阅读说明：本技术 盖上物业安全型长波长led光固化涂料、其涂装装置、方法，及在轨道交通工具上的应用 (Safety type long-wavelength LED photocureable coating for covering property, coating device and method thereof, and application of coating device and method to rail vehicles ) 是由 辛杰 王智刚 陈琪 侯文军 缪振华 谢述武 宁超 罗爱芳 许俊 赵亮 于 2021-01-19 设计创作，主要内容包括：本发明公开了一种长波长LED光固化涂料及利用其进行涂装的装置和方法,属于轨道交通车体环保涂装技术领域。所述长波长LED光固化涂料包括：(1)至少一种含烯键的不饱和可辐射聚合物质；和(2)至少一种在360-780纳米长波光波波长区域有活性吸收的光敏引发剂物质。该长波长LED光固化涂料具备高闪点、低气味、低或零VOC释放特征,属于环境友好型涂料。本发明进一步将所述长波长LED光固化涂料新材料与利用其进行涂装的装置结合,结合创造性的方法,提供一种一体化成套技术,具有重大的产业化应用前景和具有突出的经济和社会效益。(The invention discloses a long-wavelength LED photocureable coating, and a device and a method for coating by using the same, and belongs to the technical field of environment-friendly coating of rail transit vehicle bodies. The long wavelength LED photocurable coating includes: (1) at least one ethylenically unsaturated radiation polymerizable species; and (2) at least one photoinitiator species having active absorption in the wavelength region of 360-780 nm long-wave light. The long-wavelength LED photocureable coating has the characteristics of high flash point, low odor and low or zero VOC (volatile organic Compounds) release, and belongs to an environment-friendly coating. The invention further combines the new long-wavelength LED photocureable coating material with a device for coating by using the new long-wavelength LED photocureable coating material and combines a creative method, provides an integrated complete technology, and has great industrial application prospect and outstanding economic and social benefits.)

1. A long wavelength LED photocurable coating, comprising:

(1) at least one ethylenically unsaturated radiation polymerizable species; and

(2) at least one photoinitiator substance with active absorption in the wavelength region of 360-780 nanometer long-wave light.

2. The long wavelength LED photocurable coating of claim 1 wherein the ethylenically unsaturated radiation polymerizable species is a compound or mixture that can be crosslinked by free radical polymerization of the ethylenic linkage.

3. The long wavelength LED photocurable coating of claim 2 wherein the ethylenically unsaturated radiation polymerizable species is a monomer, oligomer or prepolymer, mixtures or copolymers thereof, or water soluble or aqueous dispersions thereof.

4. The long wavelength LED photocurable coating of claim 3 wherein the monomer is an acrylate, acrylamide, acrolein, an olefin, a conjugated diene, styrene, maleic anhydride, fumaric anhydride, vinyl acetate, vinyl pyrrolidone, vinyl imidazole, acrylic acid, or an acrylic acid derivative.

5. The long wavelength LED photocurable coating according to any one of claims 1-4, wherein the photoinitiator species having active absorption in the wavelength region of 360-780 nm long wavelength light is any one of or a mixture of any two or more of the photoinitiator compounds having the structural formulas I-IX, a reactive amine and a photoinitiator species having a dye as a substantial photosensitizer:

，

wherein, the compound has a structural formula I and is a hydroxy ketone type photoinitiator compound; (II) aminoketone type photoinitiator compounds having the structural formula II; having the structural formula III is a phosphono photoinitiator compound; oxime ester type photoinitiator compounds having the structural formula IV; a benzophenone-type photoinitiator compound having the structural formula V; a benzoylformate type photoinitiator compound having the structural formula VI; having the structural formula VII is a thioxanthone type photoinitiator compound; an acylsulfone-type photoinitiator compound having structural formula VIII; onium salt type cationic photoinitiator compound having structural formula IX;

Ar₁and Ar₂Independently of one another, are C-containing⁴-C⁶⁴Substituted or unsubstituted aryl or heteroaryl of (A) each containing 1 to 6C¹-C¹²Straight or branched or cyclic alkyl, alkoxy, alkylthio, alkylamino, C⁶-C¹²Aryl or halogen substituents;

R₁、R₂、R₃、R₄、R₅、R₈、R₉、R₁₀independently of one another are hydrogen, C¹-C¹²Linear or branched or cyclic alkyl, or C⁶-C¹²Substituted or unsubstituted aryl or heteroaryl;

Ar₃is a compound containing n substituentsC of (A)⁶-C²⁴Aryl, n has a value of 1-6, and the substituent is C¹-C¹²Straight or branched or cyclic alkyl, alkoxy, alkylamino, CH₂OH、CH₂SH、CH₂Cl、CH₂OAc、CH₂O-C(O)-CH=CH₂、CH₂O-C(O)-C(CH₃)=CH₂、

CH₂NH-C(O)-CH=CH₂、CH₂NH-C(O)-C(CH₃)=CH₂、

X-Ar₃-C(O)-P(O)R₆R₇X is divalent C²-C¹²A linking group interrupted by 1-6 non-consecutive oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, carbonyl groups, hydroxyl groups, ester groups, carboxyl groups;

