CN101353549B - Modified polyurethane gloss oil and use thereof - Google Patents
Modified polyurethane gloss oil and use thereof Download PDFInfo
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- CN101353549B CN101353549B CN2008101983955A CN200810198395A CN101353549B CN 101353549 B CN101353549 B CN 101353549B CN 2008101983955 A CN2008101983955 A CN 2008101983955A CN 200810198395 A CN200810198395 A CN 200810198395A CN 101353549 B CN101353549 B CN 101353549B
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- modified polyurethane
- gloss oil
- polyurethane gloss
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Abstract
The invention discloses modified polyurethane gloss oil and an application thereof. The film-forming material for the modified polyurethane of the invention is modified phthalic anhydride polyester-based polyurethane; the formula thereof is simple; and the production is convenient. The modified polyurethane gloss oil has good thermal property, especially low-temperature flexibility, complies with the use environment of polyolefin films, uses products derived from stearic acid monoglyceride modified phthalic anhydride polyester polyols, has good wetting property of polyolefin substrate, excellent solvent resistance, low cost and good gloss, and can be well applied to polyolefin plastic products.
Description
Technical field
The invention belongs to the coating material field, be specifically related to a kind of modified polyurethane gloss oil and application thereof.
Background technology
Polyolefin plastic products such as polyethylene, polypropylene, polyhutadiene, ethylene-propylene copolymer material have the performance of good physics and chemistry, owing to contain less polar material, the corrosion of the most of acid of ability, alkali in its molecular structure.Be insoluble to general solvent at normal temperatures, and because its linear structure and high crystalline energy, make resulting product have better plasticity and also have impact-resistance preferably simultaneously, therefore be widely used in and be prepared into film, pipeline, various goods such as sheet material, thereby in light packing, water supply and sewerage pipeline, household utensils, industries such as materials used in auto manufacturing are occupied critical role.Owing to contain less polar material in the polyolefin plastics molecular structure, caused this class material to have low polarity or nonpolar surface, this apolar surfaces is to covering with paint, lacquer, colour wash, etc. printing or the bonding difficulty of having brought on the polyolefin plastic products, for reaching the good result that this class base material is applied and prints, usually need carry out surface active to base material, this activation is in order to improve the surface energy of plastics, increase its surface tension, also promptly generate some polar groups or in addition alligatoring, so that coating is easier to be wetting and be adsorbed in the product surface at frosting.Practice is found, polyolefin substrate through surface activation process is enhanced on capillary raising and printing adaptability really, but,, lost and stablized inactive surface originally owing to change through the polyolefin substrate surface properties of surface activation process, therefore, treated surface cover with paint, lacquer, colour wash, etc. or sticking and after can obtain to have good solvent resistance, rub resistance, high-low temperature resistant by the mode of oil polish, high light, the product surface of excellent properties such as high-luster.
This series products of being sold in the market has more defective, not enough as polyamide-based product frost resistance, be gelatin in the time of 0 ℃, be unsuitable for winter or north use, silicone based product then cost is higher, and vinylformic acid and esters of acrylic acid product application are in film mechanical property deficiency etc. then.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of fill a prescription form simple, convenient for production, have particularly low temperature flexibility of good thermal characteristics, and can be good at being applicable to the modified polyurethane gloss oil of polyolefin plastic products.
Another object of the present invention is to provide the application of above-mentioned modified polyurethane gloss oil on copolymer material product surfaces such as polyolefin plastic products such as polyethylene, polypropylene, polyhutadiene, ethylene-propylene.
Above-mentioned purpose of the present invention is achieved by following scheme:
A kind of modified polyurethane gloss oil, form by each component of following weight percent:
Modified poly ester polyvalent alcohol 20%～60%
Solidifying agent 5%～30%
Solvent 30%～70%
Defoamer 0.1%～1%.
Above-mentioned modified polyurethane gloss oil, the optimization of C of its each component is:
Modified poly ester polyvalent alcohol 25%～40%
Solidifying agent 10%～20%
Solvent 40%～60%
Defoamer 0.1%～1%.
Above-mentioned solidifying agent can be commercially available polyisocyanates, also can use tolylene diisocyanate (TDI) and TriMethylolPropane(TMP) to react products obtained therefrom with 3: 1 molar ratio.
