CN102850897B - A kind of photocuring hydrophilic coating and preparation method thereof - Google Patents
A kind of photocuring hydrophilic coating and preparation method thereof Download PDFInfo
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- CN102850897B CN102850897B CN201110181992.9A CN201110181992A CN102850897B CN 102850897 B CN102850897 B CN 102850897B CN 201110181992 A CN201110181992 A CN 201110181992A CN 102850897 B CN102850897 B CN 102850897B
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Abstract
Do are the invention discloses a kind of photocuring hydrophilic coating, this coating composition and mass percent: sulfonate monomer 10 ~ 30% photocuring emulsion 30 ~ 70% multifunctional reactive thinner 8 ~ 30% light trigger 0.5 ~ 5% auxiliary agent 0.1 ~ 2% solvent surplus sulfonate monomer is the polymerisable monomer simultaneously containing sulfonate groups and double bond.The present invention has avoided sulfonate monomer and this difficult problem of photocuring oil paint Miscibility difference, is added in photocuring emulsion by sulfonate monomer strong for wetting ability, provides the waterborne radiation curable coating that a kind of sulfonate monomer solvability is good.
Description
Technical field
The present invention relates to ultraviolet-curing paint technical field, particularly relate to a kind of photocuring hydrophilic coating and preparation method thereof.
Background technology
Photo-cured coating (photocurablecoatings) refers under the irradiation of ultraviolet (Ultra-Violet), light trigger (Initiator) in liquid coating is stimulated and becomes free radical or positively charged ion, thus there is chemical reaction between the material (Oligomer or Monomer) in initiation coating with reactive behavior, finally cause the formation of three dimensional structure, thus make paint solidification; It is mainly used in the material surfaces such as woodenware, paper, plastics coating, glass, metal material, liquid crystal plaque.Can claim photoactive coating again, take UV-light as the also title ultraviolet-curing paint of the paint solidification energy.
Photo-cured coating is a kind of save energy, resource-saving, nuisanceless, the high efficiency coating new variety of rising in recent years, utilize the energy of light cause low molecule performed polymer in coating or oligomer and as reactive thinner monomer molecule between polymerization and crosslinking reaction, obtain the paint film that hardens; Advantage is set time short (part second is to several minutes), solidification value is low, volatile matter is low.
Sulfonate monomer often plays conclusive effect for the water-wet behavior of hydrophilic coating, and in ultraviolet light polymerization oiliness coating system, the solvability of sulfonate monomer is very limited, can not be dispersed in coating well, ultraviolet light curing anti fogging coating composite (CN101602913A) as a kind of in Chinese patent.
At present, the photo-cured coating that a kind of solvability of sulfonate monomer is good is needed.
Summary of the invention
The embodiment of the present invention has avoided sulfonate monomer and this difficult problem of photocuring oil paint Miscibility difference, is added in photocuring emulsion by sulfonate monomer strong for wetting ability, provides the photo-cured coating that a kind of solvability of sulfonate monomer is good.
For achieving the above object, the embodiment of the present invention provides following technical scheme:
A kind of photocuring hydrophilic coating, this coating composition and mass percent are:
Sulfonate monomer 10 ~ 30%
Photocuring emulsion 30 ~ 70%
Multifunctional reactive thinner 8 ~ 30%
Light trigger 0.5 ~ 5%
Auxiliary agent 0.1 ~ 2%
Balance of solvent
Described sulfonate monomer is the polymerisable monomer simultaneously containing sulfonate groups and double bond.
Preferably, this sulfonate monomer is at least one in vinyl sulfonic acid sodium, sodium allyl sulfonate, methacrylic acid hydroxypropyl sulfonic acid sodium, allyloxy hydroxide sodium dimercaptosulphanatein.
Preferably, this photocuring emulsion is at least one in Epoxy-Acrylate Emulsion, polyurethane-acrylate emulsion, polyester acrylate emulsion.
Preferably, this multifunctional reactive thinner is at least one in tripropylene glycol acrylate, Viscoat 295, hexanediyl ester, neopentylglycol diacrylate, pentaerythritol triacrylate, pungent penta tetrol triacrylate, Isooctyl acrylate monomer.
Preferably, this light trigger is at least one in 2-methyl-2-hydroxyl-1-phenyl-acetone, 1-hydroxy cyclohexylphenyl benzoylformaldoxime, 2,4,6-trimethylbenzoy-dipheny phosphorus oxide, benzophenone, active ammonia.
