CN107057547B - Acrylic acid-polyurethane type finishing varnish composition, preparation method and application thereof - Google Patents
Acrylic acid-polyurethane type finishing varnish composition, preparation method and application thereof Download PDFInfo
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- CN107057547B CN107057547B CN201710337408.1A CN201710337408A CN107057547B CN 107057547 B CN107057547 B CN 107057547B CN 201710337408 A CN201710337408 A CN 201710337408A CN 107057547 B CN107057547 B CN 107057547B
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- 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
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Abstract
The invention discloses an acrylic acid-polyurethane type finishing varnish composition, which comprises the following components in parts by weight: the component A comprises the following components in parts by weight: 20-40 parts of high-solid thermosetting hydroxy acrylic resin, 5-15 parts of polyester resin, 10-20 parts of cross-linking agent, 10-30 parts of diurea compound modified acrylic resin, 1.61-5.7 parts of varnish auxiliary agent and 5-30 parts of first diluent; the component B comprises the following components in parts by weight: 50-80 parts of isocyanate resin and 20-50 parts of second diluent; the mass ratio of the component A to the component B is 100 (28-32). The acrylic acid-polyurethane type finishing varnish composition prepared by the invention has high construction solid content, high construction sagging limit and high scratch resistance, is particularly suitable for automobile external coating, and is also suitable for external coating of automobile hubs, motorcycles, engineering machinery, light industrial products and the like.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to an acrylic acid-polyurethane type finishing varnish composition for an automobile, a preparation method and application thereof.
Background
Since 2009, china automobile production and sales volume has continuously remained world first. Environmental issues arising from the manufacturing and use of automobiles are becoming a focus of increasing social attention. According to research, the emission of VOCs in the automobile industry is an important factor in the formation process of composite air pollution, and the emission of Volatile Organic Compounds (VOCs) of the coating becomes the central importance of national air pollution control. In 2015, 4% of consumption tax is imposed on the coating with the content of Volatile Organic Compounds (VOCs) being more than 420g/L in the construction state from 2 months and 1 days issued by the Ministry of finance and national tax administration. In addition, countries are formally charged for VOCs emissions from 10/1/2015.
In view of the above, there is a strong need in the art to develop an environmentally friendly automotive topcoat varnish having excellent appearance properties, which is required to meet the requirements of having Volatile Organic Compounds (VOCs) of less than 420g/L in the applied state, a high sag limit, and high scratch resistance.
Disclosure of Invention
It is an object of the present invention to provide an acrylic-polyurethane type overprint varnish composition which in the as-applied state has a Volatile Organic Content (VOCs) of less than 420g/L and which meets the requirements of high scratch resistance and high sag limit.
It is another object of the present invention to provide a method for preparing the acrylic-polyurethane type overprint varnish composition.
It is a further object of the present invention to provide a use of said acrylic-polyurethane type overprint varnish composition.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
one aspect of the present invention provides an acrylic-polyurethane type overprint varnish composition, comprising the following components in parts by weight:
the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
50-80 parts of isocyanate resin,
20-50 parts of a second diluent;
the mass ratio of the component A to the component B is 100 (28-32).
The number average molecular weight of the thermosetting hydroxyl acrylic resin with high solid content is 3000-5000, the hydroxyl value is 120-200 mgKOH/g, the hydroxyl value is preferably 150-180mgKOH/g, the acid value of the solid resin is 7.0-11.0mgKOH/g, and the high solid content means that the solid content is more than or equal to 75 weight percent.
The polyester resin is a higher branched polyester resin with lower viscosity, and specifically is at least one of Nepets SETAL1606 BA-80, Digao Yingchuang SILIKOTE 900 and BB 600.
The cross-linking agent can provide additional auxiliary cross-linking effect to make the coating film have firmer rigid chain structure, specifically butyl etherified amino resin, and is selected from at least one of Nepetes amino resin SETAMINE US-146 BB-72, SETAMINE US-138 BB-70, and Nepetes LUWIPAL 018.
The diurea compound in the diurea compound modified acrylic resin refers to a compound obtained by reacting aliphatic diisocyanate with amine, the diurea compound modification amount of the diurea compound modified acrylic resin is 3.2-4.2%, and specifically is at least one of Nepetes SETALUX 91757 VX-60, SETALUX 91760 SS-53, SETALUX 91767 VX-60, SETALUX 91780 VS-60 and SETALUX 91796 SS-69.
