CN108300292B - Acrylate-modified organic silicon resin-containing high-weather-resistance photocureable coating - Google Patents
Acrylate-modified organic silicon resin-containing high-weather-resistance photocureable coating Download PDFInfo
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- CN108300292B CN108300292B CN201810209031.6A CN201810209031A CN108300292B CN 108300292 B CN108300292 B CN 108300292B CN 201810209031 A CN201810209031 A CN 201810209031A CN 108300292 B CN108300292 B CN 108300292B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
Abstract
The invention discloses an acrylate-modified organic silicon resin-containing high-weather-resistance photocureable coating, which comprises the following components in parts by weight: 60-80 parts of acrylate modified organic silicon resin, 5-20 parts of acrylate modified polyurethane resin, 10-20 parts of acrylate monomer, 1-3 parts of photoinitiator, 0.6-2 parts of light stabilizer and 0.2-0.4 part of flatting agent. The acrylate modified organic silicon resin has the advantages of organic silicon resin and acrylic resin, and has excellent weather resistance, stain resistance, low surface energy and other properties. The photocuring coating prepared by the invention is environment-friendly, can be cured quickly, has strong adhesive force to a base material, can form a coating film with high hardness, scratch resistance and high weather resistance on the automobile lamp, can effectively protect the automobile lamp mask, and prolongs the service life of the automobile lamp mask.
Description
Technical Field
The invention belongs to the field of photocureable coating, and particularly relates to an acrylate-modified organic silicon resin-containing photocureable coating with high weather resistance.
Background
The organic silicon resin has the advantages of excellent weather resistance, heat resistance, gloss retention, acid rain resistance, stain resistance, moisture resistance, water repellency, electrical insulation, high and low temperature resistance and the like, and also has the characteristics of radiation resistance, oil resistance, solvent resistance and the like, so that the organic silicon resin is widely applied. However, silicone resins also have some disadvantages, such as: poor stability to chemicals, and poor mechanical strength, adhesion and resistance to hot water. This is because the Si — O bond in the silicone resin has a large polarity and is easily cleaved by electrophilic or nucleophilic attack. These disadvantages severely limit further applications of silicone resins.
Acrylic resins have the advantages of light color, color retention, gloss retention, weather resistance, corrosion resistance and the like, and are widely used for coating automobiles, airplanes, machinery, electronics, furniture, buildings, leather, paper, industrial plastics and daily necessities. With the development of petrochemical technology, the price of acrylic acid and its ester monomers is greatly reduced, and the development and application of acrylic resin are further promoted. The organic silicon resin is modified by the acrylate, so that the novel weather-resistant acrylate modified organic silicon resin can be obtained, the inherent advantages of the organic silicon resin are guaranteed, the characteristics of weather resistance and corrosion resistance of the acrylic resin are achieved, and the application range is expanded.
The photocuring coating has the advantages of no volatile organic compound and little environmental pollution, and meanwhile, the photocuring coating has high curing speed, good performance of cured products, energy conservation, suitability for high-speed automatic production, and is increasingly popularized and developed at a high speed. However, the formulation of the photo-curing coating contains photosensitive small molecules, which limits the use of the photo-curing coating in the occasions with high requirement on weather resistance.
Disclosure of Invention
The invention aims to provide a high-weather-resistance photocureable coating containing acrylate modified silicone resin based on the prior art.
The object of the invention can be achieved by the following measures:
the high weather resistance photocureable coating containing acrylate modified organosilicon resin comprises the following components in parts by weight:
in a preferred scheme, the high-weatherability photocureable coating containing the acrylate modified silicone resin comprises the following components in parts by weight: 60-75 parts of acrylate modified organic silicon resin, 10-20 parts of acrylate modified polyurethane resin, 11-18 parts of acrylate monomer, 1-3 parts of photoinitiator, 0.6-2 parts of light stabilizer and 0.2-0.4 part of flatting agent.
In a preferred embodiment, the acrylate-modified silicone resin is an aliphatic acrylate-modified silicone resin. The acrylate modified organic silicon resin in the scheme can increase the weather resistance, stain resistance and hardness of the coating film under the coordination of other components. Specific aliphatic acrylate-modified silicone resins are, for example: jetta UA890, Cycote EB350, Saduoma CN990, etc.