R₆is hydrogen, m-valent C¹-C¹²Straight or branched or cyclic alkyl, alkoxy, alkylamino, C⁶-C¹²Substituted or unsubstituted aryl or heteroaryl, m has the value of 1-24;

R₇is OR₁、SR₁、NHR₁、NR₁R₂OM or C (O) Ar₁M is a metal cation or a quaternary ammonium or phosphonium salt cation;

R₁₁，R₁₂，R₁₃，R₁₄independently of one another is C¹-C¹²Straight or branched or cyclic alkyl, alkoxy, alkylthio, alkylamino, halogen, or C⁶-C¹²Substituted or unsubstituted aryl or heteroaryl;

R₁₅is C¹-C¹²Linear or branched or cyclic alkyl, or C⁶-C¹²Substituted or unsubstituted aryl or heteroarylaryl;

Q^-is a counter anion of the compound (I),

preferably, the photoinitiator substance with active absorption in the wavelength region of 370-780 nanometer long-wave light is at least one selected from the following substances:

。

6. the long wavelength LED photocurable coating according to claim 1, wherein the long wavelength LED photocurable coating contains moisture in a mass percentage of 0-90%, preferably 0-80%, more preferably 0-70%, even more preferably 0-60%,

further, the addition amount of the photoinitiator substance having active absorption in the wavelength region of 360-780 nm long wavelength light is 0.01-30% by mass, preferably 0.1-20% by mass, more preferably 1-20% by mass, and still more preferably 1-15% by mass.

7. The long wavelength LED photocurable coating of claim 6 wherein the coating is at least one of a primer, a topcoat and a midcoat, respectively, suitable for use in at least one of a putty, a basecoat, a midcoat, or a topcoat process.

8. A device for coating the material surface by using the long wavelength LED photocureable coating as claimed in claim 1, which is characterized by comprising an LED photocureable light source system with the wavelength of 360-780 nm light wave and with water cooling or air cooling refrigeration, wherein the power density of the LED photocureable light source system is preferably in the range of 0.01-100000mW/cm²The illumination value range is 0.01-100000mJ/cm²More preferably, the LED light curing light source system is a handheld LED light source, a slide rail LED light source, or a tunnel LED light source;

further, the device also comprises a manual or robot or manipulator spraying system with a negative pressure paint mist recovery function, preferably, the manual or robot or manipulator spraying system with the negative pressure paint mist recovery function is a manual or robot or manipulator spraying workstation with a spraying position vertical surface and the ground and a latticed negative pressure paint mist recovery device;

furthermore, the device also comprises a temperature control dehumidifying device, preferably, the working parameters of the temperature control dehumidifying device are that the temperature is-10-60 ℃, and the relative humidity is 5% -95%;

still further, the apparatus further comprises an automated conveyor line;

furthermore, the device also comprises tail-end VOCs treatment equipment; the VOCs treatment equipment is connected with the air outlet of the device, and the relative relation between the air inlet and the air outlet of the device can be air outlet from the left side and the right side, or air outlet from the front side and the rear side, or air outlet from the upper side and the lower side, or vice versa.

9. A method for coating a material surface by using the long wavelength LED light-cured paint of claim 1, which comprises the step of performing LED light-cured coating on the material surface by using the long wavelength LED light-cured paint as at least one of putty, primer, paint and finish, preferably, the material is a whole car body (outer body and inner body) or a part or part (bogie) of a rail vehicle, further, the material surface is a material inner surface and/or a material outer surface; preferably, the coating is spraying, brushing, wiping, curtain coating, or roller coating.

10. Use of a thermal curing coating in combination with a long wavelength LED photo-curing coating according to any one of claims 1 to 7 on a rail vehicle, wherein the long wavelength LED photo-curing coating comprises:

(1) at least one epoxy-type resin material;

(2) at least one zinc-containing pigment; and

(3) dimethyl carbonate is the solvent.

Technical Field

The invention belongs to the technical field of environment-friendly coating, and particularly relates to a long-wavelength LED photocureable coating, a device and a method for coating by using the same, and more particularly to a long-wavelength LED photocureable coating which is suitable for coating a whole vehicle or a part of a rail vehicle under a property scene, and a device and a method for coating the whole vehicle or the part of the rail vehicle by using the same.

Background

The China railway transportation industry has been developed with attention from the quality and quantity, and tends to be gentle after the business of new vehicles is increased at a high speed in 2018, the existing gauge model of the railway vehicle body is considerable and continuously increased, and large batches of vehicles gradually enter a high-level maintenance stage, so that the requirements of field recoating, renovation and changing new and important markets are brought.

Meanwhile, for the pollution control of VOCs (Volatile Organic Compounds) in the industrial coating process, relevant laws and regulations are shifted from a transition period to a mandatory execution period (relevant national standards such as GB 24409-. Traditional Solvent-based coating products are facing ever-increasing operating pressure and are seeking to be transformed into corresponding Waterborne products (Waterborn coatings/Inks) or "100% solventless products (100% Solid and Solvent-Free coatings/Inks)" due to the widespread high emission of VOCs organic compounds, such as volatile Solvent diluents.

