CN106867357A - A kind of nanometer modified high-solid body point epoxy primer - Google Patents

A kind of nanometer modified high-solid body point epoxy primer Download PDF

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Publication number
CN106867357A
CN106867357A CN201510920753.9A CN201510920753A CN106867357A CN 106867357 A CN106867357 A CN 106867357A CN 201510920753 A CN201510920753 A CN 201510920753A CN 106867357 A CN106867357 A CN 106867357A
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Prior art keywords
epoxy resin
nanometer
epoxy
nanometer modified
nano
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CN201510920753.9A
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CN106867357B (en
Inventor
张玉忠
梁璐
熊瑜
李静
关振威
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BEIJING INSTITUTE OF AERONAUTICAL MATERIALS CHINA AVIATION INDUSTRY GROUP Corp
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BEIJING INSTITUTE OF AERONAUTICAL MATERIALS CHINA AVIATION INDUSTRY GROUP Corp
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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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • 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
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm

Abstract

The present invention relates to a kind of nanometer modified high-solid body point epoxy primer, the priming paint is mixed by a certain percentage by two components；Component one is made up of nanometer modified epoxy resin, Chrome-free anticorrosive pigment/filler, auxiliary agent and organic solvent etc., and component two is curing agent.Epoxy primer of the invention, the coating formed after construction is good in the metal surface such as steel, aluminium adhesive force, after the coating soaks 30 days in water, wet adhesion still reaches more than 18MPa, and after the solidifying priming paint, salt fog resistance, humidity resistance reach more than 5000h, environmental protection simultaneously, solvent discharge is few.

