Orange-figured auxiliary agent, water-based two-component orange-figured paint, and preparation method and application of water-based two-component orange-figured paint

Abstract

The invention belongs to the technical field of coatings, and particularly relates to an orange-figured assistant, a water-based two-component orange-figured paint, and a preparation method and application of the water-based two-component orange-figured paint. The orange-figured auxiliary agent contains fluorine, methoxyl and F atoms, the fluorine, methoxyl and F atoms have low surface tension and can form large tension difference with atoms in an orange-figured paint system so as to promote a paint film to form a surface effect with strong stereoscopic impression, the methoxyl groups in the orange-figured auxiliary agent contribute to improving the crosslinking density of a product, and the orange-figured auxiliary agent has the advantages that the orange-figured auxiliary agent can be applied to the production of the orange-figured paint, so that the service life of the orange-figured paint is prolonged, and the service life of the orange-figured paint is prolonged. The adhesive force is improved. Therefore, after the orange-figured assistant is applied to the orange-figured paint, the adhesive force and the impact property of the orange-figured paint can be better improved, and the orange-figured effect and the stereoscopic impression of a paint film can be improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of coatings, and particularly relates to an orange peel additive, a water-based two-component orange peel paint, and a preparation method and application thereof. Background Art

[0002] Orange peel paint is an artistic paint. Since the surface of the paint film has a shape like an orange peel, it is called orange peel paint. Orange peel paint is commonly used in the field of steel structures, such as the coating of machining centers, instruments, and mechanical surfaces. At present, most of the commonly used orange peel paints are mainly oil-based paints, but oil-based paints have environmental protection problems. Therefore, it is particularly important to develop environmentally friendly water-based orange peel paints. At present, the water-based orange peel paints on the market generally have problems such as difficulty in achieving the orange peel effect, weak three-dimensional sense on the surface of the paint film, exposing the bottom layer, and insufficient adhesion.

[0003] Therefore, it is of great significance to provide an orange peel paint with a strong three-dimensional sense on the surface of the paint film, an obvious orange peel effect, and good adhesion. Summary of the Invention

[0004] The present invention aims to solve one or more of the above-mentioned technical problems existing in the prior art, and at least provides a beneficial option. Specifically, the present invention provides an orange peel additive, and the paint film prepared by the orange peel additive has a strong three-dimensional sense on the surface, an obvious orange peel effect, good adhesion, and is green and environmentally friendly.

[0005] The inventive concept of the present invention: The orange peel additive of the present invention has a specific structure. The F atom has a low surface tension and can form a large surface tension difference with the atoms in the orange peel paint system to promote the formation of a surface effect with a strong three-dimensional sense; and the methoxy group in the orange peel additive helps to improve the crosslinking density of the product and improve the adhesion. Through the combined action of fluorine and methoxy group, not only can the three-dimensional sense and orange peel beauty of the paint film be improved, but also the adhesion of the orange peel paint can be improved.

[0006] Therefore, in the first aspect of the present invention, an orange peel additive is provided.

[0007] Specifically, the structural formula of the orange peel additive is:

[0008]

[0009] In the second aspect of the present invention, a preparation method of the orange peel additive according to the first aspect of the present invention is provided.

[0010] Specifically, the preparation method of the orange peel additive includes the following steps:

[0011] Mix perfluorobutanol, acrylic monomer and trimethoxysilane, and react to obtain the orange peel additive.

[0012] Specifically, the reaction is an esterification reaction.

[0013] Preferably, the preparation method of the orange peel additive comprises the following steps:

[0014] (1) Mix the perfluorobutanol, acrylic monomer, first catalyst, and solvent, introduce nitrogen, heat, and keep warm to obtain an intermediate product;

[0015] (2) Mix the intermediate product obtained in step (1) with a second catalyst and trimethoxysilane, and react to obtain the orange peel additive.

[0016] Preferably, in step (1), the molar ratio of the perfluorobutanol to the acrylic monomer is (0.45 - 0.9):1; more preferably, the molar ratio of the perfluorobutanol to the acrylic monomer is (0.5 - 0.8):1.

[0017] Preferably, in step (1), the addition amount of the first catalyst accounts for 2.7 - 5.5% of the total mass of the perfluorobutanol and the acrylic monomer; more preferably, the addition amount of the first catalyst accounts for 3 - 5% of the total mass of the perfluorobutanol and the acrylic monomer.

[0018] Preferably, the first catalyst includes sodium aluminate.

[0019] Preferably, in step (1), the addition amount of the solvent is 45 - 110 times the sum of the molar numbers of the perfluorobutanol and the acrylic monomer; more preferably, the addition amount of the solvent is 50 - 100 times the sum of the molar numbers of the perfluorobutanol and the acrylic monomer.

[0020] Preferably, in step (1), the solvent includes cyclohexane.

[0021] Preferably, in step (1), the temperature for heat preservation is 90 - 130°C, and the time for heat preservation is 13 - 22 h; more preferably, in step (1), the temperature for heat preservation is 100 - 120°C, and the time for heat preservation is 15 - 20 h.

[0022] Preferably, in step (1), stirring is carried out during the heat preservation process.

