CN108912807A - A method of improving aqueous polyurethane coating wearability - Google Patents
A method of improving aqueous polyurethane coating wearability Download PDFInfo
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- CN108912807A CN108912807A CN201810940234.2A CN201810940234A CN108912807A CN 108912807 A CN108912807 A CN 108912807A CN 201810940234 A CN201810940234 A CN 201810940234A CN 108912807 A CN108912807 A CN 108912807A
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- China
- Prior art keywords
- aqueous polyurethane
- polyurethane coating
- wearability
- galactomannans
- coating
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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
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Abstract
The invention discloses a kind of methods for improving aqueous polyurethane coating wearability, can effectively improve the wearability of aqueous polyurethane coating in the case where not changing coating hardness added with galactomannans component in aqueous polyurethane coating.The molecular weight ranges of addition 1% are 0.4 × 10 in water paint4~1.5 × 104The wearability of the low molecular weight galactomannans of Da, coating improves 5.58%-49.11%.The method of raising aqueous polyurethane coating wearability of the invention, with simple process, condition is easily controllable, paint film property is good, can be widely applied to the fields such as decoration, furniture, building, machinery, chemical industry.
Description
Technical field
The invention belongs to technical field of environmental protection paint, and in particular to a kind of side for improving aqueous polyurethane coating wearability
Method.
Background technique
Coating be it is a kind of can securely be covered on body surface, the chemistry for playing protection, decoration, mark and other specific uses is mixed
Close object.According to the difference of solvent in coating, coating can be divided into organic solvent type coatings and water paint etc..Wherein, solvent type
The decentralized medium of coating is organic solvent, plays the role of dissolving resin and dilution coating.Solvent based coating solidified in film forming
Cheng Zhong, organic solvent volatilization after the dry and hard film forming of film forming matter, form hard protective film, to the substrates such as woodwork play protection and
The effect of beautification.Solvent based coating mainly has the volatile organic matter of benzene series, organic ketone, amine, alcohol, ether, ester, acid etc., these are waved
Many photochemical reactions can occur under the action of sunlight for volatile material, form the bigger secondary pollution of toxicity, as ozone,
Aldehydes, Peroxyacetyl nitrate etc..By institutes such as these oxynitrides, hydrocarbon compound and its photochemically reactive intermediate products
The special mixture of composition is photochemical fog, and the generation of ozone is the mark of photochemical fog.Therefore, low pollution, environmental protection
The research and development of type have become the new direction of coating industry development.
Water paint is free of or less containing volatile materials and air pollutants, small to environmental and human health impacts harm, has become
For the research hotspot of the fields green environmental friendly coatings such as furniture and building.But compared with traditional solvent based coating, water paint
Lower hardness, wearability are poor, are unsuitable for the strong field of the coating abrasiveness such as machinery, chemical industry.Therefore, it is wear-resisting to improve water paint
Property feature, be improve its coating industry application field important measure.
Summary of the invention
Goal of the invention：In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of raising aqueous polyurethane coatings
The low molecular weight galactomannans of certain molecular weight range is dispersed in water paint, not by the method for wearability
In the case where changing coating hardness, the wearability and glossiness of water paint are improved.There is the method simple process, condition to be easy to control
System, paint film property are good, can be widely applied to the fields such as decoration, furniture, building, machinery, chemical industry.
Technical solution：In order to achieve the above-mentioned object of the invention, technical scheme is as follows：
A method of aqueous polyurethane coating wearability is improved, it is poly- added with galactomannan in aqueous polyurethane coating
Saccharic composition.
The g/mL additive amount of the galactomannans is 1~3%.
The molecular weight ranges of the galactomannans are 0.4 × 104~1.5 × 104Da。
The molecular weight ranges of the galactomannans are 1.5 × 104Da。
The method of the raising aqueous polyurethane coating wearability, in aqueous polyurethane coating before use, gala is added
Mannan component is uniformly mixed.
The method of the raising aqueous polyurethane coating wearability, every 100mL aqueous polyurethane coating contain 71.4mL
Polyurethane polyhydroxy pre-polymerization dispersion liquid and 28.6mL polyisocyanate curing agent.