Preferably, this auxiliary agent is at least one in flow agent or defoamer.
Preferably, this solvent is more than one in butylacetate, propyl acetate, ethyl acetate, acetone, butanone, benzene,toluene,xylene, propyl carbinol, Virahol, ethanol.
The present invention also provides the preparation method of above-mentioned a kind of photocuring hydrophilic coating, accurately takes and adds described sulfonate monomer, photocuring emulsion, multifunctional reactive thinner, auxiliary agent and solvent successively, mixing; Add described light trigger again, after stirring evenly, namely obtain photocuring hydrophilic coating.
Compared with prior art, the present invention has following beneficial effect:
1, wetting ability is strong: added by sulfonate monomer strong for wetting ability in the aqueous photo-curing emulsion of acrylic system, utilize parent/hydrophobic property that vinylformic acid is suitable, the highly Ionized hydrophilic sulfonic acid group in surface of separating film of polymer grafting, significantly improves the wetting ability of polymer separation film.The contact angle of modified separatory membrane obviously declines, and show that the wetting ability of separatory membrane improves greatly, and function monomer is fixed on film surface with the form of chemical bond, therefore wetting ability can keep for a long time.It is 2-9 ° that the paint sample that the embodiment of the present invention obtains records initial stage contact angle, and continuous contact angle is 16-25 °.
2, light-cured performance is strong: sulfonate monomer contains double bond, the acrylic-functional contained in acrylic system is also containing double bond, double bond is easily caused fracture by the free radical excited by ultraviolet lighting, linear polymeric instantaneous crosslink is made to reticulate structure, and the softening temperature of maximum speed of reaction, cured film and Tg improve with the increase of double bond concentration, possess excellent photosensitivity, there is higher laser curing velocity.
Embodiment
Be clearly and completely described to the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
In following embodiment, by as follows for the step that the photo-cured coating of this formula is coated on aluminium foil surface: by this photocuring hydrophilic coating roller coat in the aluminium foil surface of existing photocuring counterdie, place 8 seconds in 100 DEG C of baking ovens, then with the ultraviolet lamp radiation 5 seconds of 4KW.
Initial stage contact angle testing method: the diaphragm cutting 3cm × 7cm, measures its initial stage contact angle.
Protracted hydrophilicity testing method: the diaphragm cutting 3cm × 7cm, is placed on drying and watering cycle machine, takes out after placing 42h at 20 DEG C, and room temperature dries its surface hydrophilic angle of rear measurement.
Sulfonate monomer strong for wetting ability adds in aqueous photo-curing emulsion by the embodiment of the present invention, provides the photo-cured coating that a kind of solvability of sulfonate monomer is good.It is below specific embodiment.
Embodiment one,
| Material | Vinyl sulfonic acid sodium | Epoxy-Acrylate Emulsion (EA) | Tripropylene glycol acrylate, pentaerythritol triacrylate | 2-methyl-2-hydroxyl-1-phenyl-acetone | Flow agent | Butylacetate |
| Quality (g) | 15 | 60 | 10 | 1 | 1.5 | 12.5 |
The present embodiment initial stage contact angle is 7 °, and continuous contact angle is 20 °.
Embodiment two,
| Material | Sodium allyl sulfonate | Polyurethane-acrylate emulsion (PUA), polyester acrylate emulsion | Viscoat 295 | 1-hydroxy cyclohexylphenyl benzoylformaldoxime | Flow agent | Propyl acetate |
| Quality (g) | 25 | 45 | 15 | 0.5 | 1 | 13.5 |
The present embodiment initial stage contact angle is 7 °, and continuous contact angle is 25 °.
Embodiment three,
| Material | Methacrylic acid hydroxypropyl sulfonic acid sodium, sodium allyl sulfonate | Epoxy-Acrylate Emulsion | Tripropylene glycol acrylate | 2,4,6-trimethylbenzoy-dipheny phosphorus oxide | Defoamer | Butylacetate, propyl acetate |
| Quality (g) | 20 | 30 | 20 | 5 | 1.5 | 23.5 |
The present embodiment initial stage contact angle is 5 °, and continuous contact angle is 19 °.
Embodiment four,
| Material | Allyloxy hydroxide sodium dimercaptosulphanatein | Polyester acrylate emulsion | Hexanediyl ester | 2-methyl-2-hydroxyl-1-phenyl-acetone | Defoamer | Ethyl acetate |
| Quality (g) | 10 | 70 | 10 | 3 | 2 | 5 |
The present embodiment initial stage contact angle is 6 °, and continuous contact angle is 22 °.
