CN106010044B - A kind of self-cleaning anti-pollution coating of the bullet train containing micro biological bactericide - Google Patents

A kind of self-cleaning anti-pollution coating of the bullet train containing micro biological bactericide Download PDF

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CN106010044B
CN106010044B CN201610454919.7A CN201610454919A CN106010044B CN 106010044 B CN106010044 B CN 106010044B CN 201610454919 A CN201610454919 A CN 201610454919A CN 106010044 B CN106010044 B CN 106010044B
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bullet train
containing micro
cleaning anti
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CN106010044A (en
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陆阿定
胡建坤
李娟�
宋伟
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Zhejiang Marine Development Research Institute
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Zhejiang Marine Development Research Institute
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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
    • 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
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • 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
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Plant Pathology (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to a kind of antifouling paint, more particularly to a kind of self-cleaning anti-pollution coating of the bullet train containing micro biological bactericide.A kind of bullet train self-cleaning anti-pollution coating containing micro biological bactericide, which be mixed to prepare with second component by first component as follows based on mass fraction：First component：Ternary random copolymerization acrylic resin 40 50%, hydroxy silicon oil 4 8%, fluorocarbon resin 2 6%, acrylamide 2 5%, adhesion promoter 2 8%, triphenylboron pyridine 3 5%, zineb 3 5%, talcum powder 3 5%, titanium dioxide 15 25%, pigment 0 8%, polyamide wax pulp 1 6%；Second component：Aliphatic isocyanates tripolymer, wherein first component and the mass ratio of second component are 24:1.