In a preferred embodiment, the acrylate-modified polyurethane resin is an aliphatic urethane acrylate. The acrylic ester modified polyurethane resin in the scheme can increase the crosslinking density and molecular weight of the coating film under the coordination of other components, and improve the water resistance and acid and alkali resistance of the coating film. Specific acrylate-modified polyurethane resins are such as: yangxing 6145-100, Shadoma CN9010, Shadoma CN9001 and the like.
In a preferred embodiment, the acrylate monomer is one or a combination of HDDA (1,6 hexanediol diacrylate), PETA (pentaerythritol triacrylate), TMPTA (trimethylolpropane triacrylate), DPHA (dipentaerythritol hexaacrylate), and Di-TMPTA (ditrimethylolpropane hexaacrylate). The acrylate monomer in the scheme can reduce the viscosity of the coating under the coordination of other components, increase the photopolymerization reaction speed and the crosslinking density of the coating, and improve the high-temperature resistance and the cold resistance of the coating.
In a preferable scheme, the photoinitiator is one or a combination of more of benzil, aroylphosphine oxide, benzophenone, alkylbenzene ketone and benzoyl formate. It produces free radical under the irradiation of ultraviolet light to make resin and monomer crosslink and polymerize.
In a preferable scheme, the light stabilizer is one or a combination of more of amino-containing hindered amine light stabilizer, ether-containing hindered amine light stabilizer, triazole ultraviolet light absorber and benzophenone ultraviolet light absorber. The light stabilizer absorbs ultraviolet light in sunlight under natural conditions, quenches free radicals generated in a coating film in time and assists in increasing the weather resistance of the coating film.
In a preferred embodiment, the leveling agent is an organosilicon leveling agent.
The preparation method of the acrylate modified silicone resin-containing high-weather-resistance photocureable coating comprises the following steps:
(1) adding acrylic monomer and acrylic ester modified polyurethane resin into a reaction kettle, stirring, and carrying out frequency: 600 + 800r/min, temperature: 30-45 ℃;
(2) adjusting the stirring frequency to 200-;
(3) adjusting the stirring frequency to 200-300r/min, adding the photoinitiator, the light stabilizer and the flatting agent into the reaction kettle, and adjusting the stirring frequency to 600-800r/min for stirring to obtain the high-performance silicon-based organic silicon-based.
The invention provides a preparation method of a more specific acrylate-modified silicone resin-containing high-weather-resistance photocureable coating, which comprises the following steps:
(1) adding 10-20 parts of acrylic monomer and 5-20 parts of acrylate modified polyurethane resin into a reaction kettle, starting stirring for 10 minutes, and frequency: 600 + 800r/min, temperature: 30-45 ℃;
(2) adjusting the stirring frequency to 200-;
(3) adjusting the stirring frequency to 200-300r/min, adding 1-3 parts of photoinitiator, 0.6-2 parts of light stabilizer and 0.2-0.4 part of flatting agent into the reaction kettle, adjusting the stirring frequency to 800-min, and stirring for 20 minutes. Then stopping stirring, discharging and checking.
The invention has the beneficial effects that:
(1) the acrylate modified organic silicon resin has the advantages of organic silicon resin and acrylic resin, and has excellent weather resistance, stain resistance, low surface energy and other properties. The resin is compatible with other components of a photocuring system to obtain the photocuring coating which is environment-friendly, strong in binding power, wear-resistant and good in weather resistance.
(2) The photocureable coating prepared by the invention is environment-friendly and can be cured quickly; the high-weather-resistance photocureable coating has the advantages of strong adhesion to a substrate, high surface hardness, wear resistance and good weather resistance, can form a tough paint film on the surface of the substrate, can effectively protect the substrate, is suitable for the field of substrates with high weather resistance requirements such as automobile lamps and the like, can effectively protect the automobile lamp mask, and prolongs the service life of the automobile lamp mask.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The preparation method of the coating of each example comprises the following steps:
(1) adding acrylic monomer and acrylate modified polyurethane resin into a reaction kettle, starting stirring for 10 minutes, wherein the frequency is as follows: 600 + 800r/min, temperature: 30-45 ℃.
