CN117801604A - White nanometer color paste preparation method and application thereof - Google Patents

White nanometer color paste preparation method and application thereof Download PDF

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Publication number
CN117801604A
CN117801604A CN202311864155.5A CN202311864155A CN117801604A CN 117801604 A CN117801604 A CN 117801604A CN 202311864155 A CN202311864155 A CN 202311864155A CN 117801604 A CN117801604 A CN 117801604A
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white
color paste
stirring
solution
titanium dioxide
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阳全美
劳星乔
于法猛
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Shenzhen Anycubic Technology Co Ltd
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Shenzhen Anycubic Technology Co Ltd
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Abstract

The invention provides a white nanometer color paste and a preparation method and application thereof; the white nanometer color paste comprises the following components in percentage by mass: 30% -50% of acrylate monomer; silica coated titanium dioxide 40% -65%; 5% -20% of dispersing auxiliary agent; 0.1 to 1 percent of coupling agent; 0.1% -1% of wetting agent; 0.05 to 0.5 percent of stabilizer. Compared with the prior art, the white nanometer color paste provided by the invention adopts specific components with specific content, especially introduces silicon oxide to coat titanium dioxide, realizes better interaction as a whole, has higher color saturation, good stability, difficult sedimentation, good weather resistance and high universality; further applied to 3D printing of white photosensitive resin, the obtained 3D printing white photosensitive resin has the advantages of good stability, high color saturation, high tensile strength and good compatibility.

Description

The method comprises the following steps of: white color nanometer color paste preparation method and application thereof
Technical Field
The invention relates to the technical field of 3D printing, in particular to a white nanometer color paste and a preparation method and application thereof.
Background
The 3D printing technology is a subversion and perfection of the traditional manufacturing mode, is used as a rapid and simple forming technology, and is widely applied to the fields of industrial manufacturing, aerospace, constructional engineering, biomedical treatment, education, personalized customization and the like. Among them, the photo-curing 3D printing technology is the most attractive technology at present, and has the advantages of high forming speed, high precision and the like.
With the continuous development of material performance and printing technology, the three-dimensional solid body is manufactured while being endowed with colorful appearance, and the method is one of important development trends in the field of additive manufacturing. At present, only the UV light curing ink-jet printing technology can realize real color three-dimensional printing, objects manufactured by the light curing 3D printing technology are all monochromatic, colors are coated after the objects are printed, and white is widely applied to multi-color light curing 3D printing because of excellent covering effect of white and can be used as a base color to highlight color patterns.
The white UV nano color paste is an important component in the 3D printing white photosensitive resin, and directly influences the stability of the photosensitive resin. The existing white color paste is generally titanium dioxide, has large specific gravity and difficult dispersion, and is easy to have the problems of low color saturation, floating color, sedimentation and the like. Therefore, development of a white nanometer color paste with good stability, high color saturation and good compatibility is needed.
Disclosure of Invention
In view of the above, the invention aims to provide a white nanometer color paste, a preparation method and application thereof, and the white nanometer color paste provided by the invention has higher color saturation, good stability, difficult sedimentation, good weather resistance and high universality.
The invention provides a white nanometer color paste, which comprises the following components in percentage by mass:
30% -50% of acrylate monomer;
silica coated titanium dioxide 40% -65%;
5% -20% of dispersing auxiliary agent;
0.1 to 1 percent of coupling agent;
0.1% -1% of wetting agent;
0.05 to 0.5 percent of stabilizer.
Optionally, the acrylate monomer is a monofunctional acrylate monomer and/or a difunctional acrylate monomer; the monofunctional acrylate monomer comprises one or more of acyl morpholine acrylate, lauryl acrylate, 2-phenoxy-ethyl acrylate and tetrahydrofuran acrylate; the difunctional acrylate monomer comprises one or more of 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate and diethylene glycol diacrylate.
Optionally, the preparation method of the silica coated titanium dioxide specifically comprises the following steps:
mixing nano titanium dioxide with water to obtain TiO 2 A slurry;
the TiO is treated with 2 Heating the slurry to 75-100 ℃, and dripping alkaline solution to adjust the pH value to 8-11;
dropwise adding silicate solution under stirring, and carrying out reaction for a preset period of time;
neutralizing with acid solution until the pH value is 8-9, continuing stirring for 20-40 min, and cooling to obtain an intermediate;
and (3) washing, drying and crushing the intermediate in sequence to obtain the silica coated titanium dioxide.
