CN1394927A - Preparation method of high scratch resistance nano compound polyurethane paint - Google Patents

Preparation method of high scratch resistance nano compound polyurethane paint Download PDF

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Publication number
CN1394927A
CN1394927A CN 02111699 CN02111699A CN1394927A CN 1394927 A CN1394927 A CN 1394927A CN 02111699 CN02111699 CN 02111699 CN 02111699 A CN02111699 A CN 02111699A CN 1394927 A CN1394927 A CN 1394927A
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China
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nano
resin
acid resin
acryl acid
polyurethane paint
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CN 02111699
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Chinese (zh)
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CN1186414C (en
Inventor
武利民
周树学
游波
顾广新
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复旦大学
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Abstract

The polyurethane finishing paint with high scratch resistance is formed from uniformly-dispersed nano particles of SiO2 and CaCO3, etc., acrylic resin containing hydroxyl group, solidifying agent polyisocyanate and solvent, levelling agent, defoaming agent and catalyst. Its preparation method can adopt in-situ polymerization method formed from the processes of predispersion of nano particles in monomer (or with solvent) mixed phase and semi-continuous solution polymerization, also can adopt comixing method making nano particles directly disperse in high solid content acrylic resin. The nano particles are modified by surfactant or coupling agent, it can obtain better effect. The above-mentioned nano composite acrylic resin is matched with solidifying agent polyisocyanate, etc. according to a certain ratio, and dried so as to obtain high scratch resistance paint film.

Description

The preparation method of high scratch resistance nano compound polyurethane paint

Technical field

The present invention relates to chemical technology field, related to a kind of high scoring resistance polyurethane coating and preparation method thereof.

Background technology

Automobile, instrument, mechanical means, plastic components etc. are in transportation or use, and meeting tarnishes the finish paint paint film because of multiple reason or cut occurs, influences its quality.Such as, in the galloping process, the impact of sand and dust can cause the loss of gloss of automobile paint film in the air, and in the carwash process, water and impurity thereof are to the loss of gloss that also can cause the automobile paint film that washes away of paint film; The scraping of foreign matters such as branch examined or artificial destruction then can cause the cut of paint film.Influence a scoring resistance that important indicator is a paint film of above-mentioned automobile finish film properties, high scoring resistance means that paint film in use can keep high gloss the long period or not be prone to cut.

The method that tradition improves above-mentioned paint film scoring resistance is to adjust resin formula, as the content that increases hard monomer in the polymkeric substance, add the scoring resistance that method such as organo-siloxane function monomer all can improve paint film.Though aforesaid method can improve the scoring resistance of filming to a certain extent, can reduce some other performances of filming simultaneously, as shock resistance, ageing resistance, sticking power etc.

Nanoparticle is the developing outstanding representative of nano material, and the nano-powder material of existing considerable part has been realized industrialization.Because nano particle diameter is little, specific surface area is big, with polymkeric substance compound after, interface junction gets togather, reactive force is big, can make the nano-polymer composite material that obtains have the characteristic such as strong of the pliable and tough and inorganic materials of organic materials concurrently, material is transparent unaffected simultaneously.Above-mentioned nano composite material is used in paint field, then shows as when improving the paint film mechanical property and can keep the higher transparency of paint film.But little just because of nano particle diameter, surface free energy is high, easily assemble between particle, the dispersion of nanoparticle with stable be its key issue that successful Application need solve in coating.

At present, applying nano materials improve the paint film scoring resistance bibliographical information seldom.In U.S. US6020419 patent, adopt multistage seedpod of the lotus jet spread method to carry out fumed nano SiO 2Dispersion in acrylic resin soln, though made the coating of transparent scoring resistance, complex process, cost is higher, is difficult for promoting.

Summary of the invention

The purpose of this invention is to provide nano compound polyurethane paint of a kind of high scoring resistance and preparation method thereof.

The purpose of this invention is to provide good nano compound polyurethane paint of a kind of dilution property and preparation method thereof.

The purpose of this invention is to provide simple nano compound polyurethane paint of a kind of preparation technology and preparation method thereof.

Coating of the present invention is made up of hydroxy acryl acid resin, polyisocyanate curing agent, inorganic nano-particle etc., and each component concentration is (wt%):

Hydroxy acryl acid resin: 49-72;

Inorganic nano-particle: 1-30;

All the other are solvent in the nanocomposite.

During preparation coating, the curing dose of adding is:

Solidifying agent and nano combined

The proportioning of resin (OH/-NCO): 1.0～1.5.