Above-mentioned solvent can be selected from toluene, dimethylbenzene, N-BUTYL ACETATE, ethyl acetate, hexanaphthene or propylene glycol monomethyl ether, and the effect of solvent here is to regulate the product viscosity as thinner.
Above-mentioned defoamer can be silicone based defoamer and commercially available any defoamer.
Above-mentioned modified poly ester polyvalent alcohol is the main film forming substance of modified polyurethane gloss oil of the present invention.
Above-mentioned modified poly ester polyvalent alcohol, its preparation method is as follows:
Tetra hydro Phthalic anhydride, neopentyl glycol and stearic acid list glyceride are carried out polyreaction (dehydration contract and), and wherein the reaction molecular fraction of reaction raw materials Tetra hydro Phthalic anhydride, neopentyl glycol and glyceryl monostearate is:
Tetra hydro Phthalic anhydride 35%～45%
Neopentyl glycol 40%～50%
Stearic acid Tegin 55G 10%～20%.
The molecular weight ranges of above-mentioned modified poly ester polyvalent alcohol can be adjusted between 1000～6000 by reaction conditions.
Modified polyurethane gloss oil of the present invention in its preparation process, is allocated by the aforementioned formula amount, and wherein solidifying agent just adds before use.
Modified polyurethane gloss oil of the present invention; because its structure is the phthalic anhydride PAUR that is grafted with the hydrophobic alkyl side chain; therefore; product is better to the wettability of polyolefin substrate; and product acts on the good low temperature flexibility of urethane resin and good solvent resistance; its mechanical property and polyolefin articles particularly film article are quite similar, use restriction little to base material when being used as the gloss oil product of polyolefin articles, can also obtain to have simultaneously glossiness and high performance protection surface.
Modified polyurethane gloss oil product of the present invention can be used on the copolymer material product surfaces such as polyolefin plastic products such as polyethylene, polypropylene, polyhutadiene, ethylene-propylene, is particularly useful for the preparation of polyethylene and polypropylene film table printed material material and seal back gloss oil uses.
Compared with prior art, the present invention has following beneficial effect:
1. modified polyurethane gloss oil of the present invention can meet the attachment fastness inspection level of GB/T13217.7---91 standard to the sticking power excellence of polyolefin substrate;
2. remodeling polyurethane gloss oil of the present invention has good thermal characteristics, and the product of filming is investigated its blocking under warming at the heating high bake after two hours, still have good use properties;
3. the phthalic anhydride polyester urethane resin that remodeling polyurethane gloss oil of the present invention is modification is made, and it is obvious to be compared to existing more its cost advantage of polyether(poly)urethane, and solvent resistance is good.
4. modified polyurethane gloss oil of the present invention is because the characteristics that possessed on himself structure, in prescription, need not to add a large amount of small molecules tensio-active agents and come its wetting ability of modification polyolefin surfaces, hydrophobic side chain in its structure has promptly been given product to polyolefin substrate wettability preferably, thereby make products obtained therefrom in use the bad phenomenon that the small molecules auxiliary agent oozes out in a large number can not take place, can give one of product surface and have hydrophobic and stable surface.
5. in the prior art, polyamide-based polyolefin substrate print product uses more, but its frost resistance is not enough, has been gelatin in the time of 0 ℃, is unsuitable for winter or north use, need to add more auxiliary agent to promote anti-freezing property, and its blocking under warming is bad, thereby influences the final use properties of product, and silicone based excellent product performance but cost are than higher, vinylformic acid and esters of acrylic acid product application in film then mechanical property be unsuitable for the softish film product, need to add a large amount of auxiliary agents and come modification; And modified polyurethane gloss oil of the present invention is with low cost, form simple and convenient for production, good to the polyolefin substrate moistened surface ability after handling, adhere firmly, the thermal characteristics excellence has extremely important actual value aspect the wide popularization and application of market.
Embodiment
In following examples, will further illustrate content of the present invention, but not limit the present invention with this.