As judged by technical logic, the "desolvation" of conventional oil-based paint products is known to those skilled in the art by the following known technical routes, namely, so-called aqueous thermosetting one-component (1K), two-component (2K), or 100% solid content short wavelength ultraviolet radiation Curing (UV-Curing) materials, all have the greening characteristic of energy saving and emission reduction of low VOCs, and related technologies exist in the industry for many years. However, as is also well known to those skilled in the art, the above techniques have only gained sporadic use over a decade or more in several sub-divided areas of coating ink, and have not evolved into a transition upgrading of the main channel mainstream technology beyond conventional wall water-borne architectural coating applications. Practical investigations have found that the reasons for hindering the market promotion of the above-mentioned types of coating products are, above all, that their technical application results and properties are poor and difficult to compete with conventional solvent-based products.

In essence, the energy conservation and emission reduction of VOCs in the coating and painting industry are not only regulatory supervision and environmental protection upgrading requirements, but also are a deep technical revolution. For the enterprises in the entity manufacturing industry, not only the environmental protection transformation is required, but also the competitive power is required to be strengthened by continuously reducing the operating cost through technical innovation. In the past decade, active research and development activities are generated around the factors of technical innovation, cost control, coating quality, wide application and the like, but a real one-stop solution applicable to a broad spectrum is not formed; the important industries, such as rail transit vehicle coating, especially the safe and friendly coating in special environment with densely populated property, still suffer from the realistic application scene mainly comprising the traditional high-pollution solvent-based paint such as epoxy paint, polyurethane paint and the like.

The VOC tail end treatment technology, such as catalytic combustion-activated carbon adsorption, zeolite rotary wheel adsorption concentration and other methods, has the problems of large equipment and facility investment in primary treatment, high operation and maintenance costs such as later-stage material consumption, energy consumption and power consumption and the like, obviously increases the cost, and can not bear heavy load for enterprises.

Obviously, the tail end is passively treated, which is not as active as the source for emission reduction.

Meanwhile, as the 'quasi-industrial coating' link of the urban rail transit vehicle body is characterized in that the vehicle section is covered with dense property and highly sensitive to the human residential environment, the complete vehicle body is newly recoated, renovated and replaced on site, the self composition of the coating and the flammable and explosive components in the coating construction process are forbidden to meet the fire safety control except for the forced standard of VOCs emission reduction, and the corresponding fire safety certification has definite chemical substance flash point requirements on the related components (meeting the national standards GB/T3536. supplement 2008, GB/T5208. supplement 2008/ISO 3679. supplement 2004 and GB 50016. supplement 2014). Furthermore, pungent or uncomfortable peculiar smell cannot be emitted in the coating construction process, so that the influence on the living safety and the complaint of property owners are avoided.

Therefore, the industry has a urgent technical challenge to be solved, namely, a novel environment-friendly coating material and a coating automation equipment integrated solution thereof are developed, so that the novel environment-friendly coating material can replace the traditional solvent-based material and coating process with high pollution to the greatest extent, increasingly strict rules of energy conservation and emission reduction can be fulfilled, and simultaneously, the application economic cost, the coating effect and the construction efficiency can be comparable to or superior to those of solvent-based products in the same application occasions.

Disclosure of Invention

In order to solve at least one of the above technical problems, the present invention aims to provide a novel paint and a coating apparatus and method which are truly green and safe and can achieve both environmental friendliness and health of a constructor. In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

in one aspect, the present invention provides a long wavelength LED photocurable coating, including:

(1) at least one ethylenically unsaturated radiation polymerizable species; and

(2) at least one photoinitiator substance with active absorption in the wavelength region of 360-780 nanometer long-wave light.

Wherein the olefinic bond means a C = C bond, an unsaturated bond.

In the present invention, the photocurable coating is a photocurable coating. The long-wavelength LED photocureable coating is a coating which can be subjected to photopolymerization crosslinking curing under the irradiation of long-wavelength LED light. The long wavelength is 360-780 nm, preferably 360-650 nm, more preferably 360-450 nm, and even more preferably 360-420 nm.

In some embodiments of the present invention, the ethylenically unsaturated radiation polymerizable species is a compound or mixture that can be crosslinked by free radical polymerization of the ethylenic linkage.

In some embodiments of the present invention, the ethylenically unsaturated radiation polymerizable species is a monomer, oligomer, or prepolymer, a mixture or copolymer thereof, or a water soluble or aqueous dispersion thereof. Preferably, the ethylenically unsaturated radiation-polymerizable species is a macromolecular, or water-soluble, or polymer-characteristic resin of an aqueous dispersion.

Suitable free radically polymerizable monomers are, for example, ethylenically-containing polymerizable monomers including, but not limited to, (meth) acrylates, acrolein, olefins, conjugated dienes, styrene, maleic anhydride, fumaric anhydride, vinyl acetate, vinyl pyrrolidone, vinyl imidazole, (meth) acrylic acid derivatives such as (meth) acrylamide, vinyl halides, vinylidene halides, and the like.

