CN1208413C - High-fullness high-resolution environment protection polyureshane sublight uarnish - Google Patents
High-fullness high-resolution environment protection polyureshane sublight uarnish Download PDFInfo
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Abstract
The present invention relates to high fullness and high definition environmental protection polyurethane matte varnish which is composed of a varnish component, a polyurethane solidifying agent component and a diluting agent component according to the weight ratio of 1:0.5:0.6 to 0.8. The polyurethane solidifying agent component contains 50 to 70 wt% of toluene diisocynate trimer, and an addition product of 80% of toluene diisocynate and 20% of trimethylol propane as the rest. The varnish component contains 15 to 25 wt% of short oil-length soybean oil alkyd resin of 80%, 50 to 60% of modified saturated polyester resin, 0 to 5% of castor oil, 10 to 12% of aldehyde ketone resin of 60%, 3 to 5% of matting agent, 0.3 to 1.0% of polytetrafluoroethylene wax and 4% to 10% of conventional auxiliary agent and solvent. The diluting agent component contains 70 to 80 wt% of butyl acetate, 10 to 20% of compounded dioic acid dimethylster, and 10 to 15% of isophorone. The polyurethane matte varnish of the present invention has the characteristics of high definition, paint film fullness, improved hardness, improved scratch resistance and high yellowing resistance.
Description
Technical field
The present invention relates to a kind of urethane matte varnish that is used for woodwork coating.
Background technology
At furniture industry, the volatile organic compounds of urethane matte varnish (VOC) quantity discharged height, free TDI is toluene diisocyanate content and triphen too high levels, fullness is not enough during the product construction, the transparency is not good enough during recoat, is the insoluble problem of numerous paint manufacturer always.At present, the urethane matte varnish that woodenware market is used has two classes substantially: the first kind is to introduce a certain amount of nitro-cotton in its lacquer component, does not introduce the toluene diisocyanate trimer solidifying agent in curing agent component substantially.The advantage of this class urethane matte varnish is that the transparency is better behind the recoat, and shortcoming is that paint film is not plentiful, and the VOC quantity discharged is too high, and most triphen content height, and yellowing resistance is also relatively poor.The reason that causes shortcoming is a nitro-cotton, and nitro-cotton causes the viscosity height, thereby that construction contains admittedly is low, not plentiful, the VOC quantity discharged is big, and the reaction of nitro-cotton and tolylene diisocyanate causes xanthochromia again.The second class urethane matte varnish is not introduce nitro-cotton in the lacquer component, introduces the toluene diisocyanate trimer of 20-25% in the solidifying agent component.The advantage of this class varnish is that paint film is plentiful better than the first kind, and yellowing resistance is better, and shortcoming is that the transparency is relatively poor behind the recoat, and it is bad that its reason is that recoat causes interlayer to mix, and the too high paint film that causes of flatting silica or wax powder content turns white in addition, and the transparency is not good.The construction of this two classes urethane matte varnish contains all not high admittedly, and fullness is not good enough, and the VOC quantity discharged is too high, and when selecting common solidifying agent for use, free TDI content also is difficult to reach environmental requirement, and thinner is conventional component, and triphen content is difficult to reach environmental requirement.
Summary of the invention
Purpose of the present invention mainly is the problem that exists at the above-mentioned second class urethane matte varnish, provides that a kind of transparency is good, paint film is plentiful, yellowing resistance is better, low VOC quantity discharged, low-free TDI content, hangs down the urethane matte varnish of triphen content.
The object of the present invention is achieved like this: urethane matte varnish of the present invention is made up of lacquer component, polyurethane curing agent component and thinner composition, and the weight proportion of three components is 1: 0.5: 0.6-0.8; Described polyurethane curing agent component comprises the toluene diisocyanate trimer of 50-70% weight, and all the other are the affixture of 80% tolylene diisocyanate and 20% TriMethylolPropane(TMP); Described lacquer component comprises the short oil soybean oil Synolac that 80% of 15-25% weight contains admittedly, the modified saturated polyester resin of 50-60% weight, the Viscotrol C of 0-5% weight, the 60% aldehyde ketone resin that contains admittedly of 10-12% weight, the flatting silica of 3-5% weight, the tetrafluoroethylene wax of 0.3-1.0% weight, the conventional auxiliary agent and the solvent of 4%-10% weight; Described thinner composition comprises the N-BUTYL ACETATE of 70-80% weight, the different Fu Er ketone that mixes two dimethyl phthalates, 10-15% weight of 10-20% weight.
