CN104371531B - High-reflective acrylic polyurethane coating composition - Google Patents

Abstract

The invention relates to a high-reflective acrylic polyurethane coating composition which comprises a component A and a component B in a mass part ratio of 20;3. The component A in 100 parts by mass comprises the following materials in part by mass: 30-50 parts of modified hydroxyl acrylic resin, 2-6 parts of auxiliaries, 35-45 parts of heat reflective pigments, 4-8 parts of aerogel and 10-15 parts of organic solvent. The component B in 100 parts by mass comprises the following materials in part by mass: 75-90 parts of polyisocyanate and 10-25 parts of organic solvent. The modified hydroxyl acrylic resin is obtained by cold-blending modified resin and hydroxyl acrylic resin in a mass part ratio of 1-3: 1; the solid content of the modified hydroxyl acrylic resin is greater than or equals to 75wt%; the particle size of heat reflective pigments ranges from 0.55 micron to 1.2 microns; the particle size of the aerogel ranges from 1 micron to 80 microns; the pore size of the aerogel ranges from 10 nanometers to 20 nanometers; and the heat conductivity coefficient of the aerogel is less than or equals to 0.015W/(m k). The polyisocyanate is one or more of HDI (hexamethylene diisocyanate) biuret, HDI trimer and IPDI (isophorone diisocyanate) trimer curing agents. The high-reflective acrylic polyurethane coating composition is high in reflective insulation quality; and the quantity of VOC (volatile organic compounds) of the high-reflective acrylic polyurethane coating component is low.

Description

A kind of high reflectance acrylic polyurethane coating composition

technical field

The invention relates to a high reflectivity acrylic polyurethane coating composition.

Background technique

Solar energy is a necessary condition for human survival and life, but strong radiation also brings many problems and inconvenience to industrial production and daily life. With the advent of a conservation-minded society and the aggravation of the global warming effect, materials with the ability to reflect solar heat and passive radiative cooling have attracted increasing attention. Especially on the outer surface of tanks and equipment such as chemical industry storage tanks and liquefied natural gas (LNG) storage tanks, if there is no protection of heat-reflective insulation materials, it will not only cause energy loss, but also may cause serious fires and explosions and other security incidents. Among the heat-reflecting and heat-insulating materials, the solar heat-reflecting coating is a simple and effective energy-saving material, and has become a research and development hotspot. The current solar heat reflective coatings generally improve the reflectivity through the selection and compatibility of pigments and fillers to achieve heat insulation effects. The level of reflectivity is the key to the selection of pigments and fillers. Secondly, the selection principle of the resin is to require the resin to have high transparency, light transmittance above 80%, low solar absorption rate, and try to make the resin contain less heat-absorbing groups such as COC, C=O, and OH. Chinese patents CN 101205435A and CN1583908A respectively disclose a solar heat reflective heat-insulating coating and a preparation method thereof. The purpose of heat-insulating reflection is achieved by using an undercoat chlorosulfonated polyethylene insulation layer and a topcoat thermoplastic heat-reflective coating. The resins used are all thermoplastic resins, which have poor outdoor aging resistance and low solid content of the resin, resulting in large VOC emissions from the entire supporting system. Chinese patent CN1800283 discloses a heat-insulating coating and its application. It uses nano-porous _SiO2 and nano-iron oxide yellow to prepare colored heat-insulating reflective coating, which has high heat reflectivity and good thermal insulation performance. The resin used is conventional Polyester polyurethane resin, acrylic polyurethane resin and other systems. Although these resin systems have better outdoor aging performance than thermoplastic resins, their disadvantages are that the solid content is generally not high, a lot of VOC is introduced, and all nano-pigments are used, and the particle size is relatively small. Small, the reflection of light waves in the visible light region is large, while the reflection in the near-infrared region will be weakened, and the heat reflection effect will be reduced accordingly.

Contents of the invention

The object of the present invention is: provide a kind of high-reflectivity acrylic polyurethane coating composition, can be coated on the outer surface of LNG storage tank and other chemical industry storage tanks, provide excellent reflective heat insulation effect and decorative effect, VOC releases little, energy saving.