Optionally, the water is deionized water;
the alkaline solution comprises one or more of NaOH solution and KOH solution;
the silicate solution comprises Na 2 SiO 3 Solution, K 2 SiO 3 One or more of the solutions;
the acidic solution comprises H 2 SO 4 One or more of solution, HCl solution;
the mass ratio of the nano titanium dioxide to the water is (2-5): 1, a step of; the rotating speed of the stirring condition is 800 rad/min-1200 rad/min; the concentration of the silicate solution is 0.1 mol/L-1 mol/L, wherein the mass of silicate is 2% -20% of the mass of the nano titanium dioxide; the preset time length is 4-8 hours; the concentration of the alkaline solution is 5% -20%, and the concentration of the acidic solution is 5% -20%.
Optionally, the dispersing aid is an acidic dispersing agent and/or a pigment synergist for a UV system; the acid dispersant for the UV system comprises one or more of BYK111, BYK9151, BYK180, SOLSPERSE 36000, SOLSPERSE88000, SOLSPERSE 22000, EFKA4340, EFKA7701, dispers0685 and Dispers 680 UV.
Optionally, the coupling agent comprises one or more of titanate coupling agent, silane coupling agent, aluminate coupling agent and zirconium aluminate coupling agent; the wetting agent is an acrylic polymer.
Optionally, the coupling agent comprises one or more of KR-12, KH560, M-1PM, PN-130, the wetting agent comprises one or more of BYK355, BYK381, L-1980N, L-1984N, and the stabilizer comprises one or more of genrad 16, genrad 18, genrad 22.
The invention also provides a preparation method of the white nanometer color paste, which comprises the following steps:
stirring an acrylic ester monomer, a dispersing auxiliary, a wetting agent and a stabilizer to obtain a first mixture;
adding silica coated titanium dioxide and a coupling agent into the first mixture, and stirring to obtain a second mixture;
grinding the second mixture to obtain white nanometer color paste.
Optionally, the grinding the second mixture to obtain white nano color paste includes:
and respectively carrying out coarse grinding and fine grinding on the second mixture to obtain white nanometer color paste.
Optionally, the stirring speed of stirring the acrylate monomer, the dispersing auxiliary, the wetting agent and the stabilizer is 1500 rad/min-3500 rad/min, stirring for 15-25 min; and adding silicon oxide coated titanium dioxide and a coupling agent into the first mixture, and stirring at the stirring speed of 2800 rad/min-3500 rad/min for 40 min-80 min.
Optionally, the coarse grinding adopts a sand mill, wherein the filling quantity of the zirconium beads is 65-85%, and the specification of the zirconium beads is 0.25-0.3 mm; the rotating speed of the rough grinding is 1000 rad/min-2000 rad/min, and the time is 2-4 h; the fine grinding adopts a high-speed grinding machine, the ambient humidity is 40-60% RH, the temperature is 20-30 ℃, the rotating speed is 2000-3500 rad/min, and the time is 2-10 h.
The invention also provides a 3D printing white photosensitive resin, which comprises white nanometer color paste; the white nanometer color paste is the white nanometer color paste according to the technical scheme.
The invention provides a white nanometer color paste and a preparation method and application thereof; the white nanometer color paste comprises the following components in percentage by mass: 30% -50% of acrylate monomer; silica coated titanium dioxide 40% -65%; 5% -20% of dispersing auxiliary agent; 0.1 to 1 percent of coupling agent; 0.1% -1% of wetting agent; 0.05 to 0.5 percent of stabilizer. Compared with the prior art, the white nanometer color paste provided by the invention adopts specific components with specific content, especially introduces silicon oxide to coat titanium dioxide, realizes better interaction as a whole, has higher color saturation, good stability, difficult sedimentation, good weather resistance and high universality; further applied to 3D a white photosensitive resin is printed out, the obtained 3D printing white photosensitive resin has good stability high color saturation, high tensile strength and good compatibility.
In addition, the preparation method provided by the invention has the advantages of simple process, mild and easily controlled conditions, easily available raw materials, low cost and wide application prospect.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a white nanometer color paste, which comprises the following components in percentage by mass:
30% -50% of acrylate monomer;
silica coated titanium dioxide 40% -65%;
5% -20% of dispersing auxiliary agent;
0.1 to 1 percent of coupling agent;
0.1% -1% of wetting agent;
0.05 to 0.5 percent of stabilizer.
In the invention, the raw materials of the white nanometer color paste comprise acrylate monomers, silicon oxide coated titanium dioxide, a dispersing auxiliary agent, a coupling agent, a wetting agent and a stabilizer.
In the present invention, the acrylate monomer is a monofunctional acrylate monomer and/or a difunctional acrylate monomer; wherein the monofunctional acrylate monomer comprises one or more of acyl morpholine acrylate, lauryl acrylate, 2-phenoxy-ethyl acrylate and tetrahydrofuran acrylate; the difunctional acrylate monomer comprises one or more of 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate and diethylene glycol diacrylate. The source of the acrylate monomer is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the invention, the white nanometer color paste comprises 30% -50% of acrylate monomer, and specific numerical values are not limited, such as 30%,32.9%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 42.9%, 45%, 48%, 50% and the like.