Embodiment five,
| Material | Vinyl sulfonic acid sodium, allyloxy hydroxide sodium dimercaptosulphanatein | Epoxy-Acrylate Emulsion | Neopentylglycol diacrylate | Active ammonia, 2,4,6-trimethylbenzoy-dipheny phosphorus oxide | Flow agent | Acetone |
| Quality (g) | 20 | 55 | 8 | 2 | 0.1 | 14.9 |
The present embodiment initial stage contact angle is 4 °, and continuous contact angle is 17 °.
Embodiment six,
| Material | Allyloxy hydroxide sodium dimercaptosulphanatein | Polyester acrylate emulsion | Pungent penta tetrol triacrylate, hexanediyl ester | 2,4,6-trimethylbenzoy-dipheny phosphorus oxide | Defoamer | Butanone |
| Quality (g) | 30 | 20 | 30 | 4 | 0.25 | 15.75 |
The present embodiment initial stage contact angle is 2 °, and continuous contact angle is 18 °.
Embodiment seven,
| Material | Methacrylic acid hydroxypropyl sulfonic acid sodium | Epoxy-Acrylate Emulsion, polyurethane-acrylate emulsion | Isooctyl acrylate monomer, hexanediyl ester | 1-hydroxy cyclohexylphenyl benzoylformaldoxime | Flow agent | Benzene |
| Quality (g) | 29 | 10 | 25 | 3.5 | 0.35 | 32.15 |
The present embodiment initial stage contact angle is 3 °, and continuous contact angle is 20 °.
Embodiment eight,
| Material | Sodium allyl sulfonate | Polyurethane-acrylate emulsion | Pungent penta tetrol triacrylate | 1-hydroxy cyclohexylphenyl benzoylformaldoxime, benzophenone | Defoamer | Toluene |
| Quality (g) | 22 | 50 | 17 | 4.5 | 0.75 | 5.75 |
The present embodiment initial stage contact angle is 5 °, and continuous contact angle is 24 °.
Embodiment nine,
| Material | Methacrylic acid hydroxypropyl sulfonic acid sodium, allyloxy hydroxide sodium dimercaptosulphanatein | Epoxy-Acrylate Emulsion | Tripropylene glycol acrylate | Active ammonia | Defoamer | Dimethylbenzene |
| Quality (g) | 12 | 35 | 12 | 2.5 | 1.25 | 37.25 |
The present embodiment initial stage contact angle is 6 °, and continuous contact angle is 25 °.
Embodiment ten,
| Material | Vinyl sulfonic acid sodium | Polyester acrylate emulsion, Epoxy-Acrylate Emulsion | Viscoat 295 | Benzophenone | Flow agent, defoamer | Propyl carbinol |
| Quality (g) | 16 | 40 | 28 | 1.5 | 1.75 | 12.75 |
The present embodiment initial stage contact angle is 5 °, and continuous contact angle is 20 °.
Embodiment 11,
| Material | Methacrylic acid hydroxypropyl sulfonic acid sodium | Polyurethane-acrylate emulsion | Tripropylene glycol acrylate | Active ammonia | Flow agent, defoamer | Virahol |
| Quality (g) | 26 | 25 | 16 | 2.2 | 2 | 28.8 |
The present embodiment initial stage contact angle is 6 °, and continuous contact angle is 23 °.
Embodiment 12,
| Material | Sodium allyl sulfonate | Polyester acrylate emulsion | Hexanediyl ester | 1-hydroxy cyclohexylphenyl benzoylformaldoxime | Defoamer | Ethanol |
| Quality (g) | 25 | 35 | 26 | 2 | 1 | 11 |
The present embodiment initial stage contact angle is 7 °, and continuous contact angle is 21 °.
Above a kind of photocuring hydrophilic coating that the embodiment of the present invention provides is described in detail, apply specific case herein to set forth principle of the present invention and embodiment, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping; Meanwhile, for one of ordinary skill in the art, according to thought of the present invention, all will change in specific embodiments and applications, in summary, this description should not be construed as limitation of the present invention.
Claims (7)
1. a photocuring hydrophilic coating, is characterized in that, this coating composition and mass percent are:
Described sulfonate monomer is the polymerisable monomer simultaneously containing sulfonate groups and double bond; The described polymerisable monomer simultaneously containing sulfonate groups and double bond is at least one in vinyl sulfonic acid sodium, sodium allyl sulfonate, methacrylic acid hydroxypropyl sulfonic acid sodium, allyloxy hydroxide sodium dimercaptosulphanatein.