The technical solution for realizing the object of the present invention is: a high-reflectivity acrylic polyurethane coating composition, characterized in that, it is composed of A component and B component, and the mass part ratio of A component to B component is 20:3;

In 100 parts by mass of component A, 30-50 parts of modified hydroxyacrylic resin, 2-6 parts of additives, 35-45 parts of heat-reflecting pigment, 4-8 parts of airgel, 10-15 parts of organic solvent, Its pigment-to-base ratio is ≥1.5; in 100 parts by mass of component B, there are 75-90 parts of polyisocyanate and 10-25 parts of organic solvent;

The modified hydroxy acrylic resin is obtained by cold blending the modified resin and the hydroxy acrylic resin at a mass ratio of 1 to 3:1, and the obtained modified hydroxy acrylic resin has a solid content ≥ 75wt%, wherein the modified resin It is one or more of CTR 6275 and CTR 6287 of CNOOC Changzhou Environmental Protection Coatings Co., Ltd., which are based on functional monomers of isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, vinyl tertiary carbonate, tertiary Several kinds of glycidyl carbonate are produced as polymerized monomers; the hydroxyl acrylic resin is S1196 of Nuplex Company or 878N of Arkema Company;

The heat reflective pigment is one or more of rutile TiO ₂ ALTIRIS 800, rutile TiO ₂ ALTIRIS 550, nickel titanium yellow PY-53, titanium chrome yellow PBN-24, and iron red PR-101. The particle size range is 0.55～1.2μm;

The airgel is silicon aerogel, which is a kind of porous silica with a particle size of 1-80 μm, a pore size of 10-20 nm, and a thermal conductivity of ≤0.015W/(m·k);

The polyisocyanate is one or more of HDI biuret, HDI trimer, and IPDI trimer curing agent.

In component A of the above-mentioned high-reflectivity acrylic polyurethane coating composition, the weight average molecular weight of the hydroxy acrylic resin is 4000-5000, the solid content is 55-60wt%, and the hydroxyl content is 2.3-2.6wt%, as measured by a rotational viscometer The viscosity of the modified resin is 2400-3800mPa·s; the weight-average molecular weight of the modified resin is 2000-2500, the solid content is ≥80wt%, the hydroxyl content is 3.8-4.2wt%, and the viscosity measured by the rotational viscometer is 2500-3600mPa ·s.

The volume solid content of the above-mentioned high-reflectivity acrylic polyurethane coating composition is ≥ 75%, VOC release ≤ 250g/L, and heat reflectivity ≥ 0.9.

In the A component of the above-mentioned high-reflectivity acrylic polyurethane coating composition, the airgel is the product SJ 1800 of China Factor Hi-Tech Co., Ltd., the product SQ2 of China Allison Co., Ltd., and the product SF of China Nano Hi-Tech Co., Ltd. one or several.

In component A of the above-mentioned high-reflectivity acrylic polyurethane coating composition, the auxiliary agent is one of wetting and dispersing agent, defoamer, leveling agent, amine drier, anti-settling agent, and anti-sagging agent. species or several.

In the above-mentioned high-reflectivity acrylic polyurethane coating composition, the organic solvent is xylene, butyl acetate, ethyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, cyclohexanone, butanone, methyl iso One or more of butyl ketone, aromatic hydrocarbon solvent No. 100, aromatic hydrocarbon solvent No. 150, and aromatic hydrocarbon solvent No. 200.