In the invention, the preparation method of the silica coated titanium dioxide specifically comprises the following steps:
mixing nano titanium dioxide with water to obtain TiO 2 A slurry;
TiO is mixed with 2 Heating the slurry to 75-100 ℃ and dropwise adding alkaliA sexual solution for adjusting the pH value to 8-11;
dropwise adding silicate solution under stirring, and carrying out reaction for a preset period of time;
neutralizing with acid solution until the pH value is 8-9, continuing stirring for 20-40 min, and cooling to obtain an intermediate;
and (3) washing, drying and crushing the intermediate in sequence to obtain the silica coated titanium dioxide.
In the invention, the nano titanium dioxide can be rutile titanium dioxide with stable structure and good weather resistance, such as DuPont R902 and R960 from commercial sources, stone CR60-2, R980, hunsman R-FC5 and the like. In the present invention, the water is deionized water.
In the present invention, the mass ratio of the nano titanium dioxide to the water is (2-5): 1, the number of the components is 1, may be (3 to 4): 1, a step of; the nano titanium dioxide and water are mixed under the stirring condition, and the stirring speed can be 400 rad/min-1200 rad/min, and further can be 400 rad/min-600 rad/min.
In the present invention, the alkaline solution may include one or more of NaOH solution, KOH solution, such as NaOH solution; the concentration of the NaOH solution is 5% -20%, and can be 10% specifically.
In the present invention, the silicate solution may include Na 2 SiO 3 Solution, K 2 SiO 3 One or more of the solutions; na (Na) 2 SiO 3 The concentration of the solution is 0.1mol/L to 1mol/L, for example, 0.1mol/L, 0.2mol/L, 0.4mol/L, 0.6mol/L, 0.8mol/L, and 1mol/L.
In the present invention, the acidic solution includes H 2 SO 4 One or more of the solution and HCl solution, more H 2 SO 4 A solution; dilute H 2 SO 4 The concentration of (2) is 5% to 20%, for example, 5%, 10% or 20%.
The source of the above-mentioned solutions is not particularly limited in the present invention, and for example, aqueous solutions prepared from commercially available analytically pure raw materials well known to those skilled in the art may be used, or the corresponding solutions may be purchased directly.
In the present invention, the concentration of alkali metal ions in the silicate solution above 1mo/L increases the tendency of the active silicon to agglomerate, forming a complex mixture; the mass of silicate in the silicate solution is 2-20% of the mass of the nano titanium dioxide, for example, can be 5-10%;
in the invention, the rotation speed of the stirring condition for dropwise adding silicate solution under the stirring condition is 800 rad/min-1200 rad/min, such as 1000rad/min; the dripping is carried out slowly at a rate of 1 drop/1 second to 3 seconds, for example, the dripping can be carried out slowly at a rate of 1 drop/2 seconds.
In the invention, the preset time is 4-8 h, and can be specifically 6h.
In the invention, the white nanometer color paste comprises 40-65% of silicon oxide coated titanium dioxide, and specifically can comprise 40%, 43%, 45%, 48%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 63%, 65% and the like.
In the invention, the dispersing aid is at least one of an acid dispersing agent and/or a pigment synergist for a UV system; the dispersing aid may include one or more of BYK111, BYK9151, BYK180, SOLSPERSE 36000, SOLSPERSE88000, SOLSPERSE 22000, EFKA4340, EFKA7701, dispers0685, dispers 680 UV. The source of the dispersing aid is not particularly limited and commercially available products known to those skilled in the art may be used.
In the invention, the white nanometer color paste comprises 5 to 20 percent of dispersing auxiliary agent, and can be specifically 5 percent, 6 percent, 6.5 percent, 7 percent, 7.5 percent, 8 percent, 10 percent, 13 percent, 17 percent, 20 percent and the like.
In the present invention, the coupling agent includes one or more of a titanate coupling agent, a silane coupling agent, an aluminate coupling agent, and a zirconium aluminate coupling agent. Specifically, the coupling agent may include one or more of KR-12, KH560, M-1PM, PN-130. The source of the coupling agent is not particularly limited and commercially available products known to those skilled in the art may be used. In the invention, the white nanometer color paste comprises 0.1 to 1 percent of coupling agent, and can be specifically 0.1 percent, 0.2 percent, 0.3 percent, 0.4 percent, 0.45 percent, 0.5 percent, 0.55 percent, 0.6 percent, 0.8 percent, 1 percent and the like.