The better content of above-mentioned coating is (wt%):

Hydroxy acryl acid resin: 59.5-71;

Inorganic nano-particle: 3-15;

All the other are solvent in the nanocomposite.

During preparation coating, the curing dose of adding is:

Solidifying agent and nano combined

The proportioning of resin (OH/-NCO): 1.1～1.3.

Hydroxy acryl acid resin is to form inorganic nano-particle such as SiO by hydroxyl (methyl) esters of acrylic acid monomer with the copolymerization of (methyl) acrylic ester monomer in the above-mentioned coating 2, CaCO 3, TiO 2, ZnO, silicon sol etc., polyisocyanate curing agent such as hexamethylene diisocyanate (HDI), isoflurane chalcone diisocyanate aliphatics or aromatic polyisocyanates such as (IPDI).

The solvent of above-mentioned coating and other auxiliary agent are identical with the paint additive that is generally used for the automobile finishing paint as thinner, whipping agent, flow agent, defoamer, catalyzer etc.

Coating of the present invention can make with situ aggregation method or blending method.Situ aggregation method is that inorganic nano-particle is dispersed in solvent and the monomeric mixed solution, then by solution polymerization synthesis of nano composite acrylic resin.

Perhaps make coating of the present invention by blend method, promptly earlier synthetic hydroxy acryl acid resin under room temperature to 120 ℃ range temperature, directly is dispersed in inorganic nano-particle in the hydroxy acryl acid resin.

Above-mentioned nanocomposite is mixed with the solidifying agent polyisocyanates, add the conventional used additives of thinner and coating and promptly can be used as the coating use.Other auxiliary agent meal with wine property adding as required in the coating, visual execution of coating of solvent in the coating or thinner and solid content and suitably increase, color can be mixed colours on request.

The resin that the present invention adopts is the acrylic resin of high solids content, and its solid content generally＞70%.

Monomer such as methyl acrylate, ethyl propenoate, butyl acrylate, Hydroxyethyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, Rocryl 410, vinylbenzene, alpha-methyl styrene etc. when above-mentioned compound resin prepares, solvent such as dimethylbenzene, solvent oil, N-BUTYL ACETATE etc.

Monomer when compound resin of the present invention prepares is with following better:

Do the functional monomer with acrylic acid hydroxy alkyl ester or hydroxyalkyl methacrylate, it is synthetic to make comonomer with alkyl acrylate, alkyl methacrylate or alkenyl aromatic compound.For example the functional monomer is Hydroxyethyl acrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Rocryl 410 etc.; Comonomer such as ethyl propenoate, butyl acrylate, methyl methacrylate, butyl methacrylate, vinylbenzene etc.

Inorganic nano-particle selects for use suitable lipophilic surfactant or coupling agent to carry out repolymerization or blend after the oleophylic modification, its dispersiveness, combine with the interface of resin all very good.The tensio-active agent of modification such as dehydration sorbic alcohol monoleate (Span80), polyhydroxycarboxyliacid acid acyl ammonia etc., coupling agent such as sec.-propyl three (dioctylphosphoric acid ester) titanic acid ester, methacryloxypropyl trimethoxy silane etc.

Be used for inorganic nano-particle of the present invention,, be of a size of best with 1～100nm through experiment repeatedly.

Can followingly carry out inorganic nano particle modified among the present invention:

With blend by a certain percentage such as nanoparticle, properties-correcting agent, solvent such as dimethylbenzene, benzene etc., process ultrasonic wave, grinding or high speed shear etc. are more than pre-dispersed half an hour, pre-dispersed liquid is warming up to 60～140 ℃ again, carry out continuously stirring reaction 20～24 hours simultaneously, product centrifugation, drying are obtained the nanoparticle of oleophylic modification.When adopting in-situ polymerization legal system nanocomposite, methods such as palpus is ultrasonic with the employing of modified Nano particle earlier, grinding, sand milling are dispersed in solvent and the monomeric mixed solution, jitter time half an hour to 1 hour, and then by solution polymerization process synthesis of nano composite acrylic resin; When adopting blending method to prepare nanocomposite, earlier synthetic hydroxyl divides acrylic resin, then at a certain temperature, the modified Nano particle directly is dispersed in the hydroxy acryl acid resin by means such as grinding, high speed shear.Above-mentioned nanocomposite is mixed by a certain percentage with solidifying agent, and add proper amount of diluting, flow agent, defoamer, catalyzer etc., drying can obtain high scoring resistance urethane paint film under heating or room temperature.