The varnish auxiliary agent comprises the following components in parts by weight:
the ultraviolet light absorber is benzotriazole ultraviolet light absorber, and specifically is at least one of Benzotriazole 928, Tinuvin384-2, Tinuvin400 and Tinuvin 477.
The light stabilizer is a hindered amine light stabilizer, and specifically is at least one of a Pasteur Tinuvin292 light stabilizer and a Tinuvin123 light stabilizer.
The organic silicon leveling agent is a polyester modified polydimethylsiloxane leveling agent, and can achieve the best balance effects of reducing surface tension, improving smoothness and other performances by matching with other components, and specifically at least one of ByK-331, BYK-315, BYK-306, BYK-310, DigaTego-450 and Bayer BAYSILONE OL-17.
The acrylic ester flatting agent is a non-reactive acrylic ester flatting agent, and the acrylic ester flatting agent and the organic silicon flatting agent act synergistically to achieve the best appearance, and specifically at least one of ByK-358N, TegoFlow-300 Digao and Modaflow-2100 cyanogen.
The first diluent is at least one of butyl acetate, ethyl acetate, ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, mixed dibasic acid dibasic ester (DBE) and ethyl 3-ethoxypropionate (EEP).
The isocyanate resin is hexamethylene diisocyanate trimer, specifically at least one of Bayer Desmodur 3300, Baskat HI-100, and TOLONATE HI 290B.
The second diluent is at least one of butyl acetate, ethyl acetate, ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, mixed dibasic acid dibasic ester (DBE) and ethyl 3-ethoxypropionate (EEP).
Another aspect of the present invention provides a method for preparing the acrylic-polyurethane type overprint varnish composition, comprising the steps of:
preparation of component A:
under the protection of nitrogen, adding 20-40 parts of thermosetting hydroxyl acrylic resin with high solid content, 5-15 parts of polyester resin, 10-20 parts of cross-linking agent, 10-30 parts of diurea compound modified acrylic resin, 1.61-5.7 parts of varnish auxiliary agent and 5-30 parts of first diluent, and stirring to obtain the component A;
preparation of component B:
under the protection of nitrogen, adding 50-80 parts of isocyanate resin and 20-50 parts of second diluent, and stirring to obtain the component B;
and (2) mixing the component A and the component B according to the mass ratio of 100 (28-32) to obtain the acrylic-polyurethane type finishing varnish composition.
In a further aspect of the invention, there is provided the use of said acrylic-polyurethane type overprint varnish composition for the preparation of coatings.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the acrylic acid-polyurethane type finishing varnish composition has high construction solid content (organic solvent volatile is less than 420g/L), high construction sagging limit (more than 55 mu m), high scratch resistance, is particularly suitable for automobile external coating, and is also suitable for external coating of automobile hubs, motorcycles, engineering machinery, light industrial products and the like.
The acrylic acid-polyurethane type finishing varnish composition can be applied to automobile external coating, and the coating obtained by coating has good fullness, high distinctness of image and good scratch resistance, is particularly suitable for automobile external coating, and is also suitable for external coating of automobile hubs, motorcycles, engineering machinery, light industrial products and the like.
Drawings
FIG. 1 is a schematic view of the evaluation method of sagging of a coating film of an acrylic-urethane type over-coating varnish composition of the present invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
In the case where the objects of the present invention are illustrated and explained by the following examples, the components of the composition are all explained on the general standard of parts by weight. In the present invention, the term "part" is used in the same sense as part by weight for the sake of brevity without specific mention.
Various aspects of the present invention will be described in detail below, and various starting materials of the present invention are commercially available unless otherwise specified; or prepared according to conventional methods in the art. Unless defined or indicated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
The experimental procedures, in which specific conditions are not specified, in the following examples are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers. Unless otherwise indicated, all parts are parts by weight, all percentages are percentages by weight, and the molecular weight of the polymer is the number average molecular weight.
The "acrylic-urethane type" in the present application means that the present invention comprises an acrylic type resin and an isocyanate resin component.
In the present application, the high-solid thermosetting hydroxy acrylic resin can be the high-solid thermosetting hydroxy acrylic resin described in acrylic chemical and application, 4 th 12 th 2001. The solid content refers to the solid content of the thermosetting hydroxyacrylic resin.