2. a kind of photocuring hydrophilic coating according to claim 1, is characterized in that, described photocuring emulsion is at least one in Epoxy-Acrylate Emulsion, polyurethane-acrylate emulsion, polyester acrylate emulsion.
3. a kind of photocuring hydrophilic coating according to claim 1, it is characterized in that, described multifunctional reactive thinner is at least one in tripropylene glycol acrylate, Viscoat 295, hexanediyl ester, neopentylglycol diacrylate, pentaerythritol triacrylate, pungent penta tetrol triacrylate, Isooctyl acrylate monomer.
4. a kind of photocuring hydrophilic coating according to claim 1; it is characterized in that; described light trigger is at least one in 2-methyl-2-hydroxyl-1-phenyl-acetone, 1-hydroxy cyclohexylphenyl benzoylformaldoxime, 2,4,6-trimethylbenzoy-dipheny phosphorus oxide, benzophenone, active ammonia.
5. a kind of photocuring hydrophilic coating according to claim 1, is characterized in that, described auxiliary agent is at least one in flow agent or defoamer.
6. a kind of photocuring hydrophilic coating according to claim 1, is characterized in that, described solvent is more than one in butylacetate, propyl acetate, ethyl acetate, acetone, butanone, benzene,toluene,xylene, propyl carbinol, Virahol, ethanol.
7. the preparation method of a kind of photocuring hydrophilic coating as claimed in claim 1, is characterized in that, accurately takes and adds described sulfonate monomer, photocuring emulsion, multifunctional reactive thinner, auxiliary agent and solvent successively, mixing; Add described light trigger again, after stirring evenly, namely obtain photocuring hydrophilic coating.
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| CN105983514A (en) * | 2015-03-06 | 2016-10-05 | 上海维凯光电新材料有限公司 | Photocuring coating device applicable to hydrophilic aluminum foil coating and coating method based on device |
| CN108727625A (en) * | 2017-04-21 | 2018-11-02 | 北京化工大学 | The preparation method of hydrophilic modifying thin polymer film |
| CN109913017A (en) * | 2019-03-28 | 2019-06-21 | 苏州达万塑胶电子有限公司 | A kind of self-cleaning anti-fog coating of rain-proof film |
| CN109880537A (en) * | 2019-04-15 | 2019-06-14 | 苏州达万塑胶电子有限公司 | A kind of plane rain-proof view expands film and its processing technology |
| CN110922843A (en) * | 2019-12-18 | 2020-03-27 | 湖南智涂环保科技有限公司 | Super-hydrophilic coating and preparation method thereof |
| CN113372797A (en) * | 2021-06-29 | 2021-09-10 | 广东康伴新材料科技有限公司 | High-gloss high-fullness UV coating and preparation method thereof |
| CN115678328A (en) * | 2022-11-04 | 2023-02-03 | 江南大学 | Preparation method of UV-cured super-hydrophilic anti-fog coating containing sodium sulfonate compound |
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| CN1350037A (en) * | 2000-10-20 | 2002-05-22 | 东洋纺绩株式会社 | Photo-curing composition and its curing method |
| CN101302264A (en) * | 2007-05-11 | 2008-11-12 | 北京化工大学 | Polymer emulsion having unsaturated double bond and preparation thereof |
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| JP2002008620A (en) * | 2000-06-20 | 2002-01-11 | Jsr Corp | Separator for alkaline storage battery and alkaline storage battery |
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| CN1350037A (en) * | 2000-10-20 | 2002-05-22 | 东洋纺绩株式会社 | Photo-curing composition and its curing method |
| CN101302264A (en) * | 2007-05-11 | 2008-11-12 | 北京化工大学 | Polymer emulsion having unsaturated double bond and preparation thereof |
| CN101602913A (en) * | 2009-06-26 | 2009-12-16 | 广州慧谷化学有限公司 | A kind of ultraviolet light curing anti fogging coating composite and compound method thereof |
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Effective date of registration: 20201026 Address after: No.137 Dadao Road, Dieshiqiao, Sanxing Town, Haimen City, Nantong City, Jiangsu Province Patentee after: Haimen Mao Mao Art Design Co.,Ltd. Address before: Sheng Tong Industrial Park No. 109 Venus 410200 Hunan province Changsha road in Wangcheng County Patentee before: Hunan Sheng Tong Technology Group Co.,Ltd. |