Hydroxy acryl acid resin of the present invention can be a kind of, also can be that the hybrid resin and the inorganic nano-particle of hydroxy acryl acid resin or hydroxy acryl acid resin and other hydroxy-containing resin is composited more than 2 kinds, can select according to the purposes of coating.

Solidifying agent also can be mixture a kind of or polyisocyanates more than 2 kinds as mixed curing agent, depend on the needs.

Same as above, inorganic nano-particle also can be a kind of or mix more than 2 kinds and use, decide on specific requirement.

The solvent of the synthetic hydroxy acryl acid resin of the present invention is ester class or ketone, as ethyl acetate, butylacetate, Methyl amyl ketone etc.

Nanocomposite that the present invention makes and polyurethane paint film properties thereof characterize as follows:

Viscosity is measured under 750rpm by the L-90 rheometer, its non-volatile matter weight fraction (solid content, NVW) measure according to ASTM D2369-95, the pendulum-rocker hardness of paint film is pressed GB/T1730-93 and is measured, gloss is pressed GB1743-79 and is measured, wear resistance is pressed GB1768-79 and is measured, scoring resistance is by Nano Indenter XP (MTS Inc., USA) measure, the ultraviolet absorption characteristic of paint film is measured by FDAC UV-3000 ultraviolet-visible spectrometer, and ageing resistance is measured by the QUV-Se artificial accelerated aging instrument that U.S. Q-Panel company produces.After measured, polyurethane paint film hardness＞2H that the inventive method can make, scoring resistance＞6GPa.

Nanocomposite that the present invention makes and urethane paint film thereof are compared with common urethane paint film, have the following advantages:

1. the nanocomposite dilution property that obtains of the present invention is good; can keep the long period that sedimentation does not take place after the dilution; 2. improve a lot by the paint film scoring resistance that obtains behind the resin solidification of the present invention; simultaneously can keep film original high transparent and high-luster; 3. the acrylic resin viscosity after the nano-particles filled does not have obvious raising; thereby can not reduce the solid content of when construction coating; help environment protection; 4. the paint film that is made by resin of the present invention is except above-mentioned performance; also has ultraviolet shielded property; help the raising of durability of coating under paint film itself or the paint film; 5. the nanocomposite preparation of the present invention's proposition can be adopted original acrylic resin synthesis technique; not as bigger change, equipment drops into little to equipment.

The nano combined hydroxy acryl acid resin of synthetic of the present invention except being used to prepare polyurethane coating, is used for also can be used for the high scratch resistance of aircraft, industrial equipments and instrument, coiled material and plastic component etc. outside the high scoring resistance automobile finish.

Description of drawings Fig. 1 is that nanoparticle adds the changing conditions of back based finish varnish for vehicles film gloss slippage with digestion time.

Embodiment

Embodiment 1:

With nanometer SiO 2Direct and hydroxy acryl acid resin blend makes nanocomposite; Or with nanometer SiO 2Carry out modification with silane coupling agent, again with nanometer SiO 2Be pre-dispersed in the mixed solution of monomer and solvent, carry out in-situ polymerization and make nanocomposite.Experiment parameter and resin properties are as shown in table 1.Table 1 Example 1 ?2 ?3 ?4 ?5 ?6 ?7 Acrylic resin content 70％ ?67.5％ ?65％ ?70.9 ?69.4 ?68 ?50 Nanoparticle and consumption 0 ?2.5％SiO 2 ?5.0％SiO 2 1% modification SiO 2 3% modification SiO 2 5% modification SiO 2 25% modification SiO 2 The preparation method Blending method (80 ℃) Situ aggregation method Solid content 70 ?70 ?70 ?71.9 ?72.4 ?73 ?75 Viscosity (mPa.s) 2960 ?3020 ?3100 ?4700 ?3050 ?2700 ?3600 Solvent cut Better Good stability does not have precipitation