Suitable ethylenic-containing prepolymers and oligomers include, but are not limited to, (meth) acryloyl-functional (meth) acrylic copolymers, urethane (meth) acrylates, polyester (meth) acrylates, unsaturated polyesters, polyether (meth) acrylates, silicone (meth) acrylates, epoxy (meth) acrylates, and the like, as well as water-soluble or water-dispersible analogs of the foregoing.

Suitable water-dispersible or water-soluble ethylenically unsaturated resins include, but are not limited to, commercially available products such as, for example, the BASF corporation JONCRYL or Laromer brand series, the DSM corporation ReoRad brand series, the ALLNEX/CYTEC corporation UCECOAT or EBECRYL brand series, the Taiwan Changjin materials corporation ETERCURE DR brand series, the Alberdingk Boley corporation LUX brand series, the Congnis corporation Photomer brand series, and the Bayer corporation BAYHYDROL brand series.

In some embodiments of the present invention, the photoinitiator species having active absorption in the wavelength region of 360-780 nm long-wave light is any one of or a mixture of any two or more of the photoinitiator compounds having the structural formulas I-IX, an active amine and a dye as substantial photosensitizers:

namely hydroxyketone type (hydroxyketone, formula I), aminoketone type (Aminoketones, formula II), phosphono type (Acylphosphine Oxides, formula III), Oxime ester type (Oxime Esters, formula IV), benzophenone type (Benzophenones, formula V), benzoylformate type (phenylglyoylates, formula VI), thioxanthone type (Thioxanthones, formula VII), Acylsulfones (Acylsulfones, formula VIII), activated amines, onium salt type cationic photoinitiators (sulfoxides or iodonitriles or Photo-Acid Generators, formula IX, so-called PAGs), or dyes as a photoinitiator substance for substantive photosensitizers (Dye Sensitizers), or a mixture of any two or more.

Ar₁And Ar₂Independently of one another, are C-containing⁴-C⁶⁴Substituted or unsubstituted aryl or heteroaryl of (A) each containing 1 to 6C¹-C¹²Straight or branched or cyclic alkyl, alkoxy, alkylthio, alkylamino, C⁶-C¹²Aryl or halogen substituents;

R₁、R₂、R₃、R₄、R₅、R₈、R₉、R₁₀independently of one another are hydrogen, C¹-C¹²Linear or branched or cyclic alkyl, or C⁶-C¹²Substituted or unsubstituted aryl or heteroaryl;

Ar₃is C containing n substituents⁶-C²⁴Aryl, n has a value of 1-6, and the substituent is C¹-C¹²Straight or branched or cyclic alkyl, alkoxy, alkylamino, CH₂OH、CH₂SH、CH₂Cl、CH₂OAc、CH₂O-C(O)-CH=CH₂、CH₂O-C(O)-C(CH₃)=CH₂、CH₂NH-C(O)-CH=CH_2、CH₂NH-C(O)-C(CH₃)=CH₂、X-Ar₃-C(O)-P(O)R₆R₇X is divalent C²-C¹²A linking group interrupted by 1-6 non-consecutive oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, carbonyl groups, hydroxyl groups, ester groups, carboxyl groups;

R₆is hydrogen, m-valent C¹-C¹²Straight or branched or cyclic alkyl, alkoxy, alkylamino, C⁶-C¹²Substituted or unsubstituted aryl or heteroaryl, m has the value of 1-24;

R₇is OR₁、SR₁、NHR₁、NR₁R₂OM or C (O) Ar₁M is a metal cation or a quaternary ammonium or phosphonium salt cation;

R₁₁，R₁₂，R₁₃，R₁₄independently of one another is C¹-C¹²Straight or branched or cyclic alkyl, alkoxy, alkylthio, alkylamino, halogen, or C⁶-C¹²Substituted or unsubstituted aryl or heteroaryl;

R₁₅is C¹-C¹²Linear or branched or cyclic alkyl, or C⁶-C¹²Substituted or unsubstituted aryl or heteroarylaryl;

Q^-is a counter anion of the compound (I),

preferably, the photoinitiator substance with active absorption in the wavelength region of 360-780 nm long-wave light is at least one selected from the following substances: darocur 1173, Irgacure 184, API-180 (Shenzhen is technical stock control group, Inc., see the trade-in TDS and MSDS for explanation materials, the same below), API-307 (Shenzhen is technical stock control group, Inc.), API-308 (Shenzhen is technical stock control group, Inc.), API-1206 (Shenzhen is technical stock control group, Inc.), API-1207 (Shenzhen is technical stock control group, Inc.), Irgacure 2959, Irgacure MBF, Irgacure 127, Irgacure 651, Esacure KIP-150, Esacure KIP-160, Esacure KIP-1001, Esacure 01, Irgacure 907, Irgacure 500, Irgacure 2200, Irgacure 2022, Irgacure 4500, Irgacure ketone, Irgacure 379, Irgacure 819 TPO 819, Irgacure 784, Irgacure or Irgacure 784, irgacure CPTX, Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03, Irgacure OXE-04, Tronly 304 (Changzhou Strong Electron New Material Co., Ltd.), Tronly 305 (Changzhou Strong Electron New Material Co., Ltd.), Irgacure 250, ADEKA NCI-831 (Idiko Co., Ltd.), ADEKA N-1414 (Idhidaceae Co., Ltd.), Irgacure 290, Irgacure 270, and a coumarin type dye photosensitizer, etc., and they may be compounded with a corresponding Co-initiator aid (Co-initiator) such as an active amine and/or a hydrogen silane type active hydrogen donor Co-initiator.