Description

A kind of nanometer modified high-solid body point epoxy primer
Technical field
The invention belongs to coating technology, and in particular to a kind of nanometer modified high-solid body point epoxy primer.
Background technology
High-solid epoxy resin priming paint is one of important development direction of contemporary coating.The film forming of epoxy resin (EP) Performance and adhesive force are excellent, there is good corrosion resistance and permeability resistance to all kinds of media, can with various resins, Filler and auxiliary agent are miscible well, and this makes epoxy resin turn into one of main film forming matter of anti-corrosion primer.But it is low Molecule epoxy resin solidification physical property is crisp, easy to crack；Epoxy resin is poor with the wet adhesion of base material simultaneously.It is logical Processed frequently with ground, be heating and curing, the method such as corrosion inhibiter, coupling agent improves epoxy coating adhesive force, but All have some limitations.
Both at home and abroad multiple studies have shown that, be a kind of highly effective method using nanometer particle-modified epoxy.It Adhesion of epoxy resin can be not only effectively improved, toughness, decay resistance, the surface of coating can be also improved Performance etc., overcomes the epoxy resin technical barrier that performance is reduced in itself.But nanoparticle surface product is big, easy group Poly-, epoxy resin polarity is big, viscosity is high, makes it be difficult to be uniformly dispersed, and directly affects nano-particle in coating Application particularly in high solid coating.To improve this state, can be led to according to the property of nano-particle Cross nano-particle is modified, dispersant, various process for dispersing combination etc. method process.
Chinese patent " a kind of epoxy nano composite anticorrosion coating for low surface treatment and preparation method thereof " (application Number：CN200810010985.0) it is related to a kind of epoxy nano composite anticorrosion coating for low surface treatment and its preparation Method.The coating be the component of first, second two composition, by epoxy resin, nano combined mother liquor, corrosion stabilizer, Rust resisting pigment, filler, levelling agent and mixed solvent etc. are prepared in proportion, are dispersed through, ground and be configured to first group Point；Phenolic aldehyde amine, polyamide and mixed solvent is replaced to be configured to second component long-chain；Again by first component and second group Divide mixing cured, be prepared into nano composite anticorrosion coating for low surface treatment.The patent epoxy low prepared surface is received Rice composite anticorrosion coating is low to metallic substrate surface processing requirement, strong with metal base adhesion, with other paintings Material matching is good.But coating is in the case of with other coatings systems, even if during thick film application, antiseptic property Also do not protrude, such as salt spray resistance is 4000h, and wet-heat resisting is only 1500h.
The content of the invention
The purpose of the present invention is to propose to a kind of nanometer modified high-solid body point epoxy primer, the priming paint is greatly improved The wet adhesion and pliability of coating, and then greatly improve the decay resistance of coating.
In view of the above mentioned problem of prior art, according to one side disclosed by the invention, the present invention use with Lower technical scheme：
A kind of nanometer modified high-solid body point epoxy primer, is 100: 20~50 by two components by weight Ratio is mixed；Component one is by nanometer modified epoxy resin, Chrome-free anticorrosive pigment/filler, auxiliary agent and organic molten Agent etc. is constituted, and the weight part ratio of its raw material is 20~45: 25~50: 1~5: 15~30；Component two is solid Agent.
The preparation method of described nanometer modified epoxy resin is：First by weight part ratio be 100: 1~3: 0~ Nano-powder and accelerator stirring that 0.2 epoxy resin solution, silane resin acceptor kh-550 are surface-treated Uniformly, ultrasonically treated 10~20min, 12~24h of room temperature, obtain modified product；Again by modified product It is by weight 100: 10~40 mixing with epoxide resin reactive diluent, obtains nanometer modified epoxy tree Fat.
Described epoxy resin is E51, and epoxide resin reactive diluent is 501 or 692.
Described nano-powder is nano silicon, nano titanium oxide, nano-sized iron oxide, nano oxidized One or more in zinc.
Described Chrome-free anticorrosive pigment/filler be trbasic zinc phosphate, modified zinc phosphate, aluminium triphosphate, platy talc, One or more in flaky mica powder, coloring pigment, aerosil.
Described auxiliary agent is one or more in wetting dispersing agent, surface leveling agents, defoamer.
Described solvent is the one kind or several in dimethylbenzene, butyl acetate, ethyl acetate, butanone, cyclohexanone Kind.
Curing agent is cashew nut phenols epoxy hardener.
The present invention has the advantage that and beneficial effect：
1st, mechanical property is excellent：The coating formed after the coating application is good in the metal surface such as steel, aluminium adhesive force, More than 20MPa is reached, pliability is 1mm, more than impact strength 70cm；
2nd, wet adhesion is excellent：After the coating soaks 30d in water, wet adhesion still reaches more than 18MPa；
3rd, antiseptic property is excellent：After the curing of coatings, salt fog resistance, humidity resistance reach more than 5000h；
4th, environmental protection：Construction solid point is up to 70%, and solvent discharge is few.
Specific embodiment
The present invention is described in further detail with reference to embodiment, but embodiments of the present invention are not limited In this.