Example 1
The component A comprises:
a thermosetting hydroxy acrylic resin having a number average molecular weight of 4000, a hydroxyl value of 140mgKOH/g, and an acid value of 8.0mgKOH/g, wherein the high solid content means a solid content of 75% by weight or more (75% by weight or more),
the component B comprises:
330070 parts of isocyanate resin Desmodur;
30 parts of diluent butyl acetate;
the preparation method of the component A comprises the following steps:
under the protection of nitrogen, 20 parts of high-solid thermosetting hydroxy acrylic resin, 5 parts of polyester resin SETAL1606 BA-80, 10 parts of butylated amino resin SETAMINE US-146 BB-72, 15 parts of diurea compound modified polyacrylic resin SETALUX 91757 VX-60, 1 part of benzotriazole ultraviolet light absorber Tinuvin 928, 0.5 part of hindered amine light stabilizer Tinuvin292, 0.1 part of polyester modified polydimethylsiloxane leveling agent BYK-331, 0.5 part of acrylate leveling agent BYK-358N and 10 parts of diluent butyl acetate are added into a container and stirred for 30min by using a stirrer to obtain the component A.
The preparation method of the component B comprises the following steps:
under the protection of nitrogen, 30 parts of diluent butyl acetate is added, 70 parts of isocyanate resin Desmodur 3300 is added under the stirring state, and the mixture is stirred for 10min to obtain the component B.
Preparation of the acrylic-polyurethane type overprint varnish composition: the component A and the component B are mixed according to the weight ratio of 100:30 to obtain said acrylic-polyurethane type overprint varnish composition, said mixture AB having to be used up within 30 minutes. The acrylic acid-polyurethane type finishing varnish composition is a two-component high-solid varnish composition.
The steel plate after phosphorization electrophoresis is used, and the thickness of the electrophoretic coating is 20 +/-3 mu m; spraying automobile middle coating (the film thickness is 30-40 μm); spraying water-based finish paint (the film thickness is 15-20 mu m), after flash drying for 4 minutes (min), baking in an oven at 80 ℃ for 5min, then spraying the acrylic acid-polyurethane type finishing varnish composition (the film thickness is 40-50 mu m), leveling for 7min, and then placing in the oven at 140 ℃ for heat preservation for 30 min. The spraying mode can be electrostatic rotary cup spraying or manual air spray gun spraying.
The application is as follows: the acrylic acid-polyurethane type finishing varnish composition of the embodiment can be applied to automobile external coating, and the coating film obtained by coating has good fullness, high distinctness of image and good scratch resistance, is particularly suitable for automobile external coating, and is also suitable for external coating of automobile hubs, motorcycles, engineering machinery, light industrial products and the like.
Comparative example 1
The other materials in the formula are the same as those in example 1, except that the thermosetting hydroxyl acrylic resin with high solid content in the components is 120mgKOH/g (the solid content is more than or equal to 75 percent, and the molecular weight is 3000-;
the preparation method of the component A comprises the following steps:
under the protection of nitrogen, 20 parts of high-solid thermosetting hydroxy acrylic resin, 5 parts of polyester resin SETAL1606 BA-80, 10 parts of butylated amino resin SETAMINE US-146 BB-72, 15 parts of diurea compound modified polyacrylic resin SETALUX 91757 VX-60, 1 part of benzotriazole ultraviolet light absorber Tinuvin 928, 0.5 part of hindered amine light stabilizer Tinuvin292, 0.1 part of polyester modified polydimethylsiloxane leveling agent BYK-331, 0.5 part of acrylate leveling agent BYK-358N and 10 parts of diluent butyl acetate are added into a container and stirred for 30min by using a stirrer to obtain the component A.
The preparation method of the component B comprises the following steps:
under the protection of nitrogen, 30 parts of diluent butyl acetate is added, 70 parts of isocyanate resin Desmodur 3300 is added under the stirring state, and the mixture is stirred for 10min to obtain the component B.
Preparation: the acrylic-polyurethane type overprint varnish composition is obtained by mixing component A and component B in a weight ratio of 100:30, and the mixture AB is used up within 30 minutes.
The steel plate after phosphorization electrophoresis is used, and the thickness of the electrophoretic coating is 20 +/-3 mu m; spraying automobile middle coating (the film thickness is 30-40 μm); spraying water-based finish paint (the film thickness is 15-20 mu m), after flash drying for 4min, baking for 5min in an oven at 80 ℃, then spraying the high-solid acrylic-polyurethane finishing varnish composition (the film thickness is 40-50 mu m)), leveling for 7min, and then putting into the oven for heat preservation for 30min at 140 ℃. The spraying mode can be electrostatic rotary cup spraying or manual air spray gun spraying.