The technical effect of the present invention is: the high-reflectivity acrylic polyurethane coating composition of technical scheme of the present invention compares with existing similar coating, has following significant technical effect:

① In component A, the modified resin is introduced into the usual hydroxyacrylic resin to obtain a modified hydroxyacrylic resin with high solid content, low VOC release, and excellent weather resistance and aging resistance. Because the introduced modified resin is prepared from several functional monomers of isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, tertiary carbonic acid vinyl ester, and tertiary carbonic acid glycidyl ester as polymerized monomers. Using such a modified hydroxyacrylic resin as a base material can not only increase the overall solid content of the coating composition, but also improve the aging resistance and yellowing resistance of the coating polymer, and the coating has a high decorative function. When coating the outer wall of the tank, a coating thickness of 30-80 μm can significantly improve the heat reflection and heat insulation effect of the entire coating and provide long-term decorative protection;

② In component A, one or more of rutile TiO ₂ ALTIRIS 800, rutile TiO ₂ ALTIRIS 550, nickel titanium yellow PY-53, titanium chrome yellow PBN-24 and iron red PR-101 were used as Heat reflective pigments with a particle size range of 0.55 to 1.2 μm. Compared with pigments commonly used in the prior art such as ordinary rutile titanium dioxide, ordinary iron red, and ordinary iron yellow, the wavelength of the infrared spectrum region is greater than 0.76 μm The light reflectivity is high, which can significantly improve the heat reflection effect of the coating;

③In component A, the airgel used is a kind of porous silica with a particle size of 1-80 μm, a pore size of 10-20 nanometers, and a thermal conductivity of ≤0.015W/(m·k)(25°C) , due to the light weight, small particle size, and low thermal conductivity of this airgel, it can effectively fill the pores between particles, reduce the void ratio of the paint film, and minimize the black body absorption effect of the voids, thereby effectively improving the coating. The emissivity and reflectivity make the coating have the characteristics of low density, high volume solid content and good heat insulation effect;

④In component B, the polyisocyanate resin is one or more of HDI biuret, HDI trimer, and IPDI trimer. These multimers have more than three functionalities and a small relative molecular mass. , with high crosslinking activity, fast drying, high hardness of paint film, high solid content, low viscosity, can prepare high solid content coating composition and low VOC release, is an environmental protection, energy saving, high decorative High-quality heat-reflective heat-insulating coatings meet the current green and energy-saving environmental requirements.

detailed description

The present invention will be further described below in conjunction with the examples, but not limited thereto.

The raw materials used in embodiments and comparative examples are commercially available industrial supplies unless otherwise specified, and can be purchased through commercial channels, wherein:

Among the additives, the dispersant BYK 163 is a product of BYK Company in Germany; the foaming agent DF-22 is a product of EDL Company in Canada; the anti-sagging agent PLUS is a product of Hemings Company in the United States; the leveling agent EFKA 3777 is a product of EFKA Auxiliary Company in the Netherlands ;

Among the heat reflective pigments, rutile TiO ₂ ALTIRIS 550 and rutile TiO ₂ ALTIRIS 800 are products of Huntsman Company of the United States; nickel titanium yellow PY-53 is a product of China Kohler Pigment Company; the particle size range of the above pigments is 0.55～1.2 μm ;

Polyisocyanate HDI trimer N-3390 is a product of Bayer, Germany;

The preparation modified hydroxyacrylic resin of embodiment 1

① Formula

In the modified hydroxyacrylic resin of every 100 mass parts, 25 mass parts of hydroxyacrylic resin S1196, 75 mass parts of modified resin CTR 6275, wherein: hydroxyacrylic resin S1196 is the product of Nuplex (China) company, and its weight-average molecular weight is 4000-5000, the solid content is 55-60wt%, the hydroxyl content is 2.3-2.6wt%, the viscosity measured by the rotational viscometer is 2400-3800mPa·s; the modified resin CTR 6275 is a product of CNOOC Changzhou Environmental Protection Coatings Co., Ltd., they It is made of functional monomers such as isobornyl methacrylate, cyclohexyl acrylate and glycidyl tert-carbonate as comonomers, with a weight average molecular weight of 2000-2500, a solid content of ≥80wt%, and a hydroxyl content of 4.0- 4.2wt%, the viscosity measured by the rotational viscometer is 2500-3000mPa·s.

② Preparation method

In the dispersion tank, the hydroxyacrylic resin and the modified resin were evenly stirred, filtered and packaged to obtain the modified hydroxyacrylic resin with a solid content of 75 wt%, which was stored for future use.