Embodiment 1 modified polyurethane gloss oil product
The modified polyurethane gloss oil product of present embodiment, form by following each component:
Modified poly ester polyvalent alcohol (by following step self-control) 30g
Solidifying agent 10g
Solvent 59g
Defoamer 1g
The modified polyurethane gloss oil product of present embodiment, its concrete preparation method is as follows:
1, the preparation of modified poly ester polyvalent alcohol: with the 0.45mol neopentyl glycol, the 0.40mol Tetra hydro Phthalic anhydride adds in the four-hole boiling flask with about 0.3g left and right sides tosic acid, adds about 15g dimethylbenzene, installs water trap, feeds N
2Gas shield, being warming up to 100 ℃ is incubated all to melt to material and is liquid state, slowly be warming up to about 160 ℃, insulation reaction to water outlet is tentatively finished, add the 0.15mol glyceryl monostearate after being cooled to 100 ℃ again, material all melts to slowly being warming up to after the liquid state to react about 160～180 ℃ to water outlet to be finished, further be warming up to 200 ℃, connecing vacuum pump vacuumizes, begin to survey acid number after 1 hour, reduce to when acid number and to get final product cooling discharge below the 5mgNaOH/g, obtain reaction product, be the modified poly ester polyvalent alcohol for bright light yellow thick liquid;
2, by the required weight requirement of aforementioned its each component of modified polyurethane gloss oil product, take by weighing the above-mentioned modified poly ester polyvalent alcohol of 30g, the 10g diisocyanate trimer, 59g toluene, the 1g silicone antifoam agent is mixed with the modified polyurethane gloss oil product then, it is applied to PE through corona treatment, on the PP film surface, put into 80 ℃ of dryings of air dry oven 1 hour, take out cooling back numbering and be respectively PE1 number, PP1 and number be used for test.
Embodiment 2 modified polyurethane gloss oil products
The modified polyurethane gloss oil product of present embodiment, contain each component of following weight:
Modified poly ester polyvalent alcohol (by following step self-control) 35g
Solidifying agent 15g
Solvent 49.5g
Defoamer 0.5g
The modified polyurethane gloss oil product of present embodiment, its concrete preparation method is as follows:
1, the preparation of modified poly ester polyvalent alcohol: with the 0.42mol neopentyl glycol, the 0.38mol Tetra hydro Phthalic anhydride adds in the four-hole boiling flask with about 0.3g left and right sides tosic acid, adds about 18g dimethylbenzene, installs water trap, feeds N
2Gas shield, being warming up to 100 ℃ is incubated all to melt to material and is liquid state, slowly be warming up to about 160 ℃, insulation reaction to water outlet is tentatively finished, add the 0.20mol glyceryl monostearate after being cooled to 100 ℃ again, material all melts to slowly being warming up to after the liquid state to react about 160～180 ℃ to water outlet to be finished, further be warming up to 200 ℃, connecing vacuum pump vacuumizes, begin to survey acid number after 1 hour, reduce to when acid number and to get final product cooling discharge below the 5mgNaOH/g, obtain reaction product, be the modified poly ester polyvalent alcohol for bright light yellow thick liquid;
2, by the required weight requirement of aforementioned its each component of modified polyurethane gloss oil product, take by weighing the above-mentioned modified poly ester polyvalent alcohol of 35g, 15g TriMethylolPropane(TMP)-vulcabond affixture, 49.5g N-BUTYL ACETATE, the 0.5g silicone antifoam agent is mixed with the modified polyurethane gloss oil product then, it is applied to PE through corona treatment, on the PP film surface, put into 80 ℃ of dryings of air dry oven 1 hour, take out cooling back numbering and be respectively PE2 number, PP2 and number be used for test.
Embodiment 3 modified polyurethane gloss oil products
The modified polyurethane gloss oil product of present embodiment, contain each component of following weight:
Modified poly ester polyvalent alcohol (by following step self-control) 40g
Solidifying agent 20g
Solvent 39.2g
Defoamer 0.8g
The modified polyurethane gloss oil product of present embodiment, its concrete preparation method is as follows:
1, the preparation of modified poly ester polyvalent alcohol: 0.48mol neopentyl glycol, 0.42mol Tetra hydro Phthalic anhydride are added in the four-hole boiling flask with about 0.3g left and right sides tosic acid, add about 20g dimethylbenzene, install water trap, feed N
2Gas shield, being warming up to 100 ℃ is incubated all to melt to material and is liquid state, slowly be warming up to about 160 ℃, insulation reaction to water outlet is tentatively finished, add the 0.10mol glyceryl monostearate after being cooled to 100 ℃ again, material all melts to slowly being warming up to after the liquid state to react about 160～180 ℃ to water outlet to be finished, further be warming up to 200 ℃, connecing vacuum pump vacuumizes, begin to survey acid number after 1 hour, reduce to when acid number and to get final product cooling discharge below the 5mgNaOH/g, obtain reaction product, be the modified poly ester polyvalent alcohol for bright light yellow thick liquid;
2, by the required weight requirement of aforementioned its each component of modified polyurethane gloss oil product, take by weighing the above-mentioned modified poly ester polyvalent alcohol of 40g, the 20g isophorone diisocyanate trimer, 39.2g solvent is that the 0.8g silicone antifoam agent is mixed with the modified polyurethane gloss oil product then, it is applied to PE through corona treatment, on the PP film surface, put into 80 ℃ of dryings of air dry oven 1 hour, take out cooling back numbering and be respectively PE3 number, PP3 and number be used for test.