In the present invention, the wetting agent may be an acrylic polymer, and may specifically be one or more of BYK355, BYK381, L-1980N, L-1984N. The source of the wetting agent is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In the invention, the white nanometer color paste comprises 0.1 to 1 percent of wetting agent, and can be specifically 0.1 percent, 0.2 percent, 0.3 percent, 0.4 percent, 0.45 percent, 0.5 percent, 0.55 percent, 0.6 percent, 0.8 percent, 1 percent and the like.
In the present invention, the stabilizer may include one or more of genrad 16, genrad 18, genrad 22 of RAHN company. The source of the stabilizer is not particularly limited and commercially available products known to those skilled in the art may be used. In the invention, the white nanometer color paste comprises 0.05 to 0.5 percent of stabilizer, and can be specifically 0.05 percent, 0.08 percent, 0.09 percent, 0.10 percent, 0.11 percent, 0.12 percent, 0.2 percent, 0.24 percent, 0.29 percent, 0.33 percent, 0.38 percent, 0.4 percent, 0.43 percent, 0.44 percent, 0.5 percent and the like.
In the invention, the median diameter D50 of the white nanometer color paste is 100 nm-200 nm.
The invention firstly provides a silicon oxide coated nano titanium dioxide, which is prepared by coating nano TiO 2 The inorganic modification is carried out, and the silica is used for coating the titanium dioxide, so that the chalk resistance and color retention are obviously improved, and the white color paste serving as the pigment has excellent color saturation and weather resistance; the invention further provides a white nanometer color paste, which selects titanium dioxide with the grain diameter of about 300nm, and cooperates with a dispersing agent and a pigment synergist to enhance the rheological property of the color paste and improve the storage stability and coloring coverage of photosensitive resin; the white nanometer color paste provided by the invention is prepared by adding a coupling agent into TiO (titanium dioxide) in the grinding process of the nanometer color paste 2 The organic modification is carried out to lead the inorganic filler to be organized, the affinity with the acrylic resin to be enhanced, the dispersibility of the titanium pigment in the color paste to be improved, and the occurrence of the sedimentation phenomenon of the color paste to be inhibited.
The specific components with specific content are adopted, particularly the silica coated titanium dioxide is introduced, and the specific components with other specific proportions are matched, so that the overall better interaction is realized, and the product has higher color saturation, good stability, difficult sedimentation, good weather resistance and high universality; the method is further applied to the 3D printing white photosensitive resin, and the obtained 3D printing white photosensitive resin has the advantages of being good in stability, high in color saturation, large in tensile strength and good in compatibility.
The invention also provides a preparation method of the white nanometer color paste, which comprises the following steps:
stirring an acrylic ester monomer, a dispersing auxiliary, a wetting agent and a stabilizer to obtain a first mixture;
adding silica coated titanium dioxide and a coupling agent into the first mixture, and stirring to obtain a second mixture;
grinding the second mixture to obtain white nanometer color paste.
Firstly, stirring an acrylic ester monomer, a dispersing auxiliary, a wetting agent and a stabilizer to obtain a first mixture; and adding the silica coated titanium dioxide and the coupling agent into the first mixture, and stirring to obtain a second mixture. In the invention, the acrylate monomer, the dispersing aid, the wetting agent, the stabilizer, the silica coated titanium pigment and the coupling agent are the same as those in the technical scheme, and are not repeated here.
In the invention, grinding the second mixture to obtain white nanometer color paste, which comprises the following steps:
and respectively carrying out coarse grinding and fine grinding on the second mixture to obtain white nanometer color paste.
In the invention, the stirring speed of stirring the acrylic ester monomer, the dispersing auxiliary, the wetting agent and the stabilizing agent is 1500 rad/min-3500 rad/min, and further can be 1500 rad/min-2500 rad/min, and the stirring time is 15 min-25 min; adding silica coated titanium pigment and a coupling agent into the first mixture, and stirring at a stirring speed of 2800 rad/min-3500 rad/min for 40 min-80 min. The above-described stirring process may be uniformly performed in a dispersing stirrer well known to those skilled in the art.
After the second mixture is obtained, the second mixture is ground to obtain the white nanometer color paste.
In the invention, a sand mill is adopted for rough grinding, wherein the filling quantity of zirconium beads is 65-85%, and the specification of the zirconium beads is 0.25-0.3 mm; the rotation speed of the rough grinding is 1000 rad/min-2000 rad/min, and the time is 2-4 h.
In the invention, a high-speed grinding machine is adopted for fine grinding, the ambient humidity is 40-60% RH, the temperature is 20-30 ℃, the rotating speed is 2000-3500 rad/min, the time is 2-10 h, and the time can be further 6-8 h.
The preparation method provided by the invention has the advantages of simple process, mild and easily controlled conditions, easily available raw materials, low cost and wide application prospect.