Embodiment 2 prepares A component 1 (white, pigment base ratio 1.5)

① Formula

In every 100 parts by mass of A component, 40 parts of modified hydroxy acrylic resin prepared in Example 1, 39 parts of heat reflective pigments (including 26 parts of rutile TiO ₂ ALTIRIS 550 and 13 parts of rutile TiO ₂ ALTIRIS 800) , 6 parts of airgel SJ1800, 3 parts of additives (including 1 part of dispersant BYK 163, 0.5 parts of defoamer DF-220.5 parts of anti-sagging agent PLUS and 1 part of leveling agent EFKA 3777), 12 parts of organic solvent ( Contains 6 parts xylene and 6 parts butyl acetate).

② Preparation method

In the dispersion tank, add modified hydroxyacrylic resin, organic solvent, dispersant, defoamer, stir evenly, add anti-sag agent PLUS, stir at high speed for 15 minutes, make anti-sag agent PLUS fully wet and disperse, then add Heat-reflecting pigments and aerogels are stirred evenly, then moved into a sand mill, and are ground and dispersed until the slurry has a fineness of 25 μm, then discharged, stirred evenly, filtered, and packaged to obtain component A 1, which is stored for future use.

Embodiment 3 prepares A component 2 (light yellow, pigment base ratio 1.5)

① Formula

In every 100 parts by mass of A component, 40 parts of modified hydroxy acrylic resin prepared in Example 1, 39 parts of heat reflective pigments (including 26 parts of rutile TiO ₂ ALTIRIS 550, 13 parts of nickel titanium yellow PY-53) , 6 parts of airgel SJ 1800, 3 parts of additives (including 1 part of dispersant BYK 163, 0.5 parts of defoamer DF-22, 0.5 parts of anti-sagging agent PLUS, 1 part of leveling agent EFKA3777), 12 parts of organic Solvents (including 6 parts xylene and 6 parts butyl acetate).

② Preparation method

In the dispersion tank, add modified hydroxyacrylic resin, organic solvent, dispersant, defoamer, stir evenly, add anti-sag agent PLUS, stir at high speed for 15 minutes, make anti-sag agent PLUS fully wet and disperse, then add Heat reflective pigments and aerogels are stirred evenly, then moved into a sand mill, and are ground and dispersed until the slurry has a fineness of 25 μm, then discharged, stirred evenly, filtered, and packaged to obtain component A 2, which is stored for later use.

Embodiment 4 prepares B component

① Formula

In every 100 parts by mass of B component, 88 parts of HDI trimer N-3390, 12 parts of organic solvent (including 5 parts of xylene, 5 parts of urethane grade butyl acetate, 2 parts of propylene glycol methyl ether acetate).

② Preparation method

Add the organic solvent into the dispersing tank, add HDI trimer N-3390 under stirring, stir evenly, filter, pack to obtain component B, and save it for later use.

Embodiment 5 prepares high reflectivity acrylic polyurethane coating composition 1

When using, firstly stir the A component 1 obtained in Example 2 and the B component obtained in Example 4 respectively, then weigh the A component and B component respectively according to the mass part ratio of 20:3, and then mix and stir evenly to obtain the high-reflectivity acrylic polyurethane coating composition 1.

Embodiment 6 prepares high-reflectivity acrylic polyurethane coating composition 2

When using, firstly stir the A component 2 obtained in Example 3 and the B component obtained in Example 4 respectively, then weigh the A component and B component respectively according to the mass part ratio of 20:3, and then mix And stir evenly, namely high reflectance acrylic polyurethane coating composition 2.

Comparative Example 1 Preparation of Comparative Example Acrylic Polyurethane Coating Ⅰ

① Prepare the component of Comparative Example 1A

The formula is basically the same as the A component 1 prepared in Example 2, the difference is that the modified hydroxyacrylic resin prepared in Example 1 is replaced with 40 parts of hydroxyacrylic resin S1196 (solid content 60wt%); A is prepared according to Example 2 The method of component makes comparative example 1A component, preserves for subsequent use;

②Preparation of comparative example 1 acrylic polyurethane coating Ⅰ

Stir the component A of comparative example 1 prepared in step ① and the component B prepared in Example 4 evenly, respectively weigh component A and component B of comparative example 1 according to the mass part ratio of 20:3, and then mix and stir After uniformity, the acrylic polyurethane coating I of Comparative Example 1 was obtained.