Comparative example 2
The formulation is otherwise identical to example 1 except that the component butylated amino resin was removed.
The preparation method of the component A comprises the following steps:
under the protection of nitrogen, 20 parts of high-solid thermosetting hydroxy acrylic resin, 5 parts of polyester resin SETAL1606 BA-80, 15 parts of diurea compound modified polyacrylic resin SETALUX 91757 VX-60, 1 part of benzotriazole ultraviolet light absorber Tinuvin 928, 0.5 part of hindered amine light stabilizer Tinuvin292, 0.1 part of polyester modified polydimethylsiloxane leveling agent BYK-331, 0.5 part of acrylate leveling agent BYK-358N and 10 parts of diluent butyl acetate are added into a container and stirred for 30min by using a stirrer, so that the component A is obtained.
The preparation method of the component B comprises the following steps:
under the protection of nitrogen, 30 parts of diluent butyl acetate is added, 70 parts of isocyanate resin Desmodur 3300 is added under the stirring state, and the mixture is stirred for 10min to obtain the component B.
Preparation: the acrylic-polyurethane type overprint varnish composition is obtained by mixing component A and component B in a weight ratio of 100:30, and the mixture AB is used up within 30 minutes.
The steel plate after phosphorization electrophoresis is used, and the thickness of the electrophoretic coating is 20 +/-3 mu m; spraying automobile middle coating (the film thickness is 30-40 μm); spraying water-based finish paint (the film thickness is 15-20 mu m), after flash drying for 4min, baking for 5min in an oven at 80 ℃, then spraying the high-solid acrylic-polyurethane finishing varnish composition (the film thickness is 40-50 mu m)), leveling for 7min, and then putting into the oven for heat preservation for 30min at 140 ℃. The spraying mode can be electrostatic rotary cup spraying or manual air spray gun spraying.
Comparative example 3
The formulation was otherwise the same as in example 1 except that the diurea compound modified polyacrylic resin was removed.
The preparation method of the component A comprises the following steps:
under the protection of nitrogen, 20 parts of high-solid thermosetting hydroxy acrylic resin, 5 parts of polyester resin SETAL1606 BA-80, 10 parts of butylated amino resin SETAMINE US-146 BB-72, 1 part of benzotriazole ultraviolet light absorber Tinuvin 928, 0.5 part of hindered amine light stabilizer Tinuvin292, 0.1 part of polyester modified polydimethylsiloxane leveling agent BYK-331, 0.5 part of acrylate leveling agent BYK-358N and 10 parts of diluent butyl acetate are added into a container, and stirred for 30min by using a stirrer to obtain the component A.
The preparation method of the component B comprises the following steps:
under the protection of nitrogen, 30 parts of diluent butyl acetate is added, 70 parts of isocyanate resin Desmodur 3300 is added under the stirring state, and the mixture is stirred for 10min to obtain the component B.
Preparation: the acrylic-polyurethane type overprint varnish composition is obtained by mixing component A and component B in a weight ratio of 100:30, and the mixture AB is used up within 30 minutes.
The steel plate after phosphorization electrophoresis is used, and the thickness of the electrophoretic coating is 20 +/-3 mu m; spraying automobile middle coating (the film thickness is 30-40 μm); spraying water-based finish paint (the film thickness is 15-20 mu m), after flash drying for 4min, baking for 5min in an oven at 80 ℃, then spraying the high-solid acrylic-polyurethane finishing varnish composition (the film thickness is 40-50 mu m)), leveling for 7min, and then putting into the oven for heat preservation for 30min at 140 ℃. The spraying mode can be electrostatic rotary cup spraying or manual air spray gun spraying.
Example 2
The component A comprises: the thermosetting hydroxyl acrylic resin with high solid content, the number average molecular weight of which is 4000, the hydroxyl value of which is 150mgKOH/g and the acid value of the solid resin of which is 8.0mgKOH/g, the high solid content means that the solid content is more than or equal to 75 percent (more than or equal to 75 percent by weight),
the component B comprises:
60 parts of isocyanate resin Basonat HI-100;
30 parts of diluent butyl acetate.