The invention also provides a 3D printing white photosensitive resin, which comprises white nanometer color paste; the white nanometer color paste is the technology the white nanometer color paste is prepared.
In the invention, the 3D printing white photosensitive resin pigment has small particle size and good stability; no sedimentation and delamination after aging for 7 days at 70 ℃, and little change of viscosity and pigment particle size.
The invention provides a white nanometer color paste and a preparation method and application thereof; the white nanometer color paste comprises the following components in percentage by mass: 30% -50% of acrylate monomer; silica coated titanium dioxide 40% -65%; 5% -20% of dispersing auxiliary agent; 0.1 to 1 percent of coupling agent; 0.1% -1% of wetting agent; 0.05 to 0.5 percent of stabilizer. Compared with the prior art, the white nanometer color paste provided by the invention adopts specific components with specific content, especially introduces silicon oxide to coat titanium dioxide, realizes better interaction as a whole, has higher color saturation, good stability, difficult sedimentation, good weather resistance and high universality; the method is further applied to the 3D printing white photosensitive resin, and the obtained 3D printing white photosensitive resin has the advantages of being good in stability, high in color saturation, large in tensile strength and good in compatibility.
In addition, the preparation method provided by the invention has the advantages of simple process, mild and easily controlled conditions, easily available raw materials, low cost and wide application prospect.
In order to further illustrate the present invention, the following examples are provided. The raw materials used in the following examples of the present invention are all commercially available sources; the preparation method of the silica coated titanium dioxide comprises the following steps:
adding 300g of rutile type nano titanium dioxide CR60-2 and 100g of deionized water into a 2L three-neck flask with a stirrer, a thermometer and a condenser, stirring at a speed of 500rad/min, heating to 90 ℃ after stirring and mixing uniformly, dripping 10% NaOH solution to adjust the pH value of the slurry to 9-10, stirring at a speed of 1000rad/min, and slowly dripping 1L of 0.2mol/L Na at a speed of 1 drop/2 seconds 2 SiO 3 A solution; after 6H of reaction, the heating was stopped and diluted H with a concentration of 10% was used 2 SO 4 Neutralizing to pH=8-9, continuing stirring for 0.5h, and cooling to room temperature; washing for many times by deionized water, drying and crushing to obtain the silica coated titanium dioxide.
Example 1
(1) The formulation is shown in Table 1 below.
Table 1 example 1 formulation table
(2) The preparation method comprises the following steps:
dissolving a dispersing auxiliary agent, a wetting agent and a stabilizer in an acrylic ester monomer, stirring for 20min at a speed of 2000rad/min by using a dispersing stirrer, then adding silica coated titanium dioxide and a coupling agent, and stirring for 60min at a speed of 3000rad/min by using the dispersing stirrer to obtain mixed slurry;
then adding the mixed slurry into a sand mill to perform coarse grinding for 3 hours at a speed of 1500rad/min to obtain coarse grinding slurry; wherein, the filling quantity of the zirconium beads of the sand mill is 75 percent, and the specification of the zirconium beads is 0.25 mm-0.3 mm;
and transferring the coarse grinding slurry into a high-speed grinding machine, and finely grinding for 8 hours at a speed of 3000rad/min, and filtering to obtain the white nanometer color paste, wherein the grinding environment humidity is 50% RH, and the temperature is 20-30 ℃.
Examples 2 to 4 and comparative examples
The preparation method provided in the example 1 is adopted to prepare white nanometer color paste, and the difference is that: example 2 changing the solids content, example 3 changing the monomer type, example 4 changing the dispersion aid type, comparative example using commercially available titanium dioxide without coupling agent; the formulations are shown in Table 2.
Table 2 examples 2 to 4 and comparative examples formulation table
Test method and result characterization:
stability of testing the method comprises the following steps: aging at 70 ℃ for 7 days, and testing the particle size and viscosity of the aged color paste; if the particle size change is less than 10% and the viscosity change is less than 5%, the color paste has better stability.
Test results: as shown in Table 3, the viscosity changes of examples 1-4 are all less than 5%, and the particle size changes are all less than 10%, which indicates that the color paste has excellent stability; example 4 is significantly larger than examples 1-3, indicating that the addition of pigment synergist can improve grinding efficiency; the variation ranges of the particle size and the viscosity of the comparative example exceed standard values, and partial precipitation exists at the bottom, which shows that the color paste has poor stability.
Table 3 effect data of examples and comparative examples
Test item Example 1 Example 2 Example 3 Example 4 Comparative example
Initial viscosity/cps (25 ℃ C.) 52.3 93.1 43.4 54.6 56.7
Viscosity/cps after aging (25 ℃ C.) 53.4 94.6 45.1 56.3 62.4
Primary particle size/nm (D50) 164.3 176.5 167.4 203.6 194.5
Particle size/nm after ageing (D50) 170.2 181.4 175.7 212.1 240.6
Whether or not to settle and delaminate after aging Whether or not ### Whether or not Whether or not The bottom is provided with a sediment
Application examples
The specific formulation of the 3D printing white photosensitive resin prepared by using the white nano color paste provided in examples 1 to 4, respectively, is not limited.