Description

A kind of self-cleaning anti-pollution coating of the bullet train containing micro biological bactericide
Technical field
The present invention relates to a kind of antifouling paint, more particularly to a kind of bullet train containing micro biological bactericide is with self-cleaning Antifouling paint.
Background technology
With the rapid development of the national economy, bullet train traffic coverage and operating mileage are continuously increased.In operational process In, bullet train surface can be by multiple pollutant (such as：Dust, soil, rainwater etc.) adhesion and pollution, to ensure vehicle (especially develop swift and violent high ferro and motor-car in recent years) aesthetic in appearance, need to clean vehicle crust daily, so both waste of manpower, Material resources, but it is larger to the damage of vehicle paint.
Bullet train self-cleaning anti-pollution railway coating is researched and developed, can not only meet bullet train and the high-performance of coating is wanted It asks, while there is technology to promote the meaning improved with industry for the development of the rapid development and China's coating to railway traffic transport Justice.For a long time, known self-cleaning anti-pollution coating is mainly used in the fields such as building, ceramic sanitary appliance, anti-fouling paint peculiar to vessel, closely Nian Lai is gradually expanded in the application range of train.It is mainly used in railcar in foreign countries, and application range and circuit have Limit, is mainly used for anti-graffiti function.The show-how and technology application of domestic Related product not yet, in state-owned railroads standard Also the performance indicator without self-cleaning anti-pollution coating requires and relevant technical checking method.
Invention content
The purpose of the present invention is to provide a kind of self-cleaning anti-pollution coating of the bullet train containing micro biological bactericide, should Coating self-cleaning characteristic with high performance.
The technical solution adopted by the present invention to solve the technical problems is：
A kind of bullet train self-cleaning anti-pollution coating containing micro biological bactericide, the coating be by as follows with The first component of mass fraction meter is mixed to prepare with second component：First component：
Second component：Aliphatic isocyanates tripolymer, wherein first component and the mass ratio of second component are 2-4:1.
First and second components are mixed according to certain mass ratio, are constructed after stirring evenly, as bullet train is applied with self-cleaning anti-pollution Material.Pigment can be selected according to color selection requirements specific to property.
Preferably, the pigment is selected from phthalocyanine blue, lemon yellow or one or more of indigo.
Preferably, the ternary random copolymerization acrylic resin is made by raw material as follows based on mass fraction：
The ternary random copolymerization acrylic resin is compounded by rational component, to realize sterilizing function, to ring Border is friendly, is free of poisonous and harmful substance, waterproof.
Preferably, ternary random copolymerization acrylic resin is made by following methods：Equipped with blender, reflux condensation mode It manages, azodiisobutyronitrile, lauryl mercaptan, butyl acetate is added in the four-hole boiling flask of constant pressure funnel, be warming up to after mixing 100-110 DEG C, hydroxy-ethyl acrylate, acrylic acid trichlorine phenyl ester, butyl acrylate, isobornyl acrylate, azo is then added The mixed liquor of bis-isobutyronitrile and azobisisovaleronitrile, the wherein addition of azobisisovaleronitrile are the 90%-95% of formula ratio, are used Constant pressure funnel was added dropwise through 2.5-3 hours constant speed, added the azobisisovaleronitrile of surplus, continued isothermal reaction 0.5- After 0.6 hour, it is warming up to 110-115 DEG C, after the reaction was continued 2.5-3 hours, is cooled to room temperature, it is random that ternary is obtained by the reaction in completion Co-polypropylene acid resin.By the preparation of this law, a kind of special biological antibiotic type acrylic acid tree with sterilizing function is obtained Fat, the order of addition and temperature of each raw material, the control of time, to product obtain playing the role of it is vital.Azo two is different Valeronitrile is added in two portions, can to avoid by-product generate and obtain properties of product more preferably, quality comparison temperature.
The beneficial effects of the invention are as follows：The present invention is to combine other necks based on the research and development experience of self-cleaning anti-pollution paint peculiar to vessel The antifouling sterilization technology in domain, to have developed high performance self-cleaning anti-pollution coating system.
The invention is characterized in that：
(1) a kind of Hydroxylated acrylic resin containing micro biological bactericide is introduced in matrix resin system, makes resin Matrix is provided with sterilization anti-fouling effect；
(2) a kind of hydroxy silicon oil is introduced using chemical reaction, so that resin is had and be stained desorption ability, while has improved The stability of machine silicone elastomer；
(3) it is crosslinking agent using appropriate aliphatic isocyanates tripolymer, improves the compactness of paint film, enhance paint film Water resistance and surface gloss；
(4) weatherability of paint film is improved using fluorocarbon resin；
(5) adhesive force of resin is improved using the butadiene-styrene rubber adhesive of high molecular weight.
Specific implementation mode
Below by specific embodiment, technical scheme of the present invention will be further explained in detail.It should be appreciated that this hair Bright implementation is not limited to the following examples, and the accommodation in any form made to the present invention and/or changed will all be fallen Enter the scope of the present invention.
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, used equipment and raw material etc. It is commercially available or commonly used in the art.Method in following embodiments is unless otherwise instructed the normal of this field Rule method.
The synthesis of 1 ternary random copolymerization acrylic resin (PAA) of embodiment
The formula of ternary random copolymerization acrylic resin is shown in Table 1, equipped with blender, reflux condensing tube, constant pressure addition leakage 0.2g azodiisobutyronitriles (AIBN), 2.0g lauryl mercaptans, 200g butyl acetates are added in the four-hole boiling flask of bucket, is risen after mixing Then temperature is weighed to 100 DEG C comprising 12g hydroxy-ethyl acrylates, 37g acrylic acid trichlorine phenyl ester, 100g butyl acrylates, 51g third The mixed liquor of olefin(e) acid isobornyl thiocyanoacetate, 1.7g azodiisobutyronitriles and 1.7g azobisisovaleronitrile, with constant pressure funnel through 3 hours Constant speed is added dropwise, and adds 0.1g azobisisovaleronitrile, after continuing isothermal reaction 0.5 hour, is warming up to 110 DEG C, continues anti- It after answering 2.5 hours, is cooled to room temperature, completes reaction.Reaction route is shown below：
It is detected through IR and GPC, the biological antibiotic type acrylic resin double bond of the present embodiment polymerize completely, number-average molecular weight Mn It is 7128, weight average molecular weight 16964, polydispersity coefficient Mw\MnIt is 2.38.
The raw material that embodiment 1-3 is used is shown in Table 1.
Table 1
The synthesis of embodiment 2-3 ternary random copolymerization acrylic resins (PAA)
The formula of ternary random copolymerization acrylic resin is shown in Table 1, and specific method is different with embodiment 1, wherein raw material azo two Valeronitrile is put at twice, and the addition of first time azobisisovaleronitrile is the 90%-95% of formula ratio, and surplus is added for the second time Azobisisovaleronitrile.
Embodiment 4
A kind of self-cleaning anti-pollution coating of the bullet train containing micro biological bactericide, the coating are by first component and second group Divide and is mixed to prepare, white, the light blue and green bullet train containing micro biological bactericide antifouling paint first component formula Composition is shown in Table 2, and second component is aliphatic isocyanates tripolymer (Bayer Bayer N3390).The hydroxyl silicon selected in this formula The molecular weight of oil is 5000.
2 (unit of table：kg)
The mass ratio of first component and component B is 3:1, it constructs after stirring evenly.
After testing, bullet train of the invention is as shown in table 3 with antifouling paint quality index testing result：
Table 3
Inspection project Measured result The method of inspection
Adhesive force/grade ≤2 GB/T1720-79
Impact resistance/(kgcm) ≥45 GB/T1732-93
Flexibility/mm ≤2 GB/T1731-79
Contact angle/(°) ≤110 GB/T23764
Oil resistivity (room temperature, 30d) Coating is unchanged GB/T1734-93
Water resistance (100 DEG C, 72h) Coating is unchanged GB/T1733-93
Resistance to salt water (10%NaCl, room temperature, 30d) Coating is unchanged GB/T1763-79
As shown in Table 3, bullet train of the invention self-cleaning anti-pollution coating self-cleaning characteristic with high performance, with similar production Condition ratio, this product are rich in biological bactericide, have biological attachment rejection ability, can be played by the reasonable compounding in component Splendid anti-fouling effect.Also there is extraordinary oil resistivity, this coating to exist for the coating obtained after train enclosure coater simultaneously It is impregnated 30 days in oil-based solvent, coating is without blistering, swelling and obscission.Have slowly in addition, the characteristic of resin assigns coating Automatical cleaning ability, can remove surface attachment intractable spot, surface can maintain initial film color and luster for a long time.
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form Limitation, on the premise of not exceeding the technical scheme recorded in the claims also other variations and modifications.