The preparation method of the component A comprises the following steps:
under the protection of nitrogen, 30 parts of high-solid thermosetting hydroxy acrylic resin, 15 parts of polyester resin SILIKOTE 900, 20 parts of butylated amino resin SETAMINE US-138 BB-70, 30 parts of diurea compound modified polyacrylic resin SETALUX 91760 SS-53, 1 part of benzotriazole ultraviolet light absorber Tinuvin384-2, 0.5 part of hindered amine light stabilizer Tinuvin123, 0.1 part of polyester modified polydimethylsiloxane leveling agent BYK-315, 0.5 part of acrylate leveling agent TegoFlow-300 and 10 parts of diluent butyl acetate are added into a container, and stirred for 30min by using a stirrer to obtain the component A.
The preparation method of the component B comprises the following steps:
under the protection of nitrogen, 30 parts of diluent butyl acetate is added, 60 parts of isocyanate resin Basonat HI-100 is added under the stirring state, and the mixture is stirred for 10min to obtain the component B.
Preparation of the acrylic-polyurethane type overprint varnish composition: the component A and the component B are mixed according to the weight ratio of 100:30 to obtain said acrylic-polyurethane type overprint varnish composition, said mixture AB having to be used up within 30 minutes. The acrylic acid-polyurethane type finishing varnish composition is a two-component high-solid varnish composition.
The steel plate after phosphorization electrophoresis is used, and the thickness of the electrophoretic coating is 20 +/-3 mu m; spraying automobile middle coating (the film thickness is 30-40 μm); spraying water-based finish paint (the film thickness is 15-20 mu m), after flash drying for 4min, putting into an oven at 80 ℃ for baking for 5min, then spraying the acrylic acid-polyurethane type finishing varnish composition (the film thickness is 40-50 mu m), leveling for 7min, and then putting into the oven at 140 ℃ for heat preservation for 30 min. The spraying mode can be electrostatic rotary cup spraying or manual air spray gun spraying.
The application is as follows: the acrylic acid-polyurethane type finishing varnish composition of the embodiment can be applied to automobile external coating, and the coating film obtained by coating has good fullness, high distinctness of image and good scratch resistance, is particularly suitable for automobile external coating, and is also suitable for external coating of automobile hubs, motorcycles, engineering machinery, light industrial products and the like.
Example 3
The other materials in the composition are the same as in example 1 except that the high solid content thermosetting hydroxyacrylic resin is 40 parts.
The preparation method of the component A comprises the following steps:
under the protection of nitrogen, 40 parts of high-solid thermosetting hydroxy acrylic resin, 5 parts of polyester resin SETAL1606 BA-80, 10 parts of butylated amino resin SETAMINE US-146 BB-72, 15 parts of diurea compound modified polyacrylic resin SETALUX 91757 VX-60, 1 part of benzotriazole ultraviolet light absorber Tinuvin 928, 0.5 part of hindered amine light stabilizer Tinuvin292, 0.1 part of polyester modified polydimethylsiloxane leveling agent BYK-331, 0.5 part of acrylate leveling agent BYK-358N and 10 parts of diluent butyl acetate are added into a container, and stirred for 30min by using a stirrer to obtain the component A.
The preparation method of the component B comprises the following steps:
under the protection of nitrogen, 30 parts of diluent butyl acetate is added, 70 parts of isocyanate resin Desmodur 3300 is added under the stirring state, and the mixture is stirred for 10min to obtain the component B.
Preparation of the acrylic-polyurethane type overprint varnish composition: the component A and the component B are mixed according to the weight ratio of 100:30 to obtain said acrylic-polyurethane type overprint varnish composition, said mixture AB having to be used up within 30 minutes. The acrylic acid-polyurethane type finishing varnish composition is a two-component high-solid varnish composition.
The steel plate after phosphorization electrophoresis is used, and the thickness of the electrophoretic coating is 20 +/-3 mu m; spraying automobile middle coating (the film thickness is 30-40 μm); spraying water-based finish paint (the film thickness is 15-20 mu m), after flash drying for 4min, putting the mixture into an oven at 80 ℃ for baking for 5min, then spraying the high-solid acrylic acid-polyurethane type finishing varnish composition (the film thickness is 40-50 mu m), leveling for 7min, and putting the mixture into the oven at 140 ℃ for heat preservation for 30 min. The spraying mode can be electrostatic rotary cup spraying or manual air spray gun spraying.
The application is as follows: the acrylic acid-polyurethane type finishing varnish composition of the embodiment can be applied to automobile external coating, and the coating film obtained by coating has good fullness, high distinctness of image and good scratch resistance, is particularly suitable for automobile external coating, and is also suitable for external coating of automobile hubs, motorcycles, engineering machinery, light industrial products and the like.
