CN112175465A - Water-based paint and forming method thereof - Google Patents
Water-based paint and forming method thereof Download PDFInfo
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- CN112175465A CN112175465A CN202011067478.8A CN202011067478A CN112175465A CN 112175465 A CN112175465 A CN 112175465A CN 202011067478 A CN202011067478 A CN 202011067478A CN 112175465 A CN112175465 A CN 112175465A
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- water
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- aqueous coating
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a water-based paint and a forming method thereof. The water-based paint comprises: aqueous resins and hydrophilically modified polyorganosiloxanes. The hydrophilic modified polysiloxane takes polysiloxane as a starting point, and is applied to the water-based paint as an antifogging modifier after being subjected to hydrosilylation graft modification, so that the water-based paint with a lasting and efficient antifogging effect is obtained. The characteristics of low surface tension, hydrophobicity and the like of the polyorganosiloxane are fully utilized, and the grafted modified group is combined, so that the water-based paint has lasting and excellent antifogging performance.
Description
Technical Field
The invention belongs to the field of water-based paint, and particularly relates to water-based paint and a forming method thereof.
Background
Aqueous coatings are commonly used on the surface of various substrates, and depending on the environment in which the aqueous coating is used, the aqueous coating can impart various excellent surface properties, one of which is antifogging properties, to the substrate coated with the aqueous coating.
In everyday life, fog is common on various transparent substrate surfaces, e.g., glass window surfaces. Due to consumption of the transparent base materials and/or accumulation of impurities in the using process, the contact angle of the surface of the transparent base materials to water drops is gradually increased to be more than 50 degrees, so that water vapor is easily condensed into small water drops on the surface of the transparent base materials, the transmission of light is affected, the transparent base materials become fuzzy and opaque, and further adverse effects are brought. Particularly, the fog on the surface of transparent base materials such as vehicle window glass, lenses and the like is easy to generate great potential safety hazard.
In the existing water-based paint, the used antifogging modification agent improves the antifogging effect of the water-based paint to a certain extent, but still has the defects of insufficient antifogging and waterproof effects and insufficient mechanical strength, so that the antifogging effect is not durable. For this reason, the present inventors have desired to obtain an aqueous coating material having a long-lasting antifogging effect by hydrophilically modifying a polyorganosiloxane having advantages of low surface tension, water repellency, etc., and applying the modified polyorganosiloxane to the aqueous coating material.
Disclosure of Invention
In order to solve the defects of the existing water-based paint in the aspect of antifogging performance, the invention takes the polysiloxane as the starting point, and the polysiloxane is used as an antifogging modifier after being subjected to silicon-hydrogen grafting modification, so that the water-based paint with lasting and efficient antifogging effect is obtained. In the invention, the characteristics of low surface tension, hydrophobicity and the like of the polyorganosiloxane are fully utilized, and the grafted modified group is combined, so that the modified polyorganosiloxane has excellent antifogging performance.
The water-based paint of the invention comprises: the hydrophilic modified polyorganosiloxane is characterized by having a structure shown in a formula (1) and being obtained by a hydrosilylation reaction between the polyorganosiloxane shown in the formula (2) and a surface active modifier shown in the formula (3) under the action of a catalyst.
Wherein, in formulas (1) - (3), each R is independently selected from C1-C3 alkyl; r1Is alkylene selected from C1-C3; r2Is alkylene selected from C5-C20; x is selected from one of sulfonate, sulfate, benzene sulfonate or phosphate;
p is an integer of 1-5, q is an integer of 20-50, and m is an integer of 10-30.
Wherein the mass ratio of the water-based resin to the hydrophilic modified polysiloxane is 100: (5-30).
Wherein the catalyst used in the hydrosilylation reaction is chloroplatinic acid, and the dosage of the chloroplatinic acid is 0.1 to 3 weight percent of the total mass of the two reaction raw materials.
Further, the sulfonate is selected from one of sodium sulfonate, potassium sulfonate or ammonium sulfonate; the sulfate is selected from one of sodium sulfate, potassium sulfate or ammonium sulfate; the benzene sulfonate is selected from one of sodium benzene sulfonate, potassium benzene sulfonate or ammonium benzene sulfonate; the phosphate is selected from potassium phosphate and sodium phosphate.