Claims (3)

1. a kind of self-cleaning anti-pollution coating of the bullet train containing micro biological bactericide, it is characterised in that the coating is by as follows First component based on mass fraction is mixed to prepare with second component：
First component：
Ternary random copolymerization acrylic resin 40-50%
Hydroxy silicon oil 4-8%
Fluorocarbon resin 2-6%
Acrylamide 2-5%
Adhesion promoter 2-8%
Triphenylboron pyridine 3-5%
Zineb 3-5%
Talcum powder 3-5%
Titanium dioxide 15-25%
Pigment 0-8%
Polyamide wax pulp 1-6%；
Second component：Aliphatic isocyanates tripolymer,
The mass ratio of wherein first component and second component is 2-4:1；
The ternary random copolymerization acrylic resin is made by raw material as follows based on mass fraction：
Azodiisobutyronitrile 0.35-0.45%,
Azobisisovaleronitrile 0.38-0.48%,
Lauryl mercaptan 0.49-1.2%,
Butyl acetate 47-50%,
Hydroxy-ethyl acrylate 2.3-3.6%,
Acrylic acid trichlorine phenyl ester 9-10%,
Butyl acrylate 24-28%,
Isobornyl acrylate 10-13%.
2. the self-cleaning anti-pollution coating of the bullet train containing micro biological bactericide according to claim 1, feature exist In：The pigment is selected from phthalocyanine blue, lemon yellow or one or more of indigo.
3. the self-cleaning anti-pollution coating of the bullet train containing micro biological bactericide according to claim 1, feature exist It is in the preparation method of the ternary random copolymerization acrylic resin：Equipped with blender, reflux condensing tube, constant pressure funnel Four-hole boiling flask in be added azodiisobutyronitrile, lauryl mercaptan, butyl acetate, 100-110 DEG C is warming up to after mixing, is then added Hydroxy-ethyl acrylate, acrylic acid trichlorine phenyl ester, butyl acrylate, isobornyl acrylate, azodiisobutyronitrile and azo two are different The mixed liquor of valeronitrile, the wherein addition of azobisisovaleronitrile are the 90%-95% of formula ratio, with constant pressure funnel through 2.5-3 Hour constant speed is added dropwise, and adds the azobisisovaleronitrile of surplus, after continuing isothermal reaction 0.5-0.6 hours, is warming up to It 110-115 DEG C, after the reaction was continued 2.5-3 hours, is cooled to room temperature, ternary random copolymerization acrylic resin is obtained by the reaction in completion.
CN201610454919.7A 2016-06-21 2016-06-21 A kind of self-cleaning anti-pollution coating of the bullet train containing micro biological bactericide Active CN106010044B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101280148A (en) * 2008-05-06 2008-10-08 常州市天安特种涂料有限公司 Long-acting antifouling paint
CN103396712A (en) * 2013-07-15 2013-11-20 抚顺市海丰化工有限公司 Hydrolyzed marine antifouling paint and preparation method thereof
CN105367706A (en) * 2015-12-11 2016-03-02 舟山市恒泰漆业有限责任公司 Preparation method of acrylic acid antifouling resin, environment friendly ship bottom anti-fouling paint for reducing dosage of antifouling agent and preparation method of environment friendly ship bottom anti-fouling paint

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101280148A (en) * 2008-05-06 2008-10-08 常州市天安特种涂料有限公司 Long-acting antifouling paint
CN103396712A (en) * 2013-07-15 2013-11-20 抚顺市海丰化工有限公司 Hydrolyzed marine antifouling paint and preparation method thereof
CN105367706A (en) * 2015-12-11 2016-03-02 舟山市恒泰漆业有限责任公司 Preparation method of acrylic acid antifouling resin, environment friendly ship bottom anti-fouling paint for reducing dosage of antifouling agent and preparation method of environment friendly ship bottom anti-fouling paint

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Inventor after: Lu Ading

Inventor after: Hu Jiankun

Inventor after: Li Juan

Inventor after: Song Wei

Inventor before: Song Wei

Inventor before: Lu Ading

Inventor before: Hu Jiankun

Inventor before: Li Juan

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Application publication date: 20161012

Assignee: ZHEJIANG HAIFU MARINE BIOTECHNOLOGY Co.,Ltd.

Assignor: ZHEJIANG MARINE DEVELOPMENT Research Institute

Contract record no.: X2022330000405

Denomination of invention: A self-cleaning antifouling paint for high-speed trains containing trace biocides

Granted publication date: 20180918

License type: Common License

Record date: 20220811