The weight percentage of toluene diisocyanate trimer is that 50-60% is preferable in the polyurethane curing agent component of the present invention; In the lacquer component, the weight percentage of short oil soybean oil Synolac is that 15-20% is preferable, and the weight percentage of Viscotrol C is that 2-5% is preferable.
The raw material of the preferred short oil soybean oil of the present invention Synolac consists of: the phthalic anhydride of the phenylformic acid of the oleic acid of 32-34% weight, 2-4% weight, the MALEIC ANHYDRIDE of 0.5-1% weight, 38-42% weight, the tetramethylolmethane of 15.5-18% weight, the ethylene glycol of 15-18% weight, the weight percent sum of each raw material is 100%, the OH percentage composition of short oil soybean oil Synolac is 4.5-5.8%, and the K value is 1.13-1.15.The production technique production of short oil soybean oil Synolac Synolac routinely and getting.
Thinner among the present invention is the healthy thinner of the environment-friendly type of no triphen, no ethyl cellosolve acetate, butyl glycol ether.
Other raw material among the present invention all can be buied on market.
Compare with the second class urethane matte varnish on the market, advantage of the present invention is as follows:
1. environment protection health: the present invention introduces the toluene diisocyanate trimer of free TDI＜0.2% and the affixture of 80% tolylene diisocyanate and 20% TriMethylolPropane(TMP) in polyurethane curing agent, thereby free TDI content is reduced to below 0.25% from about common 0.5-0.7% when making construction; Solvent in lacquer component, curing agent component, the thinner composition does not all add triphen and CAC, the contour malicious teratogenesis solvent of BCS, and triphen content reaches the environmentfriendly products requirement far below the combination of the second class urethane matte varnish; In addition,, make volatile organic compounds (VOC) discharging, reach the environmentfriendly products requirement less than 600g/L because consolidating of resin contains height in the lacquer component; In addition, the heavy metal content that starting material are brought into is almost nil, is far smaller than 500mg/kg.More than every index all be better than the polyurethane coating green choice evaluation criteria GCP006-2002 of Chinese commodity association promulgation.
2. the recoat transparency is good: the present invention is in the polyurethane curing agent component, the weight percentage of quick-drying type polyurethane curing agent toluene diisocyanate trimer is brought up to about 50～70% from 20～25%, thereby the increase eliminate optical property, and flatting silica weight is reduced to about 3-5% from 5-6%.Above measure has all significantly improved the recoat transparency.
3. fullness is splendid: the present invention introduces height and contains (80%) soybean alkyd admittedly in the lacquer component, introduce the solidifying agent that height contains the affixture of (75%) 80% tolylene diisocyanate and 20% TriMethylolPropane(TMP) admittedly in the curing agent component, the solid content of solidifying agent is improved, thinner composition is abandoned hexichol and is all used strong solvent, brings up to about 41% thereby construction is contained admittedly from common about 35%.
4. high rigidity, high anti-scratch, good toughness, yellowing resistance are good: the present invention is in the polyurethane curing agent component, increasing the fast dried solidifying agent of toluene diisocyanate trimer increases cross-linking density, hardness improves, scratch resistance improves, introduce about 10% toughened resin, improve toughness, do not use nitro-cotton fully, keep good yellowing resistance.
The invention will be further described below in conjunction with embodiment.
Embodiment
Following percentage composition is weight percentage.
Embodiment one:
The urethane matte varnish process for preparation of present embodiment is as follows:
1. the preparation of lacquer component (being called for short component A):
In the 500ml iron flask, add modified saturated polyester resin (HS129) 180g, short oil soybean oil Synolac (1180D) 45g, Viscotrol C 15g, toughness aldehyde ketone resin (CF-60) 30g, add the unsaturated polycarboxylic acid polymeric dispersant of lower molecular weight (BYK104) 1.2g again, modified polyorganosiloxane defoamer (5500) 0.9g, polyether-modified polydimethylsiloxane flow agent (BYK306) 0.6g, polyacrylic acid copolymerized body flow agent (BYK358) 1.5g, polyether silicone flow agent (10%Tego450) 1.8g, high boiling solvent mixes two dimethyl phthalates (NME) 8.1g, add flatting silica (ED-30) 15g again, tetrafluoroethylene wax (FS421) 0.9g, above material high-speed stirring disperses to scrape fineness≤20um.
2. the preparation of polyurethane curing agent component (being called for short component B):
In a 500ml iron flask, add PU toluene diisocyanate trimer solidifying agent (50T) 150g, add PU 80% tolylene diisocyanate and the general solidifying agent of 20% TriMethylolPropane(TMP) affixture (JK-75) 150g, stir.