The experiment of embodiment 4 sticking power
Test method: GB/T13217.7---91 attachment fastness check;
Test sample: embodiment 1～3 gained PE1,2, No. 3, PP1,2, No. 3 film samples;
Assay: residual area 〉=98% that do not peel off;
Therefore, modified polyurethane gloss oil of the present invention has good adhesive ability to polyolefin articles treat surface.
Embodiment 5 anti-solvent experiments
Test method: adopt drop-burette drippage alcohol solvent, drip and wear paint film solvent for use amount and be criterion;
Test sample: embodiment 1～3 gained PE1,2, No. 3, PP1,2,3 film samples;
Assay: the drippage quantity of solvent is all greater than 10mL, and effect is better.
Therefore, gloss oil of the present invention has solvent-resisting energy preferably.
Claims (5)
1. modified polyurethane gloss oil, form by each component of following weight percent:
Modified poly ester polyvalent alcohol 20%～60%
Solidifying agent 5%～30%
Solvent 30%～70%
Defoamer 0.1%～1%;
Above-mentioned modified poly ester polyvalent alcohol is to be got through the dehydrating condensation polyreaction by following molecular fraction by Tetra hydro Phthalic anhydride, neopentyl glycol and glyceryl monostearate:
Tetra hydro Phthalic anhydride 35%～45%;
Neopentyl glycol 40%～50%;
Stearic acid Tegin 55G 10%～20%;
Above-mentioned solidifying agent is a polyisocyanates, or tolylene diisocyanate and TriMethylolPropane(TMP) were with 3: 1 molar ratio reaction products obtained therefrom.
2. according to the described modified polyurethane gloss oil of claim 1, it is characterized in that described modified polyurethane gloss oil is made up of each component of following weight percent:
Modified poly ester polyvalent alcohol 25%～40%
Solidifying agent 10%～20%
Solvent 40%～60%
Defoamer 0.1%～1%.
3. according to claim 1 or 2 described modified polyurethane gloss oils, it is characterized in that described solvent is toluene, dimethylbenzene, N-BUTYL ACETATE, ethyl acetate, hexanaphthene or propylene glycol monomethyl ether.
4. according to claim 1 or 2 described modified polyurethane gloss oils, it is characterized in that described defoamer is silicone based defoamer.
5. described each modified polyurethane gloss oil of claim 1～4 is in the application on polyolefin plastic products surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101983955A CN101353549B (en) | 2008-09-12 | 2008-09-12 | Modified polyurethane gloss oil and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101983955A CN101353549B (en) | 2008-09-12 | 2008-09-12 | Modified polyurethane gloss oil and use thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101353549A CN101353549A (en) | 2009-01-28 |
| CN101353549B true CN101353549B (en) | 2010-09-15 |
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| CN2008101983955A Expired - Fee Related CN101353549B (en) | 2008-09-12 | 2008-09-12 | Modified polyurethane gloss oil and use thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059708A (en) * | 2012-12-16 | 2013-04-24 | 青岛博益特生物材料有限公司 | Aqueous gloss oil and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103046376B (en) * | 2012-12-31 | 2014-10-29 | 东莞市宏达聚氨酯有限公司 | Yellowing-resistant moisture cured polyurethane mirror like gloss oil and preparation method thereof |
| CN103602247A (en) * | 2013-10-20 | 2014-02-26 | 安徽嘉木橡塑工业有限公司 | Finishing vanish |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059708A (en) * | 2012-12-16 | 2013-04-24 | 青岛博益特生物材料有限公司 | Aqueous gloss oil and preparation method thereof |
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| CN101353549A (en) | 2009-01-28 |
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Granted publication date: 20100915 Termination date: 20120912 |