As seen from the above table, the compound viscosity influence to acrylic resin of nanoparticle is less, thereby the VOC of the high scoring resistance coating of preparation can not improve yet.Above-mentioned respective embodiments and polyisocyanates are pressed-NCO/-OH=1.1: 1 mixed, the 30min that is heating and curing under 80 ℃ again obtains corresponding Lacquer finish paint film, and its performance index are shown in Table 2.As seen from the above table, compound hardness, the scoring resistance that improves paint film of nanoparticle, and do not reduce the gloss of paint film.Table 2 Example ????1 ????2 ????3 ????4 ????5 ????6 ????7 Gloss (60 °) ??92.9 ??92.0 ??91.5 ??92.2 ??92.1 ??91.6 ??91.6 Pendulum-rocker hardness (about 65 μ m) ??0.82 ??0.84 ??0.88 ??0.82 ??0.85 ??0.87 ??0.91 Microhardness (GPa, load 1mN) ??0.10 ??0.13 ??0.16 ??0.11 ??0.15 ??0.17 ??0.25 Scoring resistance (GPa, load 1mN) ??6.2 ??7.14 ??8.26 ??6.75 ??7.54 ??8.32 ??15.20
Embodiment 2:

Different nanoparticles are dispersed in the mixed solution of methyl methacrylate, butyl acrylate, vinylbenzene, Hydroxyethyl acrylate and N-BUTYL ACETATE, adopt semi-continuous polymerzation technology to make the Hydroxylated acrylic resin that contains nanoparticle, composite by a certain percentage with the hexa-methylene isocyanic ester, be coated in film forming on the tinplate, carry out the scoring resistance test, experimental formula and test result see Table 3.Table 3 Example 1 ?2 ?3 ?4 Monomer content 67％ 67％ 67％ 67％ Nanoparticle and content SiO 2，3％ CaCO 3，3％ TiO 2，3％ ZnO，3％ Curing agent content (NCO/-OH) 1.1 1.3 1.3 1.5 Paint film scoring resistance (GPa, load 1mN) 7.5 7.6 7.3 7.4

Embodiment 3:

Adopt methyl allyl acyloxypropyl trimethoxysilane to carry out modification in xylene solvent nanoparticle, modified nano powders such as centrifugation, drying are dispersed in the mixed solution of monomer and solvent, and polymerization technique and film are with embodiment 2.Experimental formula and test result see Table 4.

Table 4 Example 1 2 3 4 Monomer content 67％ 67％ 67％ 67％ Nanoparticle and content SiO 2，3％ CaCO 3，3％ TiO 2，3％ ZnO，3％ Surface-modifying agent Methyl allyl acyloxypropyl trimethoxysilane Curing agent content (NCO/-OH) 1.1 1.1 1.1 1.1 Paint film scoring resistance (GPa, load 1mN) 7.0 7.2 6.8 6.7

Claims (11)

1, a kind of high scoring resistance nano compound polyurethane paint is made up of hydroxy acryl acid resin, polyisocyanate curing agent, inorganic nano-particle, it is characterized in that each component concentration following (wt%):
Hydroxy acryl acid resin: 49-72;
Inorganic nano-particle: 1-30;
All the other are solvent;
Solidifying agent and nano combined
The proportioning of resin (OH/-NCO): 1.0～1.5.
2,, it is characterized in that the preferential following content (wt%) that uses of each component according to the described high scoring resistance nano compound polyurethane paint of claim 1:
Hydroxy acryl acid resin: 59.5-71;
Inorganic nano-particle: 3-15;
All the other are solvent:;
Solidifying agent and nano combined
The proportioning of resin (OH/-NCO): 1.1～1.3.
3, according to the described high scoring resistance nano compound polyurethane paint of claim 1, it is characterized in that by hydroxy acryl acid resin, polyisocyanate curing agent, inorganic nano-particle
A) make by in-situ polymerization:
Inorganic nano-particle is dispersed in solvent and the monomeric mixed solution, by the compound hydroxyl of solution polymerization process synthesis of nano
Acrylic resin;
B) or by blend method make:
Earlier synthetic hydroxy acryl acid resin directly is dispersed in the inorganic nano component in the hydroxy acryl acid resin then;
Above-mentioned nanocomposite is mixed with polyisocyanate curing agent, and adding thinner and conventional coating auxiliary material can use.
4, high scoring resistance nano compound polyurethane paint according to claim 1, it is characterized in that hydroxy acryl acid resin is to do the functional monomer with acrylic acid hydroxy alkyl ester or hydroxyalkyl methacrylate, it is synthetic to make comonomer with alkyl acrylate, alkyl methacrylate or alkenyl aromatic compound.
5, high scoring resistance nano compound polyurethane paint according to claim 1 is characterized in that making nanometer composite acrylic resin with hydroxy acryl acid resin again after inorganic nano-particle is through tensio-active agent or the modification of coupling agent oleophylic.
6, modification is with nanoparticle, lipophilic surfactant or coupling agent, solvent blend, carries out pre-dispersedly, pre-dispersed liquid is warming up to 60～140 ℃ then, stirring reaction 20-24 hour, and with product centrifugation, dry getting final product.
7, high scoring resistance nano compound polyurethane paint according to claim 1 is characterized in that the inorganic nano component is SiO 2, CaCO 3, TiO 2, ZnO, silicon sol etc., it is of a size of 1-100nm.
8, high scoring resistance nano compound polyurethane paint according to claim 1 is characterized in that hydroxy acryl acid resin is a kind of, also can be the hybrid resin of hydroxy acryl acid resin or hydroxy acryl acid resin and other hydroxy-containing resin more than 2 kinds.
9, high scoring resistance nano compound polyurethane paint according to claim 1 is characterized in that the polyisocyanates anabolica is one or more blended solidifying agent.
10, high scoring resistance nano compound polyurethane paint according to claim 7 is characterized in that nanoparticle is a kind of or the mixing of inorganic nano-particle more than 2 kinds.
11, high scoring resistance nano compound polyurethane paint according to claim 1 is characterized in that the solvent of synthetic hydroxy acryl acid resin is ester class or ketones solvent.
CNB021116997A 2002-05-16 2002-05-16 Preparation method of high scratch resistance nano compound polyurethane paint CN1186414C (en)