Further, in order to ensure the completion of the hydrosilylation reaction, the two reaction raw materials are arranged so that the molar ratio of the polyorganosiloxane represented by the formula (2) and the surface active modifier represented by the formula (3) participating in the hydrosilylation reaction is 1 to 1.2.
Further, the temperature of the hydrosilylation reaction is 80-120 ℃, and the reaction time is 3-8 h.
Further, in the formula (1), a plurality of R1May be independently selected from C1-C3 alkylene, and/or multiple R2Can be independently selected from C5-C20 alkylene, and/or a plurality of X can be independently selected from one of sulfonate, sulfate, benzene sulfonate or phosphate, and/or a plurality of m can be independently selected from an integer of 10-30. That is, a hydrophilic modified organosiloxane may be prepared by a hydrosilylation reaction of a polyorganosiloxane represented by formula (2) with a plurality of surface active modifiers satisfying the structure represented by formula (3) and having different molecular formulae. In addition, canThe hydrophilically modified organosiloxane is prepared by a hydrosilylation reaction using a plurality of polyorganosiloxanes satisfying the structure represented by formula (2) and having different molecular formulae and a plurality of surface-active modifiers satisfying the structure represented by formula (3) and having different molecular formulae.
A coating method of a water-based paint comprises the steps of coating the water-based paint on the surface of a substrate, and then carrying out drying and curing treatment. The base material is glass, plastic, ceramic, metal, wood, etc. The drying temperature is 100-150 ℃, and the drying time is 10-60 min.
The water-based paint of the present invention is added with a hydrophilically modified organosiloxane. The hydrophilic modified organic siloxane similar to long-foot centipede is obtained by grafting a surface active modifier on two sides of a main chain of the organic siloxane respectively. The trunk part is a main chain of polyorganosiloxane, has the performances of low surface tension, hydrophobicity and the like, and can ensure the antifogging, waterproof and anti-adhesion properties of the water-based paint. Each "hindfoot" of the hindfoot portion has two branches, one straight chain alkyl group terminating in an amine group and one straight chain polyether group terminating in an anionic surfactant group. The two branched chains have good hydrophilicity, good compatibility with water-based resin, good wettability and good adhesion, and can improve the hardness and the lasting antifogging property of the water-based paint.
Moreover, the arrangement of the two branched chains and the arrangement of the amine group and the anionic surfactant group at the end can further enhance the wettability and the dispersion uniformity of the polyorganosiloxane and the water-based coating resin, improve the hardness and the hydrophilic contact angle of a coating film layer and ensure that the water-based coating obtains durable and efficient antifogging performance.
Detailed Description
The hydrophilic modified polysiloxane is added into the water-based paint, so that the characteristics of low surface tension, hydrophobicity and the like of the polysiloxane are fully utilized, and the characteristics of hydrophilicity, wettability, adhesiveness and the like of the grafted surface active modified group are combined, so that the water-based paint can obtain lasting and efficient antifogging performance. In order to better illustrate and compare the technical solution of the present invention in detail, the following description is given with specific examples.
Example 1
An aqueous coating comprising: 100 parts by mass of a water-based acrylic resin and 20 parts by mass of a hydrophilic-modified polyorganosiloxane.
The hydrophilic modified polysiloxane has a structure shown in a formula (1), and is obtained by performing hydrosilylation reaction on polysiloxane shown in a formula (2) and a surface active modifier shown in a formula (3) under the action of a catalyst.
Wherein, in formulae (1) to (3), each R is methyl; r1Are all methylene groups; r2Alkylene groups each having C10; x is sodium sulfonate; p is 3, q is 50 and m is 15.
The catalyst used in the hydrosilylation reaction is chloroplatinic acid, and the dosage of the chloroplatinic acid is 1wt% of the total mass of the two reaction raw materials.
The amount ratio of the polyorganosiloxane represented by the formula (2) participating in the hydrosilylation reaction to the surface active modifier represented by the formula (3) was such that the molar ratio of C = C bond and Si — H bond in the raw materials was 1.1.
The temperature of the hydrosilylation reaction is 100 ℃, and the reaction time is 5 hours.
Example 2
An aqueous coating comprising: 100 parts by mass of aqueous polyurethane and 30 parts by mass of hydrophilic modified polyorganosiloxane.