(2) Adjusting the stirring frequency to 200-300r/min, adding the acrylate modified organic silicon resin into the reaction kettle, adjusting the stirring frequency to 1000-1200r/min, and stirring for 30 minutes.
(3) Adjusting the stirring frequency to 200-300r/min, adding a photoinitiator, a light stabilizer and a flatting agent into the reaction kettle, adjusting the stirring frequency to 600-800r/min, and stirring for 20 minutes. Then stopping stirring to obtain the coating.
Example 1
The acrylate-modified silicone resin-containing high-weather-resistance photocureable coating comprises the following components in parts by weight:
| raw materials | Ratio/by weight | Numbering |
| Aliphatic acrylate modified silicone resin | 65 | UA890 |
| Aliphatic polyurethane acrylic resin | 15 | Changxing 6145-100- |
| Aliphatic acrylate monomer | 17 | PETA |
| Photoinitiator | 1.8 | 184 |
| Light stabilizers | 0.9 | Crainen Hostavin PR-31 |
| Leveling agent | 0.3 | BYK306 |
Example 2
The acrylate-modified silicone resin-containing high-weather-resistance photocureable coating comprises the following components in parts by weight:
| raw materials | Ratio/by weight | Numbering |
| Aliphatic acrylate modified silicone resin | 65 | EB350 |
| Aliphatic polyurethane acrylic resin | 17 | Saedoma CN9010 |
| Aliphatic acrylate monomer | 15 | TMPTA |
| Photoinitiator | 1.1 | 184 |
| Photoinitiator | 0.7 | TPO |
| Light stabilizers | 1.0 | Clainn: hostavin PR-31 |
| Leveling agent | 0.2 | BYK306 |
Example 3
The acrylate-modified silicone resin-containing high-weather-resistance photocureable coating comprises the following components in parts by weight:
example 4
The acrylate-modified silicone resin-containing high-weather-resistance photocureable coating comprises the following components in parts by weight:
example 5
The acrylate-modified silicone resin-containing high-weather-resistance photocureable coating comprises the following components in parts by weight:
example 6 (comparative example)
The acrylate-modified silicone resin-containing high-weather-resistance photocureable coating comprises the following components in parts by weight:
| raw materials | Ratio/by weight | Numbering |
| Aliphatic polyurethane acrylic resin | 85 | Saedoma CN9013 |
| Aliphatic acrylate monomer | 12 | TMPTA |
| Photoinitiator | 1.0 | 184 |
| Photoinitiator | 0.7 | TPO |
| Light stabilizers | 0.7 | Clainn: hostavin 3206 |
| Light stabilizers | 0.3 | Clainn: hostavin PR-31 |
| Leveling agent | 0.3 | BYK306 |
Example 7 (comparative example)
The acrylate-modified silicone resin-containing high-weather-resistance photocureable coating comprises the following components in parts by weight:
| raw materials | Ratio/by weight | Numbering |
| Aliphatic acrylate modified silicone resin | 30 | UA890 |
| Aliphatic polyurethane acrylic resin | 55 | Saedoma CN9013 |
| Aliphatic acrylate monomer | 12 | TMPTA |
| Photoinitiator | 1.0 | 184 |
| Photoinitiator | 0.7 | TPO |
| Light stabilizers | 0.7 | Clainn: hostavin 3206 |
| Light stabilizers | 0.3 | Clainn: hostavin PR-31 |
| Leveling agent | 0.3 | BYK306 |
The test method of the above examples is as follows:
hundred lattice (adhesion): grade 5 (i.e., 100% non-shedding).
Pencil hardness: the coating was not scratched with 1 kilogram force, 2H, on PC substrate.
Acid and alkali resistance test: soaking with 0.1M NaOH at 55 deg.C for 24 hr; at 20 ℃ with H at a concentration of 0.05M2SO4After the coating is soaked for 24 hours, the coating has no crack and no color change, and the requirement of the hundred lattice is 5 grades.
And (3) high temperature resistance test: and (3) continuously baking for 240 hours at 100 ℃, wherein the coating has no crack and no color change, and the requirement of the hundred lattice is 5 grade.
Water resistance test: and when the coating is soaked in water at 40 ℃ for 240 hours, the coating has no crack and no color change, and the requirement of the hundred lattice is 5 grade.
Cold resistance test: the coating is placed for 24 hours at the temperature of minus 40 ℃, the appearance of the coating does not crack or change color, and the requirement of the hundred lattice is 5 grade.
Weather resistance: and after an artificial aging test is carried out for more than 3000 hours, the appearance of the coating has no undesirable phenomena such as cracking, crazing, layering and the like, and the yellowing is less than 3.0.
The results of the performance testing of the above examples are shown in the following table:
as can be seen from the above table, the high weather resistance photocureable coating prepared by the invention does not contain volatile organic compounds and is environment-friendly. Its advantages are high adhesion and high antiwear and weatherability.
The above is a description of specific embodiments of the invention, but the invention is not limited to the specific embodiments described above, and those skilled in the art can make various modifications within the scope of the claims without affecting the essence of the invention.
Claims (8)
1. The high-weather-resistance photocureable coating containing the acrylate modified organic silicon resin is characterized in that the composition consists of the following components in parts by weight:
60-80 parts of acrylate modified organic silicon resin,
5-20 parts of acrylate modified polyurethane resin,
10-20 parts of acrylic ester monomer,
1-3 parts of a photoinitiator,
0.6 to 2 portions of light stabilizer,
0.2-0.4 part of leveling agent;
the organic silicon resin modified by the acrylic ester is organic silicon resin modified by aliphatic acrylic ester;
the acrylate-modified silicone resin is selected from Jew's Da UA890, Cyanote EB350 or Sadoma CN 990.
2. The highly weather-resistant photocurable coating material containing acrylate-modified silicone resin according to claim 1, characterized in that the acrylate-modified urethane resin is aliphatic urethane acrylate.
3. The high weather resistant photo-curable coating containing acrylate-modified silicone resin as claimed in claim 2, wherein the acrylate-modified polyurethane resin is selected from the group consisting of Changxing 6145-100, Sadoma CN9010 and Sadoma CN 9001.
4. The acrylate-modified silicone resin high-weatherability photocurable coating according to claim 1, characterized in that the acrylate monomer is one or a combination of HDDA, PETA, TMPTA, DPHA, Di-TMPTA.
5. The photo-curable coating with high weather resistance containing acrylate modified silicone resin of claim 1, wherein the photo-initiator is one or a combination of more of benzoyl, aroylphosphine oxide, benzophenone, alkylbenzene ketone and benzoyl formate.
6. The high-weatherability photocuring coating containing acrylate-modified silicone resin according to claim 1, wherein the light stabilizer is one or a combination of more of an amino-containing hindered amine light stabilizer, an ether-containing hindered amine light stabilizer, a triazole ultraviolet light absorber and a benzophenone ultraviolet light absorber.
7. The photo-curing coating with high weather resistance containing acrylate modified silicone resin of claim 1, wherein the leveling agent is a silicone leveling agent.
8. The photo-curable coating with high weather resistance containing acrylate modified silicone resin of claim 1, wherein the preparation method of the coating comprises:
(1) adding acrylic monomer and acrylic ester modified polyurethane resin into a reaction kettle, stirring, and carrying out frequency: 600 + 800r/min, temperature: 30-45 ℃;
(2) adjusting the stirring frequency to 200-;
(3) adjusting the stirring frequency to 200-300r/min, adding the photoinitiator, the light stabilizer and the flatting agent into the reaction kettle, and adjusting the stirring frequency to 600-800r/min for stirring to obtain the high-performance silicon-based organic silicon-based.
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| CN110922886A (en) * | 2019-11-15 | 2020-03-27 | 上海翰飞新材料科技有限公司 | Steel wool-resistant and fingerprint-resistant UV coating and preparation method thereof |
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