Comparative Example 2 Preparation of Comparative Example Acrylic Polyurethane Coating II

①Preparation of the component of Comparative Example 2A

The formula is basically the same as that of the component A of Comparative Example 1, the difference being that 39 parts of rutile titanium dioxide R-902 is used to replace the heat-reflecting pigment, and 6 parts of glass microspheres are used to replace the airgel; the component A is prepared according to Example 2 The method for making comparative example 2A component is preserved for subsequent use;

② Preparation of Comparative Example 2 Acrylic Polyurethane Coating II

Stir the component A of comparative example 2 prepared in step ① and the component B prepared in Example 4 evenly, respectively weigh component A and component B of comparative example 2 according to the mass part ratio of 20:3, and then mix and stir After uniformity, the acrylic polyurethane coating II of Comparative Example 2 was obtained.

Test coating properties

(1) Testing the performance of the coating itself

① Detection method

appearance, visual inspection;

The volume solid content is measured according to GB/T 9272-2007;

VOC content is measured according to GB/T 23985-2009;

Flexibility is measured according to GB/T 1731-1993, the test plate is a tinplate plate, and the thickness of the coating film is 20±3μm;

Impact test according to GB/T 1732-1993, the test plate is tin plate, film thickness 20±3μm;

Pull-off method adhesion test according to GB/T 5210-2006, the test plate is sandblasted steel plate, film thickness 320±20μm.

② The test results are shown in Table 1.

Table 1

As can be seen from the results in Table 1, the high-reflectivity acrylic polyurethane coating composition of the present invention (embodiment 6 and embodiment 6 system), because A component has used the modified hydroxyl acrylic resin in the technical scheme, and has added heat reflection Pigment and aerogel, pigment base ratio ≥ 1.5, use HDI trimer N-3390 as B component and A component to cooperate, make the coating composition of the present invention and current acrylic polyurethane coating (comparative example 1, comparative example 2 system) In comparison, it has higher volume solids content, lower VOC emission, higher gloss, and good mechanical properties at the same time.

(2) Detect the coordination performance of paint and coating system

The high-reflectivity acrylic polyurethane coating composition of the present invention can be used as the coating that bottom surface combines, also can be mixed with epoxy primer, acrylic primer, epoxy zinc-rich primer, epoxy cloud iron paint, inorganic zinc silicate Primer and other anti-corrosion coatings are used in supporting construction to form an ultra-high-performance anti-corrosion and aging-resistant heat-insulating reflective coating system.

Listed below is the matching coating detection data of the coating composition of the present invention as the heat-shielding reflective finish paint and the anti-corrosion primer that the chemical industry tank uses in the marine corrosive environment:

①Prototype making

For detecting embodiment 5 and 6, the test plate of the matching performance of comparative example 1 and 2 paint coating system is the thick blasting steel plate of 3～5mm;

Taking MC-EP-1 epoxy zinc-rich primer as primer, MC-EI-1 epoxy miracic iron paint as intermediate paint, the coating that embodiment 5, embodiment 6 or comparative example 1, comparative example 2 make is The topcoat constitutes the coating system, first spray the primer (dry film thickness 60 μm), then spray the intermediate paint (dry film thickness 150 μm) and topcoat (dry film thickness 40 μm), the dry film thickness of the coating system is 250 ±20μm.

② Detection method

The salt spray resistance test is carried out according to GB/T 1763;

The artificial weathering resistance test is carried out according to Appendix A of ISO 20340-2009;

The solar heat reflectance is tested according to GB/T 25261-2010;

Hemispherical emissivity is tested according to GB/T 2680-1994;

The thermal conductivity is tested according to GJB 1201.1-91;

③ The test results are shown in Table 2.