Example 4
The other materials in the composition were the same as in example 1 except that the amount of the diluent in component A was increased to 30 parts.
The preparation method of the component A comprises the following steps:
under the protection of nitrogen, 20 parts of high-solid thermosetting hydroxy acrylic resin, 5 parts of polyester resin SETAL1606 BA-80, 10 parts of butylated amino resin SETAMINE US-146 BB-72, 15 parts of diurea compound modified polyacrylic resin SETALUX 91757 VX-60, 1 part of benzotriazole ultraviolet light absorber Tinuvin 928, 0.5 part of hindered amine light stabilizer Tinuvin292, 0.1 part of polyester modified polydimethylsiloxane leveling agent BYK-331, 0.5 part of acrylate leveling agent BYK-358N and 30 parts of diluent butyl acetate are added into a container and stirred for 30min by using a stirrer to obtain the component A.
The preparation method of the component B comprises the following steps:
under the protection of nitrogen, 30 parts of diluent butyl acetate is added, 70 parts of isocyanate resin Desmodur 3300 is added under the stirring state, and the mixture is stirred for 10min to obtain the component B.
Preparation of the acrylic-polyurethane type overprint varnish composition: the component A and the component B are mixed according to the weight ratio of 100:30 to obtain said acrylic-polyurethane type overprint varnish composition, said mixture AB having to be used up within 30 minutes. The acrylic acid-polyurethane type finishing varnish composition is a two-component high-solid varnish composition.
The steel plate after phosphorization electrophoresis is used, and the thickness of the electrophoretic coating is 20 +/-3 mu m; spraying automobile middle coating (the film thickness is 30-40 μm); spraying water-based finish paint (the film thickness is 15-20 mu m), after flash drying for 4min, putting the mixture into an oven at 80 ℃ for baking for 5min, then spraying the high-solid acrylic acid-polyurethane type finishing varnish composition (the film thickness is 40-50 mu m), leveling for 7min, and putting the mixture into the oven at 140 ℃ for heat preservation for 30 min. The spraying mode can be electrostatic rotary cup spraying or manual air spray gun spraying.
The application is as follows: the high-solid acrylic-polyurethane finishing varnish composition of the embodiment can be applied to automobile exterior coating, and a coating obtained by coating has good fullness, high distinctness of image and good scratch resistance, is particularly suitable for automobile exterior coating, and is also suitable for exterior coating of automobile hubs, motorcycles, engineering machinery, light industrial products and the like.
Example 5
The other materials in the components are the same as the materials in the embodiment 1, except that the weight portion of the acrylic ester flatting agent Modaflow-2100 is 0.5 portion;
the preparation method of the component A comprises the following steps:
under the protection of nitrogen, 20 parts of high-solid thermosetting hydroxy acrylic resin, 5 parts of polyester resin SETAL1606 BA-80, 10 parts of butylated amino resin SETAMINE US-146 BB-72, 15 parts of diurea compound modified polyacrylic resin SETALUX 91757 VX-60, 1 part of benzotriazole ultraviolet light absorber Tinuvin 928, 0.5 part of hindered amine light stabilizer Tinuvin292, 0.1 part of polyester modified polydimethylsiloxane leveling agent BYK-331, 0.5 part of acrylate leveling agent Modaflow-2100 and 10 parts of diluent butyl acetate are added into a container and stirred for 30min by using a stirrer to obtain the component A.
The preparation method of the component B comprises the following steps:
under the protection of nitrogen, 30 parts of diluent butyl acetate is added, 70 parts of isocyanate resin Desmodur 3300 is added under the stirring state, and the mixture is stirred for 10min to obtain the component B.
Preparation of the acrylic-polyurethane type overprint varnish composition: the component A and the component B are mixed according to the weight ratio of 100:30 to obtain said acrylic-polyurethane type overprint varnish composition, said mixture AB having to be used up within 30 minutes. The acrylic acid-polyurethane type finishing varnish composition is a two-component high-solid varnish composition.
The steel plate after phosphorization electrophoresis is used, and the thickness of the electrophoretic coating is 20 +/-3 mu m; spraying automobile middle coating (the film thickness is 30-40 μm); spraying water-based finish paint (the film thickness is 15-20 mu m), after flash drying for 4min, putting the mixture into an oven at 80 ℃ for baking for 5min, then spraying the high-solid acrylic acid-polyurethane type finishing varnish composition (the film thickness is 40-50 mu m), leveling for 7min, and putting the mixture into the oven at 140 ℃ for heat preservation for 30 min. The spraying mode can be electrostatic rotary cup spraying or manual air spray gun spraying.