In this application, the 3D printing white photosensitive resin may include, in terms of mass fraction:
mixing the above materials according to the set components, stirring uniformly by using ultrasonic waves or a stirrer, and filtering by using a 100-mesh filter screen to obtain the white photosensitive resin.
Wherein the acrylic resin comprises at least one of aliphatic polyurethane acrylic resin, aromatic polyurethane acrylic resin, epoxy acrylic resin, polyester acrylic resin, hyperbranched acrylic resin, modified acrylic resin and the like.
Wherein the reactive diluent comprises at least one of monofunctional monomers, difunctional monomers and polyfunctional monomers. The reactive diluent may specifically include at least one of acryloylmorpholine, tetrahydrofurfuryl acrylate, isobornyl acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol diacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, bisphenol a diacrylate, and the like.
The free radical photopolymerization initiator comprises at least one of N, N-dimethylamino acetophenone, 2-dimethoxy-2-phenyl acetophenone, bis (2, 4, 6-trimethyl benzoyl) -phenyl phosphine oxide, 2-ethyl anthraquinone, 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide and the like.
The ultraviolet absorber can reduce light penetration in the resin after absorbing ultraviolet light so as to improve the printing precision of the resin, and specifically can comprise at least one of UV-P, UV-1130, tinuvin 326, tinuvin 327, tinuvin 234 and the like.
The addition of the polymerization inhibitor can reduce the sensitivity of the 3D printing photosensitive resin to light, improve the printing precision of the photo-curing resin, and improve the storage stability of the resin. The polymerization inhibitor comprises 2-tertiary butyl hydroquinone, 2, 5-di-tertiary butyl hydroquinone at least one of para-hydroxyanisole, methyl hydroquinone, etc.
Performance testing was performed on the 3D printed white photosensitive resin obtained in the application example, wherein:
stability test: aging at 70 ℃ for 7 days, and testing the particle size and viscosity of the aged resin. If the particle diameter change is less than 10% and the viscosity change is less than 5%, the resin stability is good.
Compatibility test: the stability of the color paste in the photosensitive resin formulation of various different systems has good compatibility with most of raw materials, and the color paste has good compatibility when the color paste is placed for a certain time without layering and sedimentation.
Tensile property test: the printed photosensitive resin sample strip is tested for tensile strength and elongation at break by using a universal tensile testing machine.
The results are shown in Table 4 below.
Table 4 application example effect data
White nanometer color paste Example 1 Example 2 Implementation of the embodiments example 3 Example 4
Stability of No sedimentation and no delamination No sedimentation and no delamination No sedimentation and no delamination No sedimentation and no delamination
Elongation at break/% 42 51 46 44
Tensile Strength 46 42 48 45
Compatibility of Jiajia (good) Jiajia (good) Jiajia (good) Jiajia (good)
Experimental results show that the 3D printing white photosensitive resin prepared from the white nanometer color paste provided in the examples 1-4 has the advantages of good stability, high elongation at break, large tensile strength and good compatibility.
In summary, the invention provides a white nanometer color paste, a preparation method and application thereof, and has the following beneficial effects:
(1) The invention provides a silicon oxide coated nano titanium dioxide, most titanium dioxide in the market is only coated by aluminum oxide,the invention further coats the commercial titanium dioxide with silicon oxide, and the silicon oxide is firmly bonded on TiO in a hydroxyl form 2 The surface, the chemical bonding of the secondary coating forms a coating film with uniform thickness and compact structure, so that TiO 2 The chalk resistance, gloss retention and weather resistance are enhanced, and the color saturation of the white color paste is improved.
(2) The invention provides a white nanometer color paste, wherein a coupling agent is added in the grinding process to carry out organic modification on titanium white, a part of groups of the coupling agent form chemical bonding with hydroxyl groups on the surface of the titanium white, so that the affinity between the titanium white and an organic base material is enhanced, the viscosity is reduced, the grinding time is shortened, the dispersibility of the titanium white in the color paste is improved, and meanwhile, the tensile strength of photosensitive resin is improved.
(3) The invention provides a 3D printing white photosensitive resin, which comprises the white nanometer color paste for the 3D printing photosensitive resin; the photosensitive resin pigment has small particle size and good stability; no sedimentation and delamination after aging for 7 days at 70 ℃, and extremely small change of viscosity and pigment particle size; the 3D printing white photosensitive resin prepared from the white nanometer color paste has the advantages of good stability, high color saturation, high tensile strength, good compatibility and the like.