It using mannose is that basic structural unit passes through β-Isosorbide-5-Nitrae-that galactomannans (Galactomannan, GM), which is a kind of,
Glycosidic bond form main chain, the non-linear heteroglycan on main chain is connected to by α -1,6- glycosidic bond with galactolipin, with acid and alkali-resistance,
The characteristics such as thermal stability is good, molecular weight is high, viscosity is big, hydroxy radical content is high and water solubility is strong.The application is equal by galactomannans
It is even to be scattered in coating, in polysaccharide hydroxyl abundant can and water paint in the alcoholic extract hydroxyl group of polyalcohol Hydrogenbond, gala occurs
Mannosan and crosslinking coatings form compound, to assign water paint some properties.
Beneficial effect：There is the prior art to compare, the present invention adds certain molecular weight range in aqueous polyurethane coating
Galactomannans can effectively improve the wearability of water paint in the case where not changing coating hardness.The method has work
Skill is simple, condition is easily controllable, paint film property is good, can be widely applied to the fields such as decoration, furniture, building, machinery, chemical industry.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated.Embodiment is for the illustrative and not limiting present invention.
Any those of ordinary skill in this field can do appropriate it will be appreciated that these embodiments, do not limit the invention in any way
Modification and without prejudice to essence of the invention and deviate the scope of the present invention.
In following embodiment, galactomannan molecule amount (Mw) is measured using efficient liquid phase gel permeation chrommatograph.Chromatograph：
HPLC high performance liquid chromatograph；Chromatographic column：Waters Ultrahydrogel TM 2000(7.8×300mm),Waters
Three column of Ultrahydrogel TM 250 (7.8 × 300mm) and Waters Ultrahydrogel TM 120 (7.8 × 300mm)
It is sequentially connected in series,；Mobile phase：Ionized water, flow velocity 0.6mL/min；Column temperature：65℃；Composition distribution detection；Standard sample：It is poly-
Ethylene glycol (molecular weight 360-120000Da).
Embodiment 1
Low molecular weight galactomannans preparation method
(1) prepared by galactomannans extract.It air-dries sesbania albumen tablet to be mechanically pulverized, is added and distills by 1: 50 solid-to-liquid ratio
Water is centrifuged 10min after 50 DEG C of extractings for 24 hours under the conditions of 10000 revs/min, obtains supernatant, is added into supernatant anhydrous
Ethyl alcohol is precipitated, and sediment is vacuum dried to obtain galactomannans powdery solid.
(2) inscribe mannase selective hydrolysis galactomannans.The galactomannans weighed in step (1) mentions
It takes object 20.0g in 2L enzyme reaction tank, distilled water is added, inscribe mannonase 1mol/L citrate buffer solution makes reaction solution
Volume is 1000mL, is sufficiently mixed uniformly, in concentration of substrate 10%, enzyme dosage 20U/g galactomannans, 4.8,50 DEG C of pH value
Under the conditions of react for 24 hours, after enzymatic hydrolysis reaction, protease hydrolysate is placed at 100 DEG C and handles 10min, makes inscribe mannosan
Enzyme inactivation, is centrifuged 10min under the conditions of 10000 revs/min, and supernatant is the enzymatic hydrolysis of the incomplete catabolite containing galactomannans
Liquid.
(3) the low molecular weight galactomannans component preparation of different molecular weight ranges.Take the galactomannan in step (2)
Glycan digests supernatant 1000mL, and dehydrated alcohol is added under agitation, makes concentration of alcohol 40% (v/v) in system, in
It is centrifuged 10min under the conditions of 10000 revs/min, obtains supernatant and precipitating.Precipitating divides 3 with the ethanol water 30mL of 40% (v/v)
Secondary washing, centrifugation (10000 revs/min, 10min), freeze-drying obtain solid sample P1, and measure its molecular weight.Supernatant after
Continue the classification separation for next stage.