3. the preparation of diluent composition (abbreviation component C):
In a 500ml iron flask, add N-BUTYL ACETATE 240g, high boiling solvent mixed two dimethyl phthalates (NME) 30g, different Fu Er ketone 30g, mix.
4, join lacquer:
Get component A300g, B component 150g, component C240g (by A: B: C=1: 0.5: 0.8 weight ratio) mix, promptly be mixed with high plentiful, high definition environment-protecting polyurethane matte varnish 690g.The NCO/OH=100% of the product of embodiment one, construction contains admittedly up to 41.6%.
In the present embodiment, model is the short oil soybean oil Synolac of 1180D, produce voluntarily by company's alkyd resin production method routinely, its raw material consists of: the phthalic anhydride of the phenylformic acid of the oleic acid of 34% weight, 2% weight, the MALEIC ANHYDRIDE of 0.5% weight, 40% weight, the tetramethylolmethane of 15.5% weight, the ethylene glycol of 16.2% weight, its OH percentage composition is 4.75%, and the K value is 1.132.
The source of all the other raw materials is as follows:
Modified saturated polyester resin (HS129) is the resin that Italian SAPICI company produces;
Viscotrol C is import or home-made refined caster oil;
Toughness aldehyde ketone resin (CF-60) is the 60% A-81 aldehyde ketone resin by the production of German BASF AG that contains admittedly, adopts the N-BUTYL ACETATE dissolving;
NME is the mixture of the dimethyl succinate produced of our company, Methyl glutarate, dimethyl adipate, can use the DBE of Du Pont;
Polyether-modified polydimethylsiloxane flow agent (BYK306), polyacrylic acid copolymerized body flow agent (BYK358) are the leveling auxiliary agent of German Bi Ke chemistry; The unsaturated polycarboxylic acid polymeric dispersant of lower molecular weight (BYK104) is the dispersing auxiliary of Bi Ke chemistry;
Polyether silicone flow agent (10%Tego450) becomes 10% solution for the TEGO450 leveling auxiliary agent of German TEGO (enlightening height) chemical company with xylene soluble.
Tetrafluoroethylene wax (FS421) is the tetrafluoroethylene and the poly blended wax of the U.S.'s three phyllodies.
Flatting silica (ED-30) is the flatting silica of U.S. GRACE company.
The 60T solidifying agent of the Italian SAPICI of PU toluene diisocyanate trimer solidifying agent (50T) employing company contains admittedly with N-BUTYL ACETATE latting drown 50%.
The L-75 solidifying agent of 80% tolylene diisocyanate and the German BAYER of the general solidifying agent of 20% TriMethylolPropane(TMP) affixture (JK-75) employing company.
Embodiment two:
Among the component A with embodiment one, modified saturated polyester resin (HS129) changes 165g into, short oil soybean oil Synolac (1180D) changes 60g into, Viscotrol C changes 6g into, aldehyde ketone resin (CF-60) changes 30g into, and flatting silica (ED-30) changes 12g into, and tetrafluoroethylene wax (FS-421) changes 1.5g into, mix diacid dioctyl phthalate (NME) and change 19.5g into, other is constant.In the B component with embodiment one, toluene diisocyanate trimer 50T changes 180g into, and 80% tolylene diisocyanate and 20% TriMethylolPropane(TMP) affixture (JK75) change 120g into.Join lacquer and the time get component A300g, B component 150g, component C210g (by A: B: C=1: 0.5: 0.7 weight ratio) mix, promptly be mixed with plentiful, the high definition environment-protecting polyurethane matte varnish 660g of height.The NCO/OH=99.2% of the product of embodiment two, construction contains admittedly up to 41.6%.
Embodiment three:
Among the component A with embodiment one, modified saturated polyester resin (HS129) changes 150g into, short oil soybean oil Synolac (1180D) changes 75g into, Viscotrol C changes 0 into, aldehyde ketone resin (CF-60) changes 36g into, flatting silica (ED-30) changes 9g into, tetrafluoroethylene wax (FA-421) changes 3g into, mix two dimethyl phthalate NME and change 6g into, other is constant, in the B component with embodiment one, toluene diisocyanate trimer (50T) changes 210g into, and 80% tolylene diisocyanate and 20% TriMethylolPropane(TMP) affixture (JK75) change 90g into.Join lacquer and the time get component A300g, B component 150g, component C180g (by A: B: C=1: 0.5: 0.6 weight ratio) mix, promptly be mixed with plentiful, the high definition environment-protecting polyurethane matte varnish 630g of height.The NCO/OH=94.4% of the product of embodiment three, construction contains admittedly up to 42.8%.
Embodiment four:
Scheme by example one is made matte varnish equally.But the short oil soybean oil Synolac (1181D) in this example is different with example one, two, three.Construction contains admittedly up to 41.6%.