In other embodiments, reference numeral 1, the present application further provides a white nano-paste, comprising, in mass fraction:
30% -50% of acrylate monomer;
silica coated titanium dioxide 40% -65%;
5% -20% of dispersing auxiliary agent;
0.1 to 1 percent of coupling agent;
0.1% -1% of wetting agent;
0.05 to 0.5 percent of stabilizer.
2, on the basis of the mark 1, the acrylate monomer is a monofunctional acrylate monomer and/or a difunctional acrylate monomer; the monofunctional acrylate monomer comprises one or more of acyl morpholine acrylate, lauryl acrylate, 2-phenoxy-ethyl acrylate and tetrahydrofuran acrylate; the difunctional acrylate monomer comprises one or more of 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate and diethylene glycol diacrylate.
The reference number 3, on the basis of the reference number 1, is that the preparation method of the silica coated titanium pigment specifically comprises the following steps:
mixing nano titanium dioxide with water to obtain TiO 2 A slurry;
TiO is mixed with 2 Heating the slurry to 75-100 ℃, and dripping alkaline solution to adjust the pH value to 8-11;
under the condition of stirring, silicate solution is added dropwise, carrying out a reaction for a preset time period;
neutralizing with acid solution until the pH value is 8-9, continuing stirring for 20-40 min, and cooling to obtain an intermediate;
and (3) washing, drying and crushing the intermediate in sequence to obtain the silica coated titanium dioxide.
Reference numeral 4, on the basis of reference numeral 3, the water is deionized water;
the alkaline solution comprises one or more of NaOH solution and KOH solution;
silicate solution comprising Na 2 SiO 3 Solution, K 2 SiO 3 One or more of the solutions;
the acidic solution comprises H 2 SO 4 One or more of solution, HCl solution;
the mass ratio of the nano titanium dioxide to the water is (2-5): 1, a step of; the rotation speed of the stirring condition is 800 rad/min-1200 rad/min; the concentration of silicate solution is 0.1 mol/L-1 mol/L, wherein the mass of silicate is 2% -20% of the mass of the nano titanium dioxide; the preset time is 4-8 hours; the concentration of the alkaline solution is 5% -20%, and the concentration of the acidic solution is 5% -20%.
Reference numeral 5, on the basis of reference numeral 1, the dispersion aid is an acidic dispersant and/or pigment synergist for a UV system; the acidic dispersing agent for UV system comprises one or more of BYK111, BYK9151, BYK180, SOLSPERSE 36000, SOLSPERSE88000, SOLSPERSE 22000, EFKA4340, EFKA7701, dispers0685 and Dispers 680 UV.
Reference numeral 6, based on reference numeral 1, the coupling agent comprises one or more of titanate coupling agent, silane coupling agent, aluminate coupling agent, and zirconium aluminate coupling agent; the wetting agent is an acrylic polymer.
Reference numeral 7, based on reference numeral 6, the coupling agent comprises one or more of KR-12, KH560, M-1PM, PN-130, the wetting agent comprises one or more of BYK355, BYK381 and L-1980N, L-1984N, and the stabilizer comprises one or more of GENORAD 16, GENORAD 18 and GENORAD 22.
Reference numeral 8, on the basis of any one of reference numerals 1 to 7, comprises the following steps:
stirring an acrylic ester monomer, a dispersing auxiliary, a wetting agent and a stabilizer to obtain a first mixture;
adding silica coated titanium dioxide and a coupling agent into the first mixture, and stirring to obtain a second mixture;
grinding the second mixture to obtain white nanometer color paste.
Reference numeral 9, grinding the second mixture on the basis of reference numeral 8 to obtain white nano-paste, comprising:
and respectively carrying out coarse grinding and fine grinding on the second mixture to obtain white nanometer color paste.
The reference numeral 10, on the basis of the reference numeral 8, the stirring speed of stirring the acrylate monomer, the dispersing auxiliary, the wetting agent and the stabilizer is 1500 rad/min-3500 rad/min, and the stirring time is 15 min-25 min; adding silica coated titanium pigment and a coupling agent into the first mixture, and stirring at a stirring speed of 2800 rad/min-3500 rad/min for 40 min-80 min.
11, on the basis of 9, coarsely grinding by adopting a sand mill, wherein the filling quantity of zirconium beads is 65-85%, and the specification of the zirconium beads is 0.25-0.3 mm; the rotation speed of the rough grinding is 1000 rad/min-2000 rad/min, and the time is 2-4 h; the fine grinding adopts a high-speed grinding machine, the ambient humidity is 40-60% RH, the temperature is 20-30 ℃, the rotating speed is 2000-3500 rad/min, and the time is 2-10 h.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. The white nanometer color paste is characterized by comprising the following components in percentage by mass:
30% -50% of acrylate monomer;
silica coated titanium dioxide 40% -65%;
dispersing auxiliary 5 the percentage is between 20 percent and 20 percent;
coupling agent 0.11 percent to 1 percent;
0.1% -1% of wetting agent;
stabilization agent 0.05 and (3) 0.5%.