More preferably, the photoinitiator substance having active absorption in the wavelength region of 360-780 nm long-wave light is at least one selected from the following substances:

in some embodiments of the present invention, the long wavelength LED photocurable coating contains 0 to 90% by mass of moisture, preferably 0 to 80%, more preferably 0 to 70%, and still more preferably 0 to 60%. Accordingly, the long wavelength LED photocurable coating contains 10 to 100% by mass of a film forming substance, preferably 20 to 100%, more preferably 30 to 100%, and still more preferably 40 to 100%.

Further, the long-wavelength LED photocureable coating also contains a flame-retardant or non-combustible substance, wherein the main component of the flame-retardant or non-combustible substance is a substance which meets the requirement that the closed cup flash point value is more than 100 ℃ and meets the national standards GB/T3536-.

Further, the addition amount of the photoinitiator substance having active absorption in the wavelength region of 360-780 nm long wavelength light is 0.01-30% by mass, preferably 0.1-20% by mass, more preferably 1-20% by mass, and still more preferably 1-15% by mass.

In some embodiments of the invention, the coating is at least one of a primer, a topcoat and a midcoat, and accordingly, is suitable for at least one of a putty, a basecoat, a midcoat, or a topcoat process.

A second aspect of the present invention provides an apparatus for coating a surface of a material with the long wavelength LED photocurable coating according to the first aspect of the present invention, comprising:

（A) The LED photocuring light source system with the wavelength of 360-780 nanometer light wave and water-cooling or air-cooling refrigeration is preferably used, and the power density range is 0.01-100000mW/cm²The illumination value range is 0.01-100000mJ/cm²More preferably, the LED light curing light source system is a handheld LED light source, a slide rail LED light source or a tunnel LED light source.

（B) The manual or robot spraying system with the negative pressure paint mist recovery function is preferably a manual or robot or manipulator spraying workstation with a spraying position vertical surface and a ground surface and with a latticed negative pressure paint mist recovery device.

（C) The temperature control dehumidification equipment is any one or combination of more than two of a dehumidifier, an infrared heater or an air energy heating dehumidification device; the temperature and humidity in the production workshop can be uniform, or preferably, the temperature and humidity in the production workshop can be removed by evaporation of leveling and/or moisture, and the temperature and humidity control dehumidification equipment has gradient characteristics, and preferably, the working parameters are that the temperature is-10-60 ℃ and the relative humidity is 5% -95%.

（D) The automatic conveying line is a rail type or suspension wire type automatic conveying line.

（E) And the tail-end VOCs treatment equipment comprises, but is not limited to, an RTO zeolite rotary wheel treatment device, a catalytic combustion activated carbon adsorption device and the like. The VOCs treatment equipment is connected with the air outlet of the device, and the relative relation between the air inlet and the air outlet of the device can be air outlet from the left side and the right side, or air outlet from the front side and the rear side, or air outlet from the upper side and the lower side, or vice versa.

The device at least comprises the aboveA(ii) a Preferably, the device comprises at least the aboveAAndB(ii) a More preferably, the device comprises the aboveA，B，C，D(ii) a Even more preferably, the device comprises the aboveA，B，C，D，E(ii) a And associated other ancillary equipment or conditions including, but not limited to, on-line or off-line sanding stations, sanding polishes, non-recovery dry spray booths, dust and dust removal facilities.

The devices of the apparatus of the invention are coupled in a manner for use in the first aspect of the inventionIn one aspect, the long wavelength LED photocurable coating is as described aboveA-B-C-D-EThe coating operation is carried out under the layout condition of the production line consisting of the equipment so as to achieve the beneficial effects of recycling paint mist, improving the efficiency and reducing the cost of LED second-level rapid photocuring and realizing low or zero emission of VOC sources, which have not been realized in the industry before.

The third aspect of the invention provides a method for coating the surface of a material by using the long-wavelength LED photocureable coating of the first aspect of the invention, which comprises the step of performing LED photocureable coating on the surface of the material by using the long-wavelength LED photocureable coating as at least one of putty, primer, color correction paint and finish paint, preferably, the material is a whole vehicle or a part of a rail vehicle, further, the surface of the material is the inner surface of the material and/or the outer surface of the material, preferably, the coating is spraying, brushing, curtain coating, wiping or roll coating.

In the present invention, coating is performed using the apparatus according to the second aspect of the present invention.