(4) supernatant after taking step (3) to be separated by solid-liquid separation, dehydrated alcohol is added under agitation, makes ethyl alcohol in system
Concentration is 50% (v/v), is centrifuged 10min under the conditions of 10000 revs/min, obtains supernatant and precipitating.50% (v/v) of precipitating
Points of 3 times washings of ethanol water 30mL, centrifugation (10000 revs/min, 10min), freeze-drying obtains solid sample P2, and survey
Its fixed molecular weight.Supernatant continues on for the classification separation of next stage.
(5) supernatant after taking step (4) to be separated by solid-liquid separation, dehydrated alcohol is added under agitation, makes ethyl alcohol in system
Concentration is 65% (v/v), is centrifuged 10min under the conditions of 10000 revs/min, obtains supernatant and precipitating.65% (v/v) of precipitating
Points of 3 times washings of ethanol water 30mL, centrifugation (10000 revs/min, 10min), freeze-drying obtains solid sample P3, and survey
Its fixed molecular weight.
The result shows that the molecular weight of low molecular weight galactomannans P1, P2 and P3 of resulting different molecular weight are distinguished
It is 1.5 × 104Da、0.8×104Da and 0.4 × 104Da。
Embodiment 2
The preparation of high-wearing feature aqueous polyurethane coating, steps are as follows
(1) commercially available polyurethane polyhydroxy pre-polymerization dispersion liquid (solid content 40%, w/v) and polyisocyanate is taken to solidify
Agent (solid content 80%, w/v), according to pre-polymerization dispersion liquid: the ratio of curing agent 10: 4 (v: v) measures 71.4mL polyurethane
Polyhydroxy pre-polymerization dispersion liquid and 28.6mL polyisocyanate curing agent disperse 10min using homogenizer at 25 DEG C, obtain water
Property polyurethane coating.
(2) in the 100mL aqueous polyurethane coating that step (1) obtains according to 1%, 2% and 3% low molecular weight gala
Mannosan additive amount, the galactomannans (P1, P2 and P3) that 1g, 2g and 3g different molecular weight is added are used as modifying agent,
Disperse 10min using homogenizer at 25 DEG C, obtains modified aqueous polyurethane coating.
Embodiment 3
Aqueous polyurethane coating made from Example 2 and modified polyurethane paint will be modified respectively using pressure injection
The aqueous polyurethane coating of front and back is coated on surface of wooden substrate.Wood substrate used is multi-plywood, size is 10 ×
10cm, coating thickness are 60 μm.After the paint solidification film forming of surface of wooden substrate, substrate is placed in 50 DEG C of air dry ovens
Extra moisture in dry 120min vaporizing coating material, after room temperature divulges information and places 7d, carry out adhesive force, glossiness, abrasion loss and
Pencil hardness detection.
The results of property of aqueous polyurethane coating and modified aqueous polyurethane coating is as shown in table 1.
1 aqueous polyurethane coating of table and modified aqueous polyurethane coating performance
| Number | Additive amount (%) | Adhesive force grade | Pencil hardness | Abrasion loss (g) | Wearability increase rate (%) |
| Water paint | 0 | 2 | 5H | 0.0167 | - |
| P1+ water paint | 1 | 2 | 5H | 0.0085 | 49.11 |
| P1+ water paint | 2 | 2 | 5H | 0.0091 | 45.51 |
| PI+ water paint | 3 | 2 | 5H | 0.0104 | 37.72 |
| P2+ water paint | 1 | 2 | 5H | 0.0103 | 38.32 |
| P2+ water paint | 2 | 2 | 5H | 0.0105 | 37.13 |
| P2+ water paint | 3 | 2 | 4H | 0.0117 | 29.94 |
| P3+ water paint | 1 | 2 | 5H | 0.0151 | 9.58 |
| P3+ water paint | 2 | 2 | 4H | 0.0155 | 7.19 |
| P3+ water paint | 3 | 2 | 4H | 0.0161 | 3.59 |
The result shows that the low molecular weight galactomannans modifying agent of different molecular weight is added in aqueous polyurethane coating,
The hardness of adhesive ability and coating of the coating on wood substrate is not changed.When additive amount respectively is 1%, molecular weight be 1.5 ×
104Da、0.8×104Da and 0.4 × 104When the low molecular weight galactomannans of Da, the wearability increase rate point of water paint
Not Wei 49.11%, 38.32% and 9.58%, illustrate galactomannans as the modifying agent of water paint and can improve its and is wear-resisting
Property.