2. The white nano-paste according to claim 1, wherein the acrylate monomer is a monofunctional acrylate monomer and/or a difunctional acrylate monomer; the monofunctional acrylate monomer comprises one or more of acyl morpholine acrylate, lauryl acrylate, 2-phenoxy-ethyl acrylate and tetrahydrofuran acrylate; the difunctional acrylate monomer comprises one or more of 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate and diethylene glycol diacrylate.
3. The white nanometer color paste according to claim 1, wherein the preparation method of the silica coated titanium pigment comprises the following steps:
mixing nano titanium dioxide with water to obtain TiO 2 A slurry;
the TiO is treated with 2 Heating the slurry to 75-100 deg.c and dropping alkali solution to regulate pH value8～11；
Dropwise adding silicate solution under stirring, and carrying out reaction for a preset period of time;
neutralizing with acid solution until the pH value is 8-9, continuing stirring for 20-40 min, and cooling to obtain an intermediate;
and (3) washing, drying and crushing the intermediate in sequence to obtain the silica coated titanium dioxide.
4. The white nano-paste according to claim 3, wherein the water is deionized water;
the alkaline solution comprises one or more of NaOH solution and KOH solution;
the silicate is the solution comprises Na 2 SiO 3 Solution, K 2 SiO 3 One or more of the solutions;
the acidic solution comprises H 2 SO 4 One or more of solution, HCl solution;
the mass ratio of the nano titanium dioxide to the water is (2-5): 1, a step of; the rotating speed of the stirring condition is 800 rad/min-1200 rad/min; the concentration of the silicate solution is 0.1 mol/L-1 mol/L, wherein the mass of silicate is 2% -20% of the mass of the nano titanium dioxide; the preset time length is 4-8 hours; the concentration of the alkaline solution is 5% -20%, and the concentration of the acidic solution is 5% -20%.
5. The white nano-paste according to claim 1, wherein the dispersing aid is an acidic dispersant and/or a pigment synergist for UV system; the acid dispersant for the UV system comprises one or more of BYK111, BYK9151, BYK180, SOLSPERSE 36000, SOLSPERSE88000, SOLSPERSE 22000, EFKA4340, EFKA7701, dispers0685 and Dispers 680 UV.
6. A method for preparing the white nano-paste according to any one of claims 1 to 5, comprising the steps of:
stirring an acrylic ester monomer, a dispersing auxiliary, a wetting agent and a stabilizer to obtain a first mixture;
adding silica coated titanium dioxide and a coupling agent into the first mixture, and stirring to obtain a second mixture;
grinding the second mixture to obtain white nanometer color paste.
7. The method of claim 6, wherein grinding the second mixture to obtain white nano-paste comprises:
and respectively carrying out coarse grinding and fine grinding on the second mixture to obtain white nanometer color paste.
8. The method according to claim 6, wherein the stirring speed of stirring the acrylate monomer, the dispersing aid, the wetting agent and the stabilizer is 1500 rad/min-3500 rad/min, and the stirring time is 15 min-25 min; and adding silicon oxide coated titanium dioxide and a coupling agent into the first mixture, and stirring at the stirring speed of 2800 rad/min-3500 rad/min for 40 min-80 min.
9. The preparation method according to claim 7, wherein the coarse grinding adopts a sand mill, wherein the filling amount of zirconium beads is 65% -85%, and the specification of the zirconium beads is 0.25-0.3 mm; the rotating speed of the rough grinding is 1000 rad/min-2000 rad/min, and the time is 2-4 h; the fine grinding adopts a high-speed grinding machine, the ambient humidity is 40-60% RH, the temperature is 20-30 ℃, the rotating speed is 2000-3500 rad/min, and the time is 2-10 h.
10. A white photosensitive resin for 3D printing, comprises white nanometer color paste; the white nanometer color paste is characterized in that the white nanometer color paste is any one of claims 1 to 5.
CN202311864155.5A 2023-12-29 2023-12-29 White nanometer color paste preparation method and application thereof Pending CN117801604A (en)

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CN202311864155.5A CN117801604A (en) 2023-12-29 2023-12-29 White nanometer color paste preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311864155.5A CN117801604A (en) 2023-12-29 2023-12-29 White nanometer color paste preparation method and application thereof

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Publication Number Publication Date
CN117801604A true CN117801604A (en) 2024-04-02

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Country Link
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