In the present embodiment, model is the short oil soybean oil Synolac of 1181D, is produced voluntarily according to a conventional method by company, and its raw material consists of; The tetramethylolmethane of the phthalic anhydride of the MALEIC ANHYDRIDE of the phenylformic acid of the oleic acid of 32% weight, 3% weight, 0.8% weight, 38% weight, 17% weight, the ethylene glycol of 15% weight, its OH percentage composition is 5.0%, the K value is 1.133.
Embodiment five:
Scheme by example one is made matte varnish equally.But the short oil soybean oil Synolac (1182D) in this example is different with example one, two, three, four.Construction contains admittedly up to 41.6%.
In the present embodiment, model is the short oil soybean oil Synolac of 1182D, is produced voluntarily according to a conventional method by company, and its raw material consists of; The tetramethylolmethane of the phthalic anhydride of the MALEIC ANHYDRIDE of the phenylformic acid of the oleic acid of 33% weight, 4% weight, 1% weight, 42% weight, 18% weight, the ethylene glycol of 18% weight, its OH percentage composition is 5.8%, the K value is 1.154.Consisting of of market product one:
Contain modified saturated polyester resin (HS129) 40-50% among the lacquer component A, 70% short oil soybean oil Synolac (9970D) 20-30% that contains admittedly, mute light powder ED-30 is 5-6%, polytetrafluoroethylene wax 0.3-1.0%, other is conventional solvent and auxiliary agent such as dispersion agent, anti-settling agent, defoamer, flow agent.
Contain fast dried toluene diisocyanate trimer 50T 20-30% among the solidifying agent component B, general 80% tolylene diisocyanate and 20% TriMethylolPropane(TMP) affixture PU solidifying agent (GB50) 70-80%.
Thinner is conventional thinner, and the construction weight proportion is A: B: C=1: 0.5: 0.6-0.8, constructing to contain admittedly is generally about 36%.
Consisting of of market product two:
Contain nitro-cotton 1-4% among the component A, modified saturated polyester resin (HS129) 40-50%, 70% short oil soybean oil Synolac (9970D) 20-30% that contains admittedly, mute light powder (ED-30) 3-4%, polytetrafluoroethylene wax 0.3-1.0%, other comprises solvent and auxiliary agent such as dispersion agent, anti-settling agent, defoamer, flow agent for conventional component.Component B does not contain toluene diisocyanate trimer 50T usually, uses 80% tolylene diisocyanate and the 20% general solidifying agent of TriMethylolPropane(TMP) affixture PU (GB50) entirely, and the construction weight proportion is 1: 0.5: 0.6-1, construction contains admittedly only 25-30% usually.
The performance of existing two products on the products and marketing of above-mentioned three embodiment of the present invention is compared as follows table, and the numerical value in the table is the weight percentage of each raw material in component A, B component or component C.
| Material | Example one | Example two | Example three | Product one | Product two | ||
| Component | Component A | 1.1/2 nitro-cotton | - | - | - | - | 3 |
| 2. high boiling solvent mixes NME | 2.7 | 6.5 | 2 | 2 | 4 | ||
| 3. modified saturated polyester resin HS129 60% | 60 | 55 | 50 | 50 | 50 | ||
| 4. short oil soybean oil Synolac 9970D 70% | - | - | - | 30 | 20 | ||
| 5. short oil soya-bean oil modified alkyd resin 1180D | 15 | 20 | 25 | - | - | ||
| 6. Viscotrol C | 5 | 2 | 0 | - | - | ||
| 7. aldehyde ketone resin CF-60 | 10 | 10 | 12 | - | - | ||
| 8. unsaturated polycarboxylic acid polymeric dispersant | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | ||
| 9. the modified polyorganosiloxane defoamer 5500 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | ||
| 10. acrylic copolymer flow agent | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | ||
| 11. polyether silicone flow agent 10%TEG0450 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | ||
| 12. polyether-modified polydimethylsiloxane flow agent BYK306 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | ||
| 13. mute light powder ED-30 | 5 | 4 | 3 | 5.5 | 3.5 | ||
| 14. polytetrafluoroethylene wax FS421 | 0.3 | 0.5 | 1 | 0.5 | 0.5 | ||
| 15. ester vinegar butyl ester BAC | - | - | - | 10 | 17 | ||
| B component | 1. toluene diisocyanate trimer 50T | 50 | 60 | 70 | 20 | - | |