Nanometer modified high-solid body is divided to the ratio that epoxy primer is 100: 20~50 by two components by weight Mix；Component one is by nanometer modified epoxy resin, Chrome-free anticorrosive pigment/filler, auxiliary agent and organic solvent etc. Composition, the weight part ratio of its raw material is 20~45: 25~50: 1~5: 15~35；Nanometer modified epoxy tree The preparation method of fat is：First by weight part ratio for 100: 1~3: 0~0.2 epoxy resin solution, silane The nano-powder and accelerator that coupling agent KH-550 is surface-treated stir, ultrasonically treated 10~20min, 12~24h of room temperature, obtains modified product, then by modified product and epoxide resin reactive diluent by weight Part obtains nanometer modified epoxy resin than being 100: 10~40 mixing.Epoxy resin is E51, epoxy resin Reactive diluent is 501 or 692.Chrome-free anticorrosive pigment/filler be trbasic zinc phosphate, modified zinc phosphate, aluminium triphosphate, One or more in platy talc, flaky mica powder, coloring pigment, aerosil；Auxiliary agent is One or more in wetting dispersing agent, surface leveling agents, defoamer；Solvent be dimethylbenzene, butyl acetate, One or more in ethyl acetate, butanone, cyclohexanone；Component two is cashew nut phenols epoxy hardener.
The preparation method of nanometer modified high-solid body point epoxy primer component one as described above, its preparation process It is as follows：
1st, color stuffing is dried；All color stuffings are toasted 2 hours in all should being respectively put into 110 DEG C of drying boxes, are dried It is roasting to finish, it is to be cooled to closed preservation after room temperature；
2nd, nanometer modified epoxy resin is prepared：First by weight part ratio for 100: 1~3: 0~0.2 E51 rings The nano-powder and accelerator that oxygen tree lipoprotein solution, silane resin acceptor kh-550 are surface-treated stir, Ultrasonically treated 10~20min, 12~24h of room temperature, obtain modified product, then by modified product and epoxy Resin reactive diluents 501 or 692 are by weight 100: 10~40 mixing, obtain nano modification ring Oxygen tree fat.
3rd, color stuffing is weighed：Ratio according to formulation for coating material weighs various raw materials respectively；
4th, dispensing：The color stuffing that will be weighed mixes in being put into container, then mixes with resin solution, and stir Uniformly；
5th, grind：Slurry after stirring is ground in adding sand mill, is co-mulled and made into 2~3 times, In process of lapping, remaining solvent is added step-wise in grinding charge material, grinding forms component one after finishing, Packaging.
When using, two components are reconciled in proportion.
Embodiment 1：
Nanometer modified high-solid body is divided to epoxy primer by two components by weight for 100: 25 ratio mixes Form；Component one is made up of nanometer modified epoxy resin, Chrome-free anticorrosive pigment/filler, auxiliary agent and organic solvent etc., The weight part ratio of its raw material is 25: 43: 2: 30；The preparation of nanometer modified epoxy resin：First by weight part ratio Epoxy resin E51 solution, the nanometer that is surface-treated of silane resin acceptor kh-550 for 100: 1: 0.1 Silicon-dioxide powdery and accelerator stir, ultrasonically treated 10min, room temperature 24h, obtain modified product Thing, then be by weight 100: 25 mixing by modified product and epoxide resin reactive diluent 501, obtain To nanometer modified epoxy resin；Chrome-free anticorrosive pigment/filler be trbasic zinc phosphate, aluminium triphosphate, flaky mica powder, Coloring pigment, aerosil；Auxiliary agent is wetting dispersing agent, surface leveling agents, defoamer；Solvent is Dimethylbenzene, butyl acetate, butanone；Component two is cashew nut phenols epoxy hardener.The specific weight of component one is such as Shown in following table：
Embodiment 2：
Nanometer modified high-solid body is divided to epoxy primer by two components by weight for 100: 35 ratio mixes Form；Component one is made up of nanometer modified epoxy resin, Chrome-free anticorrosive pigment/filler, auxiliary agent and organic solvent etc., The weight part ratio of its raw material is 30: 42: 3: 25；The preparation of nanometer modified epoxy resin：First by weight part ratio Epoxy resin E51 solution, the nanometer that is surface-treated of silane resin acceptor kh-550 for 100: 2: 0.1 Titanium dioxide and accelerator stir, ultrasonically treated 10min, and room temperature 24h obtains modified product, It is by weight again 100: 20 mixing by modified product and epoxide resin reactive diluent 692, is received Rice modified epoxy；Chrome-free anticorrosive pigment/filler be modified zinc phosphate, aluminium triphosphate, platy talc, Coloring pigment, aerosil；Auxiliary agent is wetting dispersing agent, surface leveling agents, defoamer；Solvent is Butyl acetate, ethyl acetate, cyclohexanone；Component two is cashew nut phenols epoxy hardener.Component one is specifically heavy Amount is as shown in the table：
Embodiment 3：
Nanometer modified high-solid body is divided to epoxy primer by two components by weight for 100: 45 ratio mixes Form；Component one is made up of nanometer modified epoxy resin, Chrome-free anticorrosive pigment/filler, auxiliary agent and organic solvent etc., The weight part ratio of its raw material is 30: 41: 4: 25；The preparation of nanometer modified epoxy resin：First by weight part ratio Epoxy resin E51 solution, the nanometer that is surface-treated of silane resin acceptor kh-550 for 100: 3: 0.1 Iron oxide and accelerator stir, ultrasonically treated 10min, and room temperature 24h obtains modified product, then It is by weight 100: 35 mixing by modified product and epoxide resin reactive diluent 501, obtains nanometer Modified epoxy；Chrome-free anticorrosive pigment/filler is trbasic zinc phosphate, aluminium triphosphate, platy talc, sheet cloud Female powder, coloring pigment, aerosil；Auxiliary agent is wetting dispersing agent, surface leveling agents, defoamer； Solvent is butyl acetate, ethyl acetate, cyclohexanone；Component two is cashew nut phenols epoxy hardener.Component one Specific weight is as shown in the table：
Embodiment 1, embodiment 2 and the coating overall performance of embodiment 3 are as follows：