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CN1186414C CN1186414C (en) 2005-01-26

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101792639A (en) * 2010-04-02 2010-08-04 德莱特恩环保涂料(北京)有限公司 Wear-resisting scratch-resisting weather-proof polyurethane coating and preparation method thereof
CN101935493A (en) * 2010-09-28 2011-01-05 江苏冶建防腐材料有限公司 Water-based innocuous long-acting antifouling coating and preparation method thereof
CN102358807A (en) * 2011-07-30 2012-02-22 吉林大学 Hydrophobic nano composite automobile finish and preparation method thereof
CN102559023A (en) * 2010-12-29 2012-07-11 佛山市天安塑料有限公司 Scratch resistance waterborne polyurethane coating and preparation method thereof
CN103627306A (en) * 2013-11-07 2014-03-12 昆山大世界油墨涂料有限公司 Mist surface hand feeling scratch-resistant coating paint and preparation method thereof
CN103642380A (en) * 2013-11-21 2014-03-19 福建农林大学 Cellulose nanorod in situ reinforced aqueous polyurethane coating material
CN104017489A (en) * 2014-05-29 2014-09-03 中国石油大学(华东) Nano-TiO2 modified acrylic polyurethane finish paint and preparation method thereof

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101792639A (en) * 2010-04-02 2010-08-04 德莱特恩环保涂料(北京)有限公司 Wear-resisting scratch-resisting weather-proof polyurethane coating and preparation method thereof
CN101792639B (en) * 2010-04-02 2012-09-05 德莱特恩环保涂料(北京)有限公司 Wear-resisting scratch-resisting weather-proof polyurethane coating and preparation method thereof
CN101935493A (en) * 2010-09-28 2011-01-05 江苏冶建防腐材料有限公司 Water-based innocuous long-acting antifouling coating and preparation method thereof
CN101935493B (en) * 2010-09-28 2013-03-13 江苏冶建防腐材料有限公司 Water-based innocuous long-acting antifouling coating and preparation method thereof
CN102559023B (en) * 2010-12-29 2014-06-04 广东天安新材料股份有限公司 Scratch resistance waterborne polyurethane coating and preparation method thereof
CN102559023A (en) * 2010-12-29 2012-07-11 佛山市天安塑料有限公司 Scratch resistance waterborne polyurethane coating and preparation method thereof
CN102358807A (en) * 2011-07-30 2012-02-22 吉林大学 Hydrophobic nano composite automobile finish and preparation method thereof
CN103627306A (en) * 2013-11-07 2014-03-12 昆山大世界油墨涂料有限公司 Mist surface hand feeling scratch-resistant coating paint and preparation method thereof
CN103627306B (en) * 2013-11-07 2015-05-13 昆山大世界油墨涂料有限公司 Mist surface hand feeling scratch-resistant coating paint and preparation method thereof
CN103642380A (en) * 2013-11-21 2014-03-19 福建农林大学 Cellulose nanorod in situ reinforced aqueous polyurethane coating material
CN104017489A (en) * 2014-05-29 2014-09-03 中国石油大学(华东) Nano-TiO2 modified acrylic polyurethane finish paint and preparation method thereof

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