| 2.80% tolylene diisocyanate and 20% TriMethylolPropane(TMP) affixture GB-50 | - | - | - | 80 | 80 | ||
| 3.80% tolylene diisocyanate and 20% TriMethylolPropane(TMP) affixture JK-75 | 50 | 40 | 30 | - | - | ||
| 4. N-BUTYL ACETATE BAC | - | - | - | - | 20 | ||
| Component C | 1. dimethylbenzene XYLENE | - | - | - | 60 | 60 | |
| 2. N-BUTYL ACETATE BAC | 70 | 70 | 80 | 20 | 20 | ||
| 3. ethoxy ethyl acetate CAC | - | - | - | 20 | 20 | ||
| 4. different fluorine that ketone | 15 | 10 | 10 | - | - | ||
| 5. high boiling solvent mixes two dimethyl phthalate NME | 15 | 20 | 10 | - | - | ||
| The rerum natura contrast | 1.A: B: C (rock field 4 #Cup 13 ") | 1∶0.5∶0.8 | 1∶0.5∶0.7 | 1∶0.5∶0.6 | 1∶0.5∶0.8 | 1∶0.5∶.1 | |
| 2. construction contains (%) admittedly | 41.6 | 41.6 | 42.8 | 35.6 | 28 | ||
| 3.VOC discharging (G/L) | 572.3 | 572.3 | 560.6 | 631.1 | 698.4 | ||
| 4. toluene xylene content (%) | 12.2 | 11.7 | 13.5 | 38.1 | 34.4 | ||
| 5. free TDI (%) | 0.23 | 0.21 | 0.24 | 0.4 | 0.3 | ||
| 6. surface drying (min) | 24 | 28 | 20 | 22 | 26 | ||
| 7. do solid work (hr) | 18 | 16 | 14 | 20 | 16 | ||
| 8. hardness (pencil hardness meter) | 2H | 2H | 2H | 2H | 2H | ||
| 9. sticking power | Can | Can | Can | Can | Can | ||
| 10. transparent (recoat three times) | Very | Very | Very | Bad | Very | ||
| 11. fullness ratio | Good | Good | Good | Can | Bad | ||
| 12. scrath resistance | Can | Can | Can | Can | Bad | ||
| 13. yellowing resistance | Can | Can | Can | Can | Bad | ||
As can be seen from the above table, the products and marketing product of three embodiment of the present invention is compared, and following advantage is arranged:
1.VOL discharging is starkly lower than market product one, two, reaches the environmentfriendly products requirement;
2. raw material is brought toluene into, xylene content is lower than market product one, two, reaches the environmentfriendly products requirement;
3. recoatability is better than market product one, and fullness ratio obviously is better than market product one, two;
4. yellowing resistance is better than market product two, and scrath resistance is better than market product one.
Claims (2)
1. urethane matte varnish is characterized in that: be made up of lacquer component, polyurethane curing agent component and thinner composition, the weight proportion of three components is 1: 0.5: 0.6-0.8; Described polyurethane curing agent component comprises the toluene diisocyanate trimer of 50-70% weight, and all the other are the affixture of 80% tolylene diisocyanate and 20% TriMethylolPropane(TMP); Described lacquer component comprises the short oil soybean oil Synolac that 80% of 15-25% weight contains admittedly, the modified saturated polyester resin of 50-60% weight, the Viscotrol C of 0-5% weight, the 60% aldehyde ketone resin that contains admittedly of 10-12% weight, the flatting silica of 3-5% weight, the tetrafluoroethylene wax of 0.3-1.0% weight, the conventional auxiliary agent and the solvent of 4%-10% weight; Described thinner composition comprises the N-BUTYL ACETATE of 70-80% weight, the different Fu Er ketone that mixes two dimethyl phthalates, 10-15% weight of 10-20% weight.
2. urethane matte varnish according to claim 1, the raw material that it is characterized in that described short oil soybean oil Synolac consists of: the phthalic anhydride of the phenylformic acid of the oleic acid of 32-34% weight, 2-4% weight, the MALEIC ANHYDRIDE of 0.5-1% weight, 38-42% weight, the tetramethylolmethane of 15.5-18% weight, the ethylene glycol of 15-18% weight, the weight percent sum of each raw material is 100%, the OH percentage composition of short oil soybean oil Synolac is 4.5-5.8%, and the K value is 1.13-1.15.
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| CN 03139925 CN1208413C (en) | 2003-07-21 | 2003-07-21 | High-fullness high-resolution environment protection polyureshane sublight uarnish |
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| CN 03139925 CN1208413C (en) | 2003-07-21 | 2003-07-21 | High-fullness high-resolution environment protection polyureshane sublight uarnish |
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| CN1208413C true CN1208413C (en) | 2005-06-29 |
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2003
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