When in use, the single or double-component thermosetting putty, the single or double-component thermosetting base coat, the single or double-component thermosetting middle coat and the LED photocuring coating are combined; preferably, the single-component or double-component thermosetting putty, the LED photocuring base coat, the single-component or double-component thermosetting middle coat and the LED photocuring top coat are used together; more preferably, the LED photocuring putty, the LED photocuring base coat, the LED photocuring middle coat and the LED photocuring top coat are used together. Preferably, the construction number of the LED photocuring putty and the LED photocuring primer is 1-3 times, and the construction number of the LED photocuring color-correcting paint and the LED photocuring finishing paint is 1-2 times.

In the present invention, the heat curable coating may be any solvent or water based coating known to those skilled in the art, including but not limited to coatings of epoxy or polyurethane character. Preferably, the preferred diluent of the thermosetting material is water, or low-VOCs or VOCs-exempt green solvent dimethyl carbonate.

Preferably, for example, thick paste type epoxy primer materials and their application for coating in the device disclosed by the invention, which meet the above requirements, are characterized in that the materials comprise: (1) at least one epoxy-type resin material; (2) at least one zinc-containing pigment; and (3) dimethyl carbonate as a solvent.

To this end, the present invention provides a cell type production line layout, as shown in FIG. 1.

In the element production lineAAndBthe distance and mutual position of (a) can be adjusted according to the need, and are not particularly limited; the element production line can be used as any one LED photocuring coating working section of putty paint, primer paint, color repair paint or finish paint, and can also perform parallel or repeated operation on the same working section, for example, the LED photocuring primer paint needs to be coated for 2 times, the 2 processes can be repeated for 2 times on the same element production line, and two element production lines can be connected in series in parallel in a mode that a lower piece area of a first line is butted with an upper piece area of a second line. Preferably, when two or more cell lines are linked in series, the polishing sections are provided in an on-line or off-line manner in the butt-joint area between the lower piece region of one line and the upper piece region of another line.

In some embodiments of the present invention, the LED photocuring element production line is exemplified by a single or linked integrated coating line (wherein the corresponding polishing section is omitted during the process):

material → protective shielding → polishing and cleaning → cleaning and decontamination → re-shielding protection → spraying LED photocuring base color paint (smooth surface or rough surface) → LED light source irradiation and drying → spraying LED photocuring finish paint → LED light source irradiation and drying → deprotection → acceptance and delivery of vehicles;

preferred solutions for the cell lines, either alone or linked into an integrated coating line, are long wavelength LED light curable cell lines and conventional UV light curing, or heat curable aqueous one or two component coatings in combination, for example using the following exemplary solutions:

material → protective shielding → polishing and cleaning → cleaning and decontamination → re-shielding protection → spraying two-component thermosetting polyurethane primer → hot air blow drying → spraying LED photocuring base color paint (smooth surface or rough surface) → hot air gun blowing to surface dry → spraying LED photocuring finish paint → LED light source irradiation drying → deprotection → acceptance and delivery of traffic vehicles;

preferably, the LED photocuring wiping putty and the LED photocuring spraying primer are high-solid-content coating formula materials with the water content of 0-30%; more preferably, the LED light-cured render putty and the LED light-cured spray primer are high solids paint formulations having a water content of between 0-15%.

Preferably, the LED photocuring spraying color-modifying paint and the LED photocuring spraying finish paint are low-solid-content paint formula materials with the water content of 10-90%; more preferably, the LED light-cured spray paint color correction paint and the LED light-cured spray paint finish paint are low-solid content paint formulation materials with the water content of 30-80%.

It is worth emphasizing that if the LED light source system disclosed by the invention is removed on the basic type production lineAMeanwhile, the thermosetting water-based single-component or two-component coating material is used for replacing the long-wavelength LED photocuring single-component coating material disclosed by the invention, so that the recycling of paint mist (for a two-component coating) cannot be realized, and the expected cost reduction and efficiency improvement effects cannot be achieved. One reason is that the film-forming crosslinking density of the thermosetting water-based single-component or double-component coating is low and is obviously lower than that of the disclosed long-wavelength LED photocureable coating material or the coating of the traditional epoxy/polyurethane paint, so that the performance of a paint film is poor and the paint film cannot be accepted by the market; the second reason is that the thermosetting water-based single or two-component paint has long waiting and actual drying time (several hours to one or two days), which is significantly longer than the long-wavelength LED photocureable paint material disclosed by the invention (several seconds) or the traditional epoxy/polyurethane paint (several hours), so that the cost is high.