The application is as follows: the high-solid acrylic-polyurethane finishing varnish composition of the embodiment can be applied to automobile exterior coating, and a coating obtained by coating has good fullness, high distinctness of image and good scratch resistance, is particularly suitable for automobile exterior coating, and is also suitable for exterior coating of automobile hubs, motorcycles, engineering machinery, light industrial products and the like.
And (3) performance testing:
(1) evaluation of coating film
As shown in FIG. 1, FIG. 1 is a schematic view of the evaluation method of sagging of a coating film of an acrylic-urethane type over-coating varnish composition of the present invention. A test plate A (with a circular hole diameter of 8mm) was sprayed under certain coating conditions (static voltage-90 KV, revolving cup speed of 35000rpm, molding air pressure of 0.15MPa, discharge rate of 400cc/min, gun pitch of 25cm) by using an electrostatic spinning cup coater, the spraying direction was from right to left, and the traveling speed of the spray gun was changed from slow to fast, thereby forming a coating with a film thickness of from thick to thin. The thickness of the film 1cm from the lower edge of the round hole to which the varnish sagged was measured as the sag limit film thickness of the varnish.
The results obtained for the coating films prepared according to the formulations of examples 1 and 2 and comparative examples 1 to 3 according to the following evaluation methods are shown in table 1:
TABLE 1
Note that ◎ is good, △ is slightly worse, and the Xis not qualified.
The acrylic-urethane type overprint varnish compositions obtained in examples 3 to 5 were measured for their performance, and the chemical resistance, construction solids, scratch resistance, and construction solids of the coating films all reached the specified standards, and the sagging properties of the coatings were measured by the above-mentioned evaluation methods and were all not less than 55 μm.
(2) Screening test using the ratio
The following is a screening test of the proportion of butylated amino resin (crosslinker) in component A, the performance data of the acrylic-polyurethane type overprint varnish compositions being shown in Table 2:
TABLE 2
| Butyletherified amino resin | 5 portions of | 10 portions of | 15 portions of | 20 portions of |
| Hardness of | Soft | Is softer | Hard | Is softer |
| Scratch resistance | × | △ | ◎ | △ |
| Chemical resistance | ◎ | ◎ | ◎ | ◎ |
Note that ◎ is good, △ is slightly worse, and the Xis not qualified.
The butyl etherified amino resin (cross-linking agent) in component A is 10-20 parts, which can reach better comprehensive performance. From Table 2, it is clear that the acrylic-polyurethane type overprint varnish composition has the best balance of the scratch resistance of the coating film within the range of 10 to 20 parts of the butylated amino resin (crosslinking agent).
The acrylic acid-polyurethane type finishing varnish composition has high construction solid content (organic solvent volatile is less than 420g/L), high construction sagging limit (more than 55 mu m), high scratch resistance, is particularly suitable for automobile external coating, and is also suitable for external coating of automobile hubs, motorcycles, engineering machinery, light industrial products and the like.
The acrylic acid-polyurethane type finishing varnish composition can be applied to automobile external coating, and the coating obtained by coating has good fullness, high distinctness of image and good scratch resistance, is particularly suitable for automobile external coating, and is also suitable for external coating of automobile hubs, motorcycles, engineering machinery, light industrial products and the like.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the invention and are not to be construed as limiting the embodiments of the present invention, and that various other changes and modifications may be made by those skilled in the art based on the above description. All documents mentioned in this application are incorporated by reference into this application as if each were individually incorporated by reference.