Claims (3)

1. a kind of nanometer modified high-solid body divides epoxy primer, it is characterised in that the high-solid epoxy resin priming paint By two components by weight for 100: 20~50 ratio is mixed；Component one is by nanometer modified epoxy Resin, Chrome-free anticorrosive pigment/filler, auxiliary agent and organic solvent composition, the weight part ratio of its raw material is 20~45: 25~50: 1~5: 15~30；Component two is curing agent.
The preparation method of described nanometer modified epoxy resin is：First by weight part ratio be 100: 1~3: 0~ Nano-powder and accelerator stirring that 0.2 epoxy resin solution, silane resin acceptor kh-550 are surface-treated Uniformly, ultrasonically treated 10~20 minutes, room temperature 12~24 hours obtained modified product；Again will be modified Product and epoxide resin reactive diluent are by weight 100: 10~40 mixing, obtain nanometer modified epoxy Resin；
Described Chrome-free anticorrosive pigment/filler be trbasic zinc phosphate, modified zinc phosphate, aluminium triphosphate, platy talc, One or more in flaky mica powder, coloring pigment, aerosil；
Described auxiliary agent is one or more in wetting dispersing agent, surface leveling agents, defoamer；
Described organic solvent is the one kind in dimethylbenzene, butyl acetate, ethyl acetate, butanone, cyclohexanone Or it is several；
Described curing agent is cashew nut phenols epoxy hardener.
2. a kind of nanometer modified high-solid body according to claim 1 divides epoxy primer, it is characterised in that Described epoxy resin solution is the E51 epoxy resin and 20% organic solvent of weight part ratio 80%, described ring Oxygen resin reactive diluents are 501 or 692.
3. a kind of nanometer modified high-solid body according to claim 1 divides epoxy primer, it is characterised in that The nano-powder that the silane resin acceptor kh-550 is surface-treated is nano silicon, nanometer titanium dioxide One or more in titanium, nano-sized iron oxide, nano zine oxide.
CN201510920753.9A 2015-12-11 2015-12-11 A kind of nanometer modified high-solid body divides epoxy primer Active CN106867357B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107446443A (en) * 2017-09-06 2017-12-08 王维维 A kind of switch status display device three-proofing coating
CN108676472A (en) * 2018-06-05 2018-10-19 苏州加减士空间设计装饰工程有限公司 A kind of macromolecular antiseptic organic coating
CN108795226A (en) * 2018-05-04 2018-11-13 砺剑防务技术集团有限公司 Poly- silicon ceramics Anti-ice paint and preparation method thereof
CN116875102A (en) * 2023-08-02 2023-10-13 广州工程技术职业学院 Modified filler, antirust protective paint, and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1844271A (en) * 2006-04-28 2006-10-11 彭志伟 Nano modified anti-rust special primer
CN1887992A (en) * 2006-07-19 2007-01-03 江苏中矿大正表面工程技术有限公司 Nanometer modified epoxy sealing paint and its prepn
CN102690496A (en) * 2012-06-08 2012-09-26 苏州巨峰电气绝缘系统股份有限公司 Nano modified epoxy vacuum pressure impregnation resin and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1844271A (en) * 2006-04-28 2006-10-11 彭志伟 Nano modified anti-rust special primer
CN1887992A (en) * 2006-07-19 2007-01-03 江苏中矿大正表面工程技术有限公司 Nanometer modified epoxy sealing paint and its prepn
CN102690496A (en) * 2012-06-08 2012-09-26 苏州巨峰电气绝缘系统股份有限公司 Nano modified epoxy vacuum pressure impregnation resin and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107446443A (en) * 2017-09-06 2017-12-08 王维维 A kind of switch status display device three-proofing coating
CN108795226A (en) * 2018-05-04 2018-11-13 砺剑防务技术集团有限公司 Poly- silicon ceramics Anti-ice paint and preparation method thereof
CN108676472A (en) * 2018-06-05 2018-10-19 苏州加减士空间设计装饰工程有限公司 A kind of macromolecular antiseptic organic coating
CN116875102A (en) * 2023-08-02 2023-10-13 广州工程技术职业学院 Modified filler, antirust protective paint, and preparation method and application thereof
CN116875102B (en) * 2023-08-02 2024-04-12 广州工程技术职业学院 Modified filler, antirust protective paint, and preparation method and application thereof

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