The invention has the advantages of

Compared with the prior art, the invention has the following beneficial effects:

firstly, the long wavelength LED light wave (360-780 nm) in the specific wavelength region will not excite oxygen in the air to generate ozone (O) during operation₃) The hazard does not need any special protection or tail ozone treatment facility equipment investment;

secondly, the long-wavelength light source has strong penetrating power and reflection and scattering functions, meanwhile, the light intensity and irradiance of the LED light source are flexible and adjustable, the paint film of a plane and a special-shaped workpiece is effectively cured for the first time, the paint film is suitable for both spraying and roll coating, the wide application range is obviously enhanced, and the long-term bottleneck that the traditional short-wavelength ultraviolet light can only be used for photo-curing of regular workpieces relative to a flat plate and can only be used for roll coating is broken through;

thirdly, the single-component characteristics enable the material to realize recycling of paint mist in spraying construction for the first time, waste is avoided, cost is saved (the recycling rate is more than 95%), VOC release pollution is reduced or avoided, and then investment of VOC tail end environment-friendly treatment equipment is reduced or completely eliminated. For traditional solvent-based epoxy and polyurethane paint two-component materials, the effective activation life is only short 2-4 hours, so that the method is worthy of particularly emphasizing that the industry has no subjective emission reduction desire of recycling and no objective technical practice possibility of recycling in past production practice. Under the background, the recycling of the paint mist of the single-component long-wavelength LED photocuring material is realized for the first time;

fourthly, the material breaks through the technical bottleneck, realizes highly flexible and controllable adjustment of viscosity under the condition of not adding organic solvent diluent or only adding water, particularly realizes low viscosity for spraying construction, and simultaneously avoids the release of VOCs from the source;

fifthly, the main components of the material all have the national fire safety standard of the fifth grade 'flame-retardant or non-combustible substance' with the closed cup flash point more than 100 ℃ (the upper limit of the detection limit is reached) (refer to the national standards GB/T3536-2008 and GB/T5208-2008/ISO 3679-2014), thereby meeting the fire safety requirements of operation space and covering property (refer to the national standard GB 50016-2014);

sixthly, the main components of the material, such as macromolecular resin, water absorbent and the like, have the characteristics of low odor or no peculiar smell, so that the bad odor treatment process is avoided, and the common coating construction problem that odor disturbs people is also avoided.

In conclusion, the long-wavelength LED photocureable coating has the characteristics of high flash point, low odor and low or zero VOC (volatile organic compound) release, and belongs to an environment-friendly coating.

The specific application scene of the invention relates to operation in special environment covering property with dense population, and provides unprecedented new requirements for environmental protection and safety, and an innovative system solution is urgently needed to ensure that the coating material and the process thereof must simultaneously meet the four technical requirements of high-performance coating, low or zero VOC release, fire safety and odor purification and health. The invention utilizes the long-wavelength LED photocuring coating to be mutually coupled with a matched LED photocuring light source system, an artificial or intelligent robot spraying system, a paint spray recycling system, an on-line polishing system, a tail end VOC secondary treatment system, an automatic suspension line or floor line conveying system and the like, thereby fundamentally providing a new solution for one-stop painting and renovation of the whole rail transit vehicle, which aims at the safety and the friendliness of the covering property and simultaneously meets the four technical requirements. The solution is characterized in that an LED light-curing new material and a new equipment technology are creatively integrated, the LED light-curing new material and the new equipment technology are firstly carried out in a linkage manner in the industry, and cost reduction and efficiency improvement of a coating process are firstly realized by utilizing an LED light-curing second-level efficient drying and curing technology. The technology is ahead of the international peer enterprises and leads to the success of industrialization, and is a major technical breakthrough of the independent intellectual property rights in China in the field of rail transit.

In addition, the invention relates to a new material of the LED photocureable coating with specific long wavelength and a specific novel coating series associated device (A-B-C-D-E) Creatively combined in a specific mode, and a comprehensive and one-stop cost-reducing and efficiency-improving solution is provided for the rail transit vehicle body coating industry. Thereby providing an integrated complete technology, having great industrialization application prospect and outstanding economic and social benefits.

Drawings

FIG. 1 illustrates a long wavelength LED light curable putty, primer, intercoat, or topcoat production line.

Detailed Description

In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments.

Examples

The following examples are used herein to demonstrate preferred embodiments of the invention. It will be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function in the invention, and thus can be considered to constitute preferred modes for its practice. Those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit or scope of the invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and the disclosures and references cited herein and the materials to which they refer are incorporated by reference.

Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims.

The experimental procedures in the following examples are conventional unless otherwise specified. The instruments used in the following examples are, unless otherwise specified, laboratory-standard instruments; the test materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.

Example 1 Long wavelength LED Photocurable coating formulation

Long wavelength LED photocurable coatings, i.e. sample systems containing olefinic bonds (acrylates), were prepared according to the following formulation (in weight percent):

primer material a: 60 parts of Shenzhen, namely technique stock control group Limited company APi-338 aqueous polyurethane acrylate dispersion (with the solid content of 46 wt%), 30 parts of TiO₂The paint comprises 3 parts of deionized water, 4 parts of PM/PNB mixed film-forming aid, 0.5 part of wetting agent BYK-346, 0.5 part of commercial leveling agent 3076, 1 part of flash rust inhibitor RAYBO 70 and 1 part of commercial thickener 0620.

Primer material B: 100% solids BAYER waterborne isocyanate curing agent Bayhydur XP 2655.