Claims (7)
1. An acrylic-polyurethane type overprint varnish composition characterized by: the composition is prepared from the following components in parts by weight:
the component A is prepared from the following components in parts by weight:
20-40 parts of high-solid thermosetting hydroxy acrylic resin,
5-15 parts of polyester resin,
10-20 parts of a cross-linking agent,
10-30 parts of diurea compound modified acrylic resin,
1.61-5.7 parts of varnish auxiliary agent,
5-30 parts of a first diluent;
the component B is prepared from the following components in parts by weight:
50-80 parts of isocyanate resin,
20-50 parts of a second diluent;
the mass ratio of the component A to the component B is 100 (28-32);
the number average molecular weight of the high-solid thermosetting hydroxyl acrylic resin is 3000-5000, the hydroxyl value is 120-200 mgKOH/g, the acid value of the solid resin is 7.0-11.0mgKOH/g, and the high-solid thermosetting hydroxyl acrylic resin is more than or equal to 75% by weight of the solid;
the modified amount of the diurea compound modified acrylic resin is 3.2 to 4.2 percent;
the varnish auxiliary agent comprises the following components in parts by weight:
1-2 parts of an ultraviolet light absorber,
0.5 to 1.5 portions of light stabilizer,
0.01 to 0.2 portion of organic silicon flatting agent,
0.1-2 parts of acrylate leveling agent;
the polyester resin is at least one of Nepetes SETAL1606 BA-80 and Digao Yingchuang SILIKOTOPOP E900.
2. The acrylic-polyurethane type overprint varnish composition according to claim 1, characterized in that: the cross-linking agent is butylated amino resin.
3. The acrylic-polyurethane type overprint varnish composition according to claim 1, characterized in that: the ultraviolet light absorber is a benzotriazole ultraviolet light absorber;
the light stabilizer is a hindered amine light stabilizer;
the organic silicon flatting agent is polyester modified polydimethylsiloxane flatting agent;
the acrylate leveling agent is a non-reactive acrylate leveling agent.
4. The acrylic-polyurethane type overprint varnish composition according to claim 1, characterized in that: the first diluent is at least one of butyl acetate, ethyl acetate, ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, mixed dibasic acid dibasic ester and 3-ethoxy ethyl propionate.
5. The acrylic-polyurethane type overprint varnish composition according to claim 1, characterized in that: the isocyanate resin is hexamethylene diisocyanate trimer;
the second diluent is at least one of butyl acetate, ethyl acetate, ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, mixed dibasic acid dibasic ester and 3-ethoxy ethyl propionate.
6. A process for preparing an acrylic-polyurethane type overprint varnish composition according to any one of claims 1 to 5, characterized in that: the method comprises the following steps:
preparation of component A:
under the protection of nitrogen, adding 20-40 parts of thermosetting hydroxyl acrylic resin with high solid content, 5-15 parts of polyester resin, 10-20 parts of cross-linking agent, 10-30 parts of diurea compound modified acrylic resin, 1.61-5.7 parts of varnish auxiliary agent and 5-30 parts of first diluent, and stirring to obtain the component A;
preparation of component B:
under the protection of nitrogen, adding 50-80 parts of isocyanate resin and 20-50 parts of second diluent, and stirring to obtain the component B;
and (2) mixing the component A and the component B according to the mass ratio of 100 (28-32) to obtain the acrylic-polyurethane type finishing varnish composition.
7. Use of an acrylic-polyurethane type overprint varnish composition according to any one of claims 1 to 5 for the preparation of coatings.
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| CN108192488B (en) * | 2017-12-29 | 2021-03-02 | 广州立邦涂料有限公司 | Solvent-based bi-component high-smoothness varnish composition, preparation method and application |
| CN113166578B (en) * | 2018-12-07 | 2022-08-12 | 关西涂料株式会社 | Coating composition |
| CN112442305A (en) * | 2019-08-29 | 2021-03-05 | 江苏宏源机电科技有限公司 | High-solid-content coating and preparation method thereof |
| CN111334106A (en) * | 2020-04-26 | 2020-06-26 | 江苏科环新材料有限公司 | Water-resistant salt-resistant anticorrosive paint |
| CN112708317A (en) * | 2021-01-15 | 2021-04-27 | 江阴市荣新塑化有限公司 | High-wear-resistance weather-resistant finish paint for spraying automobile aluminum material and preparation method thereof |
| CN114632684A (en) * | 2022-04-08 | 2022-06-17 | 华涂技术(深圳)股份有限公司 | Anticorrosive coating process for automobile body |
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| JP5004782B2 (en) * | 2007-12-21 | 2012-08-22 | 旭化成ケミカルズ株式会社 | Polyisocyanate composition and two-component polyurethane composition |
| CN102190933B (en) * | 2010-03-05 | 2014-09-24 | 立邦涂料（中国）有限公司 | Acrylic-amino type coating varnish composition for automobiles, varnish and application thereof |
| CN102627910A (en) * | 2012-03-24 | 2012-08-08 | 吉林建筑工程学院 | Photochromic acrylic polyurethane varnish and preparation method thereof |
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