Claims (6)
1. a kind of method for improving aqueous polyurethane coating wearability, it is characterised in that：It is added in aqueous polyurethane coating
Galactomannans component.
2. the method according to claim 1 for improving aqueous polyurethane coating wearability, which is characterized in that the gala
The g/mL additive amount of mannosan is 1~3%.
3. the method according to claim 1 or 2 for improving aqueous polyurethane coating wearability, which is characterized in that described
The molecular weight ranges of galactomannans are 0.4 × 104~1.5 × 104Da。
4. the method according to claim 1 or 2 for improving aqueous polyurethane coating wearability, which is characterized in that described
The molecular weight ranges of galactomannans are 1.5 × 104Da。
5. the method according to claim 1 or 2 for improving aqueous polyurethane coating wearability, which is characterized in that aqueous
Polyurethane coating is uniformly mixed before use, addition galactomannans component.
6. the method according to claim 1 or 2 for improving aqueous polyurethane coating wearability, which is characterized in that every 100mL
Aqueous polyurethane coating contains the polyisocyanate curing agent of polyurethane the polyhydroxy pre-polymerization dispersion liquid and 28.6mL of 71.4mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810940234.2A CN108912807B (en) | 2018-08-16 | 2018-08-16 | Method for improving wear resistance of waterborne polyurethane coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810940234.2A CN108912807B (en) | 2018-08-16 | 2018-08-16 | Method for improving wear resistance of waterborne polyurethane coating |
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| Publication Number | Publication Date |
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| CN108912807A true CN108912807A (en) | 2018-11-30 |
| CN108912807B CN108912807B (en) | 2021-02-19 |
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| CN201810940234.2A Active CN108912807B (en) | 2018-08-16 | 2018-08-16 | Method for improving wear resistance of waterborne polyurethane coating |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078883A (en) * | 2019-05-22 | 2019-08-02 | 西华大学 | A kind of water paint resin, preparation method and composition based on konjaku flour |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348530A (en) * | 2008-09-17 | 2009-01-21 | 北京林业大学 | Galactomannan gum got by irradiation degradation, preparation and use thereof |
| CN104761940A (en) * | 2015-03-25 | 2015-07-08 | 田福东 | Wear-resistant waterborne polyurethane coating |
-
2018
- 2018-08-16 CN CN201810940234.2A patent/CN108912807B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348530A (en) * | 2008-09-17 | 2009-01-21 | 北京林业大学 | Galactomannan gum got by irradiation degradation, preparation and use thereof |
| CN104761940A (en) * | 2015-03-25 | 2015-07-08 | 田福东 | Wear-resistant waterborne polyurethane coating |
Non-Patent Citations (3)
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| 付美龙等: "《油田应用化学》", 31 December 2005, 武汉大学出版社 * |
| 朱万强: "《涂料基础教程》", 30 June 2012, 西南交通大学出版社 * |
| 潘汝潭: "纳米纤维素改性水性聚氨酯及其在木器涂料中的应用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078883A (en) * | 2019-05-22 | 2019-08-02 | 西华大学 | A kind of water paint resin, preparation method and composition based on konjaku flour |
| CN110078883B (en) * | 2019-05-22 | 2021-08-03 | 西华大学 | Water-based paint resin based on konjac flour, preparation method and composition thereof |
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Application publication date: 20181130 Assignee: Suzhou Hertz Electronic Technology Co.,Ltd. Assignor: NANJING FORESTRY University Contract record no.: X2021320000035 Denomination of invention: A method to improve the wear resistance of Waterborne Polyurethane Coatings Granted publication date: 20210219 License type: Common License Record date: 20210528 |
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Application publication date: 20181130 Assignee: Suzhou Xiaohan culture media Co.,Ltd. Assignor: NANJING FORESTRY University Contract record no.: X2022320000026 Denomination of invention: Method for improving wear resistance of waterborne polyurethane coating Granted publication date: 20210219 License type: Common License Record date: 20220302 |