The hydrophilic modified polysiloxane has a structure shown in a formula (1), and is obtained by performing hydrosilylation reaction on polysiloxane shown in a formula (2) and a surface active modifier shown in a formula (3) under the action of a catalyst.
Wherein, in formulae (1) to (3), each R is ethyl; r1Are all ethylene groups; r2Alkylene groups each having C15; x is sodium benzene sulfonate; p is 1, q is 30 and m is 18.
The catalyst used in the hydrosilylation reaction is chloroplatinic acid, and the dosage of the chloroplatinic acid is 1.5wt% of the total mass of the two reaction raw materials.
The amount ratio of the polyorganosiloxane represented by the formula (2) participating in the hydrosilylation reaction to the surface active modifier represented by the formula (3) was such that the molar ratio of C = C bond and Si — H bond in the raw materials was 1.05.
The temperature of the hydrosilylation reaction is 80 ℃, and the reaction time is 8 hours.
Example 3
An aqueous coating comprising: 100 parts by mass of a water-based epoxy resin and 10 parts by mass of a hydrophilic-modified polyorganosiloxane.
The hydrophilic modified polysiloxane has a structure shown in a formula (1), and is obtained by performing hydrosilylation reaction on polysiloxane shown in a formula (2) and a surface active modifier shown in a formula (3) under the action of a catalyst.
Wherein, in formulae (1) to (3), each R is methyl; r1Are all ethylene groups; r2Alkylene groups each having C5; x is sodium sulfonate; p is 5, q is 20 and m is 10.
The catalyst used in the hydrosilylation reaction is chloroplatinic acid, and the dosage of the chloroplatinic acid is 3wt% of the total mass of the two reaction raw materials.
The amount ratio of the polyorganosiloxane represented by the formula (2) participating in the hydrosilylation reaction to the surface active modifier represented by the formula (3) is such that the two reaction raw materials are arranged so that the molar ratio of the C = C bond and the Si — H bond in the raw materials is 1.
The temperature of the hydrosilylation reaction is 120 ℃, and the reaction time is 4 hours.
Example 4
The three aqueous coating materials of examples 1 to 3 were coated on a glass substrate, dried at 120 ℃ and cured to obtain corresponding coating films, and then pencil hardness and contact angle tests were performed.
In addition, for comparison, an aqueous acrylic resin coating to which no hydrophilically modified polyorganosiloxane was added was set as comparative example 1, and an aqueous acrylic resin coating to which only the polyorganosiloxane represented by formula (2) used in example 1 was added was set as comparative example 2.
Among the tests of pencil hardness, the pencil hardness test was carried out on the coating film using A QHQ-A type pencil hardness tester with reference to GB/T6739-. In the contact angle test, the contact angle of a water droplet on the surface of a coating film after being left standing for 1 minute and the contact angle of the water of the coating film after being scraped 3000 times by a wiper blade of an automobile were measured using a contact angle meter. All test results are shown in the table below.
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Hardness of pencil | 3H | 3H | 3H | 4H | HB |
| Contact angle (°) | 23.4 | 23.5 | 24.2 | 77.7 | 36.0 |
| Contact Angle after scraping (°) | 26.0 | 26.6 | 26.8 | 82.2 | 59.2 |
As can be seen from the above table, the coating films obtained by coating the aqueous coating materials of examples 1-3 have better performances in pencil hardness, contact angle and contact angle after scratching in use than the coating films obtained by coating the aqueous coating materials of comparative examples 1-2.
In comparative example 1, although the addition of polyorganosiloxane to the aqueous coating material has a significant effect of improving the hardness of the coating film, the antifogging effect thereof is significantly insufficient.
Claims (8)
1. An aqueous coating comprising: the hydrophilic modified polyorganosiloxane is characterized by having a structure shown in a formula (1) and being obtained by a hydrosilylation reaction between the polyorganosiloxane shown in the formula (2) and a surface active modifier shown in the formula (3) under the action of a catalyst.
Wherein, in formulas (1) - (3), each R is independently selected from C1-C3 alkyl; r1Is alkylene selected from C1-C3; r2Is alkylene selected from C5-C20; x is selected from one of sulfonate, sulfate, benzene sulfonate or phosphate;
p is an integer of 1-5, q is an integer of 20-50, and m is an integer of 10-30.
