aqueous dispersion of silica, and method for the treatment of tanned leather.
Kajtna et al. Synthesis and dynamic mechanical analysis of nanocomposite UV crosslinkable 100% solid acrylic pressure sensitive adhesives
Oh et al. Adhesion performance of PSA–clay nano-composites by the in-situ polymerization and mechanical blending
Kausar Physical properties of hybrid polymer/clay composites
Javaheriannaghash et al. Preparation and characterization of water-based polyurethane–acrylic hybrid nanocomposite emulsion based on a new silane-containing acrylic macromonomer
Shen et al. Fabrication and characterization of polysiloxane/polyacrylate composite latexes with balanced water vapor permeability and mechanical properties: effect of silane coupling agent
Patil et al. Synthesis of nano CaCO3/acrylic co‐polymer latex composites for interior decorative paints
EP3455310B1 (en) Aqueous coating compositions containing polymer dispersion with low electrical conductivity and phyllosilicates for oxygen barrier coatings
NO311301B1 (en) Use of copolymers of styrene and maleic anhydride as dispersants and / or as treating agents for mineral batches, as well as thermoplastic compositions containing the copolymers
JP2007145999A (en) Hydroxyl-containing magnetic polymer and method for producing the same
Alvarez et al. Isolation of the interaction between CaCO3 filler and acrylic binder. Part I: Effect of the surfactant and functional monomer type
Alvarez et al. Isolation of the interaction between CaCO3 filler and acrylic binder. Part II: Effect of the amount and type of functional monomer

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant