CN112480779A - Polyester and epoxy resin powder coating modified by organic composite antibacterial agent and preparation method thereof - Google Patents

Polyester and epoxy resin powder coating modified by organic composite antibacterial agent and preparation method thereof Download PDF

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Publication number
CN112480779A
CN112480779A CN202011309223.8A CN202011309223A CN112480779A CN 112480779 A CN112480779 A CN 112480779A CN 202011309223 A CN202011309223 A CN 202011309223A CN 112480779 A CN112480779 A CN 112480779A
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CN
China
Prior art keywords
antibacterial agent
solid
agent
epoxy resin
modified polyester
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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.)
Pending
Application number
CN202011309223.8A
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Chinese (zh)
Inventor
刘骏
蔡璐
杨晓龙
梁成桂
曾妮
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Hunan Taizi Chemical Coatings Co ltd
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Hunan Taizi Chemical Coatings Co ltd
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Application filed by Hunan Taizi Chemical Coatings Co ltd filed Critical Hunan Taizi Chemical Coatings Co ltd
Priority to CN202011309223.8A priority Critical patent/CN112480779A/en
Publication of CN112480779A publication Critical patent/CN112480779A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D167/00Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03Powdery paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14Paints containing biocides, e.g. fungicides, insecticides or pesticides

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

Abstract

The invention relates to a polyester and epoxy resin powder coating modified by organic composite antibacterial agent and a preparation method thereof, comprising the following raw material components, by weight, 25-35% of solid epoxy resin, 25-35% of solid modified polyester resin, 5-15% of solid pigment, 2-3% of solid auxiliary agent and 15-30% of solid filler, wherein the preparation method of the solid modified polyester resin comprises the steps of adding rare earth composite antibacterial agent into the polyester resin to obtain the solid modified polyester resin, wherein the weight of the composite antibacterial agent is 2-8% of the weight of the polyester resin; the composite antibacterial agent comprises, by weight, 30-40% of a rare earth antibacterial agent and 60-70% of an organic antibacterial agent, wherein the rare earth antibacterial agent is a rare earth chloride, and the organic antibacterial agent is a mixture of chlorhexidine and dimethyl fumarate.

Description

Polyester and epoxy resin powder coating modified by organic composite antibacterial agent and preparation method thereof
Technical Field
The invention belongs to the technical field of powder coating preparation, and particularly relates to an organic composite antibacterial agent modified polyester and epoxy resin powder coating and a preparation method thereof.
Background
The powder coating is a novel solid powder coating which is prepared by mixing resin, a curing agent, pigment, filler, an auxiliary agent and the like, coating the mixture on the surface of a coated object in an electrostatic spraying mode, and then baking the mixture to melt, level and solidify the mixture. The paint does not use solvent, has the characteristics of environmental protection, recoverability, energy and resource conservation, lower labor intensity, high mechanical strength of film coating, strong corrosion resistance and the like, and becomes well-known 4E type (high production efficiency, excellent film coating performance, ecological environmental protection and economy) paint.
Epoxy powder coatings were thermosetting powder coatings developed in the last century. The film forming material epoxy resin has excellent physical and mechanical properties, and the coating film has good adhesion to a substrate, good electrical insulation and excellent chemical corrosion resistance. The coating is widely applied to the internal and external corrosion prevention of chemical industry, electrical appliances, instruments, machinery and transportation pipelines, and occupies a leading position in anticorrosive coatings. However, due to the characteristics of the epoxy resin, the epoxy powder coating has poor weather resistance and abrasion resistance in practical application, and a coating film is easy to pulverize, so that the epoxy powder coating is not suitable for outdoor coating, and the application of the epoxy powder coating is limited.
Chinese patent application No. CN201810147627.8 discloses an environment-friendly antibacterial fingerprint-resistant ultrafine powder coating, which consists of modified powder A and ultrafine base powder B: the formula of the modified powder A is as follows in parts by weight: 1.5-4 parts of rare earth chloride, 1.5-4 parts of o-hydroxy azonaphthalene, 0.6-2 parts of 4-hydroxy sodium benzoate and 0.4-3 parts of a coupling agent; the formula of the superfine base powder B is as follows in parts by weight: 25-40 parts of epoxy resin, 25-40 parts of polyester resin, 30-50 parts of filler, 0.5-1.5 parts of flatting agent, 0.2-2 parts of hardening agent, 0.5-0.8 part of defoaming agent and 0-3 parts of pigment. The rare earth chloride is added to be cerium chloride or composite rare earth chloride containing cerium chloride. In the field of biochemical research, the rare earth compound and the rare earth organic complex have excellent antibacterial and bacteriostatic effects.
Disclosure of Invention
The invention aims to provide an organic composite antibacterial agent modified polyester and epoxy resin powder coating and a preparation method thereof, which have good adhesion and toughness and good antibacterial performance.
The invention relates to an organic composite antibacterial agent modified polyester and epoxy resin powder coating, which comprises the following raw material components, by weight, 25-35% of solid epoxy resin, 25-35% of solid modified polyester resin, 5-15% of solid pigment, 2-3% of solid auxiliary agent and 15-30% of solid filler, wherein the preparation method of the solid modified polyester resin comprises the steps of adding a rare earth composite antibacterial agent into the polyester resin to obtain the solid modified polyester resin, wherein the weight of the composite antibacterial agent is 2-8% of the weight of the polyester resin; the composite antibacterial agent comprises, by weight, 30-40% of a rare earth antibacterial agent and 60-70% of an organic antibacterial agent, wherein the rare earth antibacterial agent is rare earth chloride, and the organic antibacterial agent is a mixture of chlorhexidine and dimethyl fumarate.
Preferably, the paint comprises the following raw material components, by weight, 30% of solid epoxy resin, 30% of solid polyurethane resin, 15% of solid pigment, 3% of solid auxiliary agent and 22% of solid filler.
Preferably, the weight ratio of the chlorhexidine to the dimethyl fumarate is 2: 1.
Preferably, the solid auxiliary agent further comprises a leveling agent, a brightening agent, a defoaming agent, an anti-wear agent, a delustering agent and a dispersing agent.
Preferably, the solid filler comprises, by weight, 20-40% of nickel chloride, 20-40% of sodium tungstate, 10-30% of aniline, and 10-30% of phosphoric acid.
Preferably, the solid pigment comprises one or more of titanium dioxide, carbon black, permanent yellow, iron red, phthalocyanine blue, permanent red and phthalocyanine green.
The invention provides a preparation method of organic composite antibacterial agent modified polyester and epoxy resin powder coating, which comprises the following steps,
1) after the materials are prepared, mixing and stirring the raw materials;
2) pouring the stirred raw materials into an extruder, controlling the temperature of the extruder at 100-120 ℃ to melt the raw materials, and then tabletting and crushing the raw materials;
3) and pouring the crushed materials into a powder cutting machine, and grinding into powder of 30-45 mu m to obtain the organic composite antibacterial agent modified polyester and epoxy resin powder coating.
The stirring time was 5 min.
The temperature of the extruder was controlled at 115 ℃.
The particle size of the material crushed in the step 2) is 150-300 mu m.
The invention has the beneficial effects that the common powder coating uses inorganic antibacterial agents generally, the antibacterial capability is single, and the invention adopts the polyester resin modified by the composite antibacterial agent, and improves the performance and the application range of the antibacterial agent through the synergy and the advantage complementation.
The composite antibacterial agent is prepared by combining two or more of the single antibacterial agent and other antibacterial agents in order to solve the problem of insufficient antibacterial performance of the single antibacterial agent, so that the composite antibacterial agent has a stronger antibacterial function and can prolong the antibacterial time of materials.
The powder coating has the antibacterial and bactericidal capability and can be used in medical care equipment and hospital facilities.
Detailed Description
The various chemicals and reagents used in the examples of the present invention were all commercially available.
Example 1
The organic composite antibacterial agent modified polyester and epoxy resin powder coating comprises the following raw material components, by weight, 30% of solid epoxy resin, 30% of solid polyurethane resin, 15% of solid pigment, 3% of solid auxiliary agent and 22% of solid filler, wherein the preparation method of the solid modified polyester resin comprises the steps of adding a rare earth composite antibacterial agent into the polyester resin to obtain the solid modified polyester resin, wherein the weight of the composite antibacterial agent is 5% of the weight of the polyester resin; the composite antibacterial agent comprises 30 wt% of rare earth antibacterial agent and 70 wt% of organic antibacterial agent, wherein the rare earth antibacterial agent is rare earth chloride, and the organic antibacterial agent is a mixture of chlorhexidine and dimethyl fumarate (the weight ratio is 2: 1).
The solid auxiliary agent also comprises a flatting agent, a brightening agent, a defoaming agent, an anti-wear agent, a delustering agent and a dispersing agent.
The solid pigment comprises iron yellow.
The solid filler comprises 30 weight percent of nickel chloride, 30 weight percent of sodium tungstate, 20 weight percent of aniline and 20 weight percent of phosphoric acid.
The invention provides a preparation method of epoxy resin and carboxyl polyester powder coating, which comprises the following steps,
1) after the materials are prepared, mixing the raw materials, and stirring for 5 min;
2) pouring the stirred raw materials into an extruder, controlling the temperature of the extruder at 115 ℃ to melt the raw materials, and then tabletting and crushing the raw materials, wherein the particle size of the crushed materials is 150-300 mu m;
3) and pouring the crushed materials into a powder shearing machine, and grinding into powder of 30-45 mu m to obtain the high-strength anticorrosive wear-resistant powder coating.
Comparative example 1
The present comparative example 1 is different from example 1 in that only the rare earth chloride is added and the organic antibacterial agent is not added, i.e., the composite antibacterial agent is composed of the rare earth antibacterial agent. The rest is the same as in example 1.
Comparative example 2
Comparative example 2 differs from example 1 in that the temperature of the extruder in step 2) was 100 ℃ in the preparation of the powder coating, and the material was not tabletted but directly pulverized after extrusion. The rest is the same as in example 1.
The powder coatings obtained in example 1 and comparative examples 1-2 were compared to obtain a table of results of performance tests as shown in Table 1.
Table 1 table of performance test results
Test items Example 1 Comparative example 1 Comparative example 2
Film thickness 60-100μm 80-120μm 70-100μm
Storage stability (three weeks at 40 ℃ C.) Without agglomeration Without agglomeration Slightly agglomerated
Particle size 32-38μm 30-40μm 30-40μm
Impact resistance (front and back 50 kg/cm)2) Does not crack Does not crack Cracking of
Adhesion force Level 1 Level 1 Stage 2
Antibacterial property Qualified Fail to be qualified Qualified
From the analysis of the above table 1, it can be seen that the impact resistance of the present example 1 is strong, the storage stability is significantly better than that of the comparative example, and the adhesion and antibacterial performance are better.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The organic composite antibacterial agent modified polyester and epoxy resin powder coating is characterized by comprising the following raw materials, by weight, 25-35% of solid epoxy resin, 25-35% of solid modified polyester resin, 5-15% of solid pigment, 2-3% of solid auxiliary agent and 15-30% of solid filler, wherein the preparation method of the solid modified polyester resin comprises the steps of adding a rare earth composite antibacterial agent into the polyester resin to obtain the solid modified polyester resin, and the weight of the composite antibacterial agent is 2-8% of the weight of the polyester resin; the composite antibacterial agent comprises, by weight, 30-40% of a rare earth antibacterial agent and 60-70% of an organic antibacterial agent, wherein the rare earth antibacterial agent is rare earth chloride, and the organic antibacterial agent is a mixture of chlorhexidine and dimethyl fumarate.
2. The modified polyester and epoxy resin powder coating as claimed in claim 1, which comprises the following raw materials (by weight percent), solid epoxy resin 30%, solid polyurethane resin 30%, solid pigment 15%, solid assistant 3%, and solid filler 22%.
3. The organic composite antibacterial agent-modified polyester and epoxy resin powder coating material as claimed in claim 1, wherein the weight ratio of chlorhexidine to dimethyl fumarate is 2: 1.
4. The organic composite antibacterial agent modified polyester and epoxy resin powder coating as claimed in claim 1, wherein the solid auxiliary agent further comprises leveling agent, brightening agent, defoaming agent, wear-resistant agent, matting agent and dispersing agent.
5. The organic composite antibacterial agent modified polyester and epoxy resin powder coating as claimed in claim 1, wherein the solid filler comprises, by weight, 20-40% of nickel chloride, 20-40% of sodium tungstate, 10-30% of aniline, and 10-30% of phosphoric acid.
6. The organic composite antibacterial agent modified polyester and epoxy resin powder coating as claimed in any one of claims 1 to 5, wherein the solid pigment comprises one or more of titanium dioxide, carbon black, permanent yellow, iron red, phthalocyanine blue, permanent red and phthalocyanine green.
7. A method for preparing the organic composite antibacterial agent modified polyester and epoxy resin powder coating as claimed in any one of claims 1 to 6, characterized by comprising the steps of,
1) after the materials are prepared, mixing and stirring the raw materials;
2) pouring the stirred raw materials into an extruder, controlling the temperature of the extruder at 100-120 ℃ to melt the raw materials, and then tabletting and crushing the raw materials;
3) and pouring the crushed materials into a powder cutting machine, and grinding into powder of 30-45 mu m to obtain the organic composite antibacterial agent modified polyester and epoxy resin powder coating.
8. The process according to claim 7, wherein the stirring is carried out for 5 min.
9. The process according to claim 7 or 8, wherein the temperature of the extruder is controlled to 115 ℃.
10. The process according to claim 7 or 8, wherein the particle size of the pulverized material obtained in step 2) is 150-300 μm.
CN202011309223.8A 2020-11-20 2020-11-20 Polyester and epoxy resin powder coating modified by organic composite antibacterial agent and preparation method thereof Pending CN112480779A (en)

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Application Number Priority Date Filing Date Title
CN202011309223.8A CN112480779A (en) 2020-11-20 2020-11-20 Polyester and epoxy resin powder coating modified by organic composite antibacterial agent and preparation method thereof

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114574024A (en) * 2022-03-07 2022-06-03 广东依斯特新材料有限公司 Preparation method and application of thermosetting powder coating

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1462785A (en) * 2003-06-02 2003-12-24 攀枝花钢铁有限责任公司钢铁研究院 Antibiotic type coating material of polyester-epoxy resin powder modified by inorganic nano composite antimicrobial, and its prepn. method
CN101665652A (en) * 2009-07-30 2010-03-10 老虎粉末涂料制造(太仓)有限公司 Powder coating with antibacterial function and preparation method and application thereof
CN101928506A (en) * 2010-08-27 2010-12-29 四川大学 Long-acting antibacterial nano composite modified epoxy-polyester powder coating and preparation method thereof
CN109651938A (en) * 2018-12-14 2019-04-19 佛山市顺德区蓝天实业有限公司 A kind of high-environmental powdery paints
CN109679392A (en) * 2018-12-04 2019-04-26 东北石油大学 A kind of anti-corrosion anti-attrition powdery paints and preparation method thereof
CN109749499A (en) * 2018-12-04 2019-05-14 东北石油大学 A kind of anticorrosion antiwear aqueous functional filler and the anticorrosion antiwear water paint using it
CN111763464A (en) * 2020-06-15 2020-10-13 湖南连心科技有限公司 Antibacterial powder coating and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1462785A (en) * 2003-06-02 2003-12-24 攀枝花钢铁有限责任公司钢铁研究院 Antibiotic type coating material of polyester-epoxy resin powder modified by inorganic nano composite antimicrobial, and its prepn. method
CN101665652A (en) * 2009-07-30 2010-03-10 老虎粉末涂料制造(太仓)有限公司 Powder coating with antibacterial function and preparation method and application thereof
CN101928506A (en) * 2010-08-27 2010-12-29 四川大学 Long-acting antibacterial nano composite modified epoxy-polyester powder coating and preparation method thereof
CN109679392A (en) * 2018-12-04 2019-04-26 东北石油大学 A kind of anti-corrosion anti-attrition powdery paints and preparation method thereof
CN109749499A (en) * 2018-12-04 2019-05-14 东北石油大学 A kind of anticorrosion antiwear aqueous functional filler and the anticorrosion antiwear water paint using it
CN109651938A (en) * 2018-12-14 2019-04-19 佛山市顺德区蓝天实业有限公司 A kind of high-environmental powdery paints
CN111763464A (en) * 2020-06-15 2020-10-13 湖南连心科技有限公司 Antibacterial powder coating and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114574024A (en) * 2022-03-07 2022-06-03 广东依斯特新材料有限公司 Preparation method and application of thermosetting powder coating

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Application publication date: 20210312

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