2. The aqueous coating of claim 1, wherein: the mass ratio of the water-based resin to the hydrophilic modified polysiloxane is 100: (5-30).
3. The aqueous coating of claim 1, wherein: the catalyst used in the hydrosilylation reaction is chloroplatinic acid, and the dosage of the chloroplatinic acid is 0.1 to 3 weight percent of the total mass of the two reaction raw materials.
4. The aqueous coating of claim 1, wherein: the sulfonate is selected from one of sodium sulfonate, potassium sulfonate or ammonium sulfonate; the sulfate is selected from one of sodium sulfate, potassium sulfate or ammonium sulfate; the benzene sulfonate is selected from one of sodium benzene sulfonate, potassium benzene sulfonate or ammonium benzene sulfonate; the phosphate is selected from potassium phosphate and sodium phosphate.
5. The aqueous coating of claim 1, wherein: the amount ratio of the polyorganosiloxane represented by the formula (2) participating in the hydrosilylation reaction to the surface active modifier represented by the formula (3) is such that the molar ratio of the C = C bond to the Si-H bond in the raw materials is 1 to 1.2.
6. The aqueous coating of claim 1, wherein: the temperature of the hydrosilylation reaction is 80-120 ℃, and the reaction time is 3-8 h.
7. The aqueous coating of claim 1, wherein: in the formula (1), a plurality of R1May be independently selected from C1-C3 alkylene, and/or multiple R2Can be independently selected from C5-C20 alkylene, and/or a plurality of X can be independently selected from one of sulfonate, sulfate, benzene sulfonate or phosphate, and/or a plurality of m can be independently selected from an integer of 10-30.
8. A method for forming a water-based paint, which comprises the steps of coating the water-based paint as claimed in any one of claims 1 to 7 on the surface of a substrate, and then carrying out drying and curing treatment; wherein the substrate is glass, plastic or ceramic; the drying temperature is 100-150 ℃, and the drying time is 10-60 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011067478.8A CN112175465A (en) | 2020-10-06 | 2020-10-06 | Water-based paint and forming method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011067478.8A CN112175465A (en) | 2020-10-06 | 2020-10-06 | Water-based paint and forming method thereof |
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| CN112175465A true CN112175465A (en) | 2021-01-05 |
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| CN202011067478.8A Pending CN112175465A (en) | 2020-10-06 | 2020-10-06 | Water-based paint and forming method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0665379A (en) * | 1992-08-14 | 1994-03-08 | Nippon Unicar Co Ltd | Organic-surfactant-modified organopolysiloxane |
| JPH09194492A (en) * | 1996-01-19 | 1997-07-29 | Sanyo Chem Ind Ltd | Antifogging agent |
| JPH11147949A (en) * | 1997-11-17 | 1999-06-02 | Asahi Denka Kogyo Kk | Modifier for compound having silica-h bond in molecule, fluorine-modified silicone, and surfactant |
| CN108976424A (en) * | 2018-07-24 | 2018-12-11 | 广州大学 | A kind of low-surface-energy scopiform silicone molecules and its preparation and application in the coating |
| CN109971327A (en) * | 2017-12-28 | 2019-07-05 | 财团法人工业技术研究院 | The formed method of water paint |
-
2020
- 2020-10-06 CN CN202011067478.8A patent/CN112175465A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0665379A (en) * | 1992-08-14 | 1994-03-08 | Nippon Unicar Co Ltd | Organic-surfactant-modified organopolysiloxane |
| JPH09194492A (en) * | 1996-01-19 | 1997-07-29 | Sanyo Chem Ind Ltd | Antifogging agent |
| JPH11147949A (en) * | 1997-11-17 | 1999-06-02 | Asahi Denka Kogyo Kk | Modifier for compound having silica-h bond in molecule, fluorine-modified silicone, and surfactant |
| CN109971327A (en) * | 2017-12-28 | 2019-07-05 | 财团法人工业技术研究院 | The formed method of water paint |
| CN108976424A (en) * | 2018-07-24 | 2018-12-11 | 广州大学 | A kind of low-surface-energy scopiform silicone molecules and its preparation and application in the coating |
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