Base coat material C: 50 parts of an aqueous polyurethane acrylate dispersion of UCECOAT 7788 from ALLNEX,15 parts of TMPTA monomer, 20 parts of TiO₂Pigment, 1.5 parts of TRAFe from zhejiang yue nano technologies^®Transparent iron oxide yellow pigment BTY-101W pigment, 2 parts of photoinitiator TPO-L, 1 part of photoinitiator 819, 1 part of photoinitiator DETX, 1 part of Shenzhen, namely photoinitiator APi-307 of technical stock group Limited, 2.5 parts of deionized water, 4 parts of film-forming additive, 0.5 part of wetting agent BYK-346, 0.5 part of flatting agent 3076 and 1 part of thickening agent 0620.

And (3) finishing paint material D: 28 parts of photocuring resin B-520 of Guangdong Boxing company, 18 parts of photocuring resin B-574, 6 parts of waterborne toughener WATBOND311, 30 parts of monomer TPGDA, 9 parts of deionized water, 2 parts of grinding aid PLB-500, 0.5 part of wetting agent BYK-330, 0.5 part of leveling agent 3076, 2 parts of adhesion promoter 9107, 1 part of photoinitiator TPO, 2 parts of Shenzhen photoinitiator APi-308 of technical stock control group Limited company and 1 part of photoinitiator ITX.

Water thick paste type epoxy primer material E: 18 parts of Shenzhen, namely a technical stock control group Limited waterborne polyamide dispersion (with the solid content of 40 wt%), 20 parts of zinc phosphate pigment, 20 parts of aluminum tripolyphosphate pigment, 10 parts of hydrophobic barium sulfate as a filler and 15 parts of TiO₂The coating comprises a pigment, 1 part of a carbon black pigment, 8 parts of deionized water, 4 parts of a film forming additive, 0.5 part of a wetting agent BYK-346, 0.5 part of a leveling agent 3076, 1 part of an anti-flash rust agent 340A, 1 part of a salt spray resistant additive 330 and 1 part of a thickening agent 0620.

Water thick paste type epoxy primer material F: 45 parts of Hensman Araldite 3963 aqueous epoxy resin, 45 parts of Vansen Hexion 816 liquid epoxy resin, 2 parts of epoxypropyl WD-60 and 8 parts of dimethyl carbonate.

Example 2 Long wavelength LED light-curing environmental protection coating production line layout and application

The long wavelength LED photocuring environment-friendly coating production line is formed by connecting single or a plurality of element production lines in series, and the element lines are shown in figure 1. The wavelength of light emitted by the handheld LED light source is 390-405 nm, and the power is 16W/cm.

The painted materials are an inner body, an outer body and a bogie of the track traffic vehicle body with No. 1 line and No. 3 line of Shenzhen subway group Limited, and the construction site is a paint spraying warehouse (attached drawing) reformed by the mode disclosed by the invention at the maintenance section of the sea vehicle before No. 1 line of Shenzhen subway group Limited.

The construction method comprises the following steps:

material → protective shielding → polishing and cleaning → cleaning and decontamination → re-shielding protection → spraying LED photocuring base color paint (smooth surface or rough surface) → LED light source irradiation and drying → spraying LED photocuring finish paint → LED light source irradiation and drying → deprotection → acceptance and delivery of vehicles;

or: material → protective shielding → sanding and cleaning → cleaning and decontamination → re-shielding and protection → spraying of thermosetting base color paint (smooth surface or numb surface) → placing and drying → spraying of LED photocuring finish paint → LED light source irradiation and drying → deprotection → acceptance and delivery of vehicles.

Through the layout, long wavelength LED photocuring and series equipment are organically coupled in an innovative mode, and a new solution for one-stop coating, renovation and replacement of the finished vehicle of the safe and friendly type rail transit covered with the property is fundamentally provided, so that a great transformation and upgrading green substitution technology capable of effectively substituting the traditional high-pollution solvent-based paint and coating is provided in the industrial field.

In the operation of the production line, the construction temperature is controlled to be 10-40 ℃, and the humidity is controlled to be 30-70%; after being dried and cured, the paint film has the technical indexes of scratch resistance, stain resistance, glossiness, color difference, adhesive force, paint film thickness, hardness, salt spray resistance and the like which all meet the acceptance standards of the coating quality of the related track vehicle bodies of Shenzhen subway group Limited company.

The main components of the material are tested by the Huadian test certification group and have the national fire safety standard of grade five 'difficult-to-burn or incombustible substances' with the closed cup flash point of more than 100 ℃ (the closed cup flash point is in the upper limit of the detection limit) (refer to the national standards GB/T3536-.

The recovery rates of primer and finish paint mist reach more than 95 percent, almost zero emission of source VOC is realized, and the continuous monitoring indexes (less than or equal to 5 g/L, standard GB18581-2020 and DB 32/T3500-containing materials 2019) of VOCs at the spray room opening reach the direct discharge standard.

In conclusion, the long-wavelength LED photocureable coating is used together with the coating device, so that an overall green coating solution for an outer vehicle body-inner vehicle body-bogie of a rail transit vehicle body is provided for the first time, and particularly an original solution for the first time of trampling to the ground to reach the triple standard (namely environmental protection, fire protection and smell) is realized for the first time in a manner of covering property and being safe and friendly to human habitation.

All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.