Table 2

Can know by above-mentioned detection result: compared with existing acrylic polyurethane coating (comparative example 1 and 2), the high reflectance acrylic polyurethane coating composition of the embodiment of the present invention 5 and 6 is as the finish coat in supporting coating system, makes The coating system has excellent adhesion, corrosion resistance and artificial weathering resistance; especially has excellent solar heat reflectivity, can effectively reflect solar heat, and has the function of heat insulation reflection and has a low Thermal conductivity, can play a more excellent thermal insulation effect. The above advantages prove that this coating can be completely used for the protection of the outer wall of LNG storage tanks or various chemical industrial storage tanks. It can reflect solar heat radiation, provide excellent reflective heat insulation and decorative effects, and effectively maintain a qualified daily evaporation rate. Not only environmental protection and energy saving but also improve safety.

Claims (4)

1. a high reflectivity acrylic polyurethane coating composition is characterized in that, is made of A component and B component, and the mass part ratio of A component and B component is 20:3; The volume of described coating composition Solid content ≥ 75%, VOC release ≤ 250g/L, heat reflectance ≥ 0.9; In 100 parts by mass of component A, 30-50 parts of modified hydroxyacrylic resin, 2-6 parts of additives, 35-45 parts of heat-reflecting pigment, 4-8 parts of airgel, 10-15 parts of organic solvent, Its pigment-to-base ratio is ≥1.5; in 100 parts by mass of component B, there are 75-90 parts of polyisocyanate and 10-25 parts of organic solvent; The modified hydroxy acrylic resin is obtained by cold blending the modified resin and the hydroxy acrylic resin at a mass ratio of 1 to 3:1, and the obtained modified hydroxy acrylic resin has a solid content ≥ 75wt%, wherein the modified resin It is one or more of CTR 6275 and CTR 6287 of CNOOC Changzhou Environmental Protection Coatings Co., Ltd., which are based on functional monomers of isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, vinyl tertiary carbonate, tertiary Several kinds of glycidyl carbonate are prepared as polymerized monomers, the obtained modified resin has a weight average molecular weight of 2000-2500, a solid content of ≥80wt%, a hydroxyl content of 3.8-4.2wt%, and a viscosity measured by a rotational viscometer 2500～3600mPa·s; the hydroxyacrylic resin is S1196 of Nuplex Company or 878N of Arkema Company; the weight average molecular weight of the hydroxyacrylic resin is 4000～5000, the solid content is 55～60wt%, and the hydroxyl content is 2.3～2.6wt% , the viscosity measured by the rotational viscometer is 2400-3800mPa·s; The heat reflective pigment is one or more of rutile TiO ₂ ALTIRIS 800, rutile TiO ₂ ALTIRIS 550, nickel titanium yellow PY-53, titanium chrome yellow PBN-24, and iron red PR-101. The particle size range is 0.55～1.2μm; The airgel is silicon aerogel, which is a kind of porous silica with a particle size of 1-80 μm, a pore size of 10-20 nm, and a thermal conductivity of ≤0.015W/(m·k); The polyisocyanate is one or more of HDI biuret, HDI trimer, and IPDI trimer curing agent. 2. The high-reflectivity acrylic polyurethane coating composition according to claim 1, is characterized in that, in A component, described airgel is the product SJ 1800 of China Factor Hi-Tech Company, the product of China Ai Lisheng Company. One or more of the product SQ2 and the product SF of China Nano Hi-Tech Co., Ltd. 3. The high-reflectivity acrylic polyurethane coating composition according to claim 1, wherein, in component A, the auxiliary agent is a wetting and dispersing agent, a defoamer, a leveling agent, and an amine drying agent One or more of the agent, anti-settling agent, anti-sagging agent. 4. high reflectance acrylic polyurethane coating composition according to claim 1, is characterized in that, described organic solvent is xylene, butyl acetate, ethyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate , cyclohexanone, ethyl ketone, methyl isobutyl ketone, aromatic hydrocarbon solvent No. 100, aromatic hydrocarbon solvent No. 150, and aromatic hydrocarbon solvent No. 200.