[0023] Preferably, in step (2), the mass ratio of the intermediate product to trimethoxysilane is 1:(0.7 - 2.2); more preferably, in step (2), the mass ratio of the intermediate product to trimethoxysilane is 1:(0.8 - 2).

[0024] Preferably, the addition amount of the second catalyst accounts for 9 - 33% of the total mass of the intermediate product and trimethoxysilane; more preferably, the addition amount of the second catalyst accounts for 10 - 30% of the total mass of the intermediate product and trimethoxysilane.

[0025] Preferably, the second catalyst comprises platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane.

[0026] Preferably, in step (2), the temperature of the reaction is 35-65°C.

[0027] More preferably, the temperature of the reaction is 40-60°C.

[0028] The third aspect of the present invention provides a water-based two-component orange peel paint.

[0029] Specifically, the water-based two-component orange peel paint comprises the orange peel additive described in the first aspect of the present invention.

[0030] Preferably, the water-based two-component orange peel paint comprises component A and component B;

[0031] Component A comprises a water-based resin, additives, fillers, and water;

[0032] Component B comprises a curing agent;

[0033] The additives comprise the orange peel additive.

[0034] Preferably, the water-based resin comprises a hydroxy acrylic dispersion.

[0035] Preferably, the hydroxyl value range of the hydroxy acrylic dispersion is 1.8-5.5% (based on solids); more preferably, the hydroxyl value range of the hydroxy acrylic dispersion is 2-5% (based on solids).

[0036] Preferably, the solids content of the hydroxy acrylic dispersion is 40-70%; more preferably, the solids content of the hydroxy acrylic dispersion is 45-65%.

[0037] Preferably, the fillers comprise at least one of titanium dioxide, barium sulfate, carbon black powder, talc powder, and iron black powder.

[0038] Preferably, the fillers are water-soluble fillers.

[0039] Preferably, the curing agent comprises a polyurethane curing agent; more preferably, the polyurethane curing agent is a water-based polyurethane curing agent.

[0040] Preferably, the mass fraction of isocyanate in the polyurethane curing agent is 13-33%; more preferably, the mass fraction of isocyanate in the polyurethane curing agent is 15-30%.

[0041] Preferably, the additives further comprise at least one of a dispersant, a co-solvent, an antifoaming agent, and a thickening agent.

[0042] Preferably, the mass ratio of the component A to the component B is (4.5 - 17.5):1; More preferably, the mass ratio of the component A to the component B is (5 - 16):1.

[0043] Preferably, the auxiliary agent further includes a dispersant, a cosolvent, an antifoaming agent, and a thickener; and by weight percentage, the component A includes 45 - 70% of an aqueous resin, 0.45 - 1.1% of a dispersant, 3.5 - 13% of a cosolvent, 13 - 33% of a filler, 0.1 - 0.33% of an antifoaming agent, 0.1 - 1.1% of an orange peel pattern agent, 0.1 - 1.1% of a thickener, and 9 - 22% of water.

[0044] More preferably, the auxiliary agent further includes a dispersant, a cosolvent, an antifoaming agent, and a thickener; and by weight percentage, the component A includes 50 - 65% of an aqueous resin, 0.5 - 1% of a dispersant, 4 - 12% of a cosolvent, 15 - 30% of a filler, 0.1 - 0.3% of an antifoaming agent, 0.1 - 1% of an orange peel pattern agent, 0.1 - 1% of a thickener, and 10 - 20% of water.

[0045] Preferably, the dispersant includes at least one of a polyurethane dispersant and an acrylic dispersant.

[0046] Preferably, the cosolvent includes at least one of propylene glycol methyl ether, dipropylene glycol butyl ether, butyl acetate, and acetic acid butyl ester.

[0047] Preferably, the antifoaming agent includes at least one of a silicone antifoaming agent and a mineral oil antifoaming agent.

[0048] Preferably, the thickener includes at least one of a polyurethane thickener and an alkali - swellable thickener.

[0049] Specifically, the thickener is an aqueous thickener.

[0050] Preferably, the fineness of the main paint (component A) of the orange peel paint is less than or equal to 40 μm.

[0051] The fourth aspect of the present invention provides a preparation method of the water - borne two - component orange peel paint described in the third aspect of the present invention.

[0052] Specifically, the preparation method of the water - borne two - component orange peel paint includes the following steps:

[0053] Mix the raw material components of the component A to obtain the component A;

[0054] The component A and the component B constitute the water - borne two - component orange peel paint.

[0055] Preferably, the preparation process of the component A includes:

[0056] (1) Mix the water, partial cosolvent, dispersant, defoamer, and filler, stir and grind to obtain a slurry;

[0057] (2) Mix and disperse the slurry obtained in step (1) with the waterborne resin and the remaining cosolvent to obtain a mixture;

[0058] (3) Mix the mixture obtained in step (2) with the orange peel additive, and then add the thickener to obtain the component A.

[0059] The fifth aspect of the present invention provides an application of the orange peel additive described in the first aspect of the present invention or the waterborne two-component orange peel paint described in the third aspect of the present invention in the field of metal surface coating.

[0060] Compared with the prior art, the beneficial effects of the technical solution provided by the present invention are as follows:

[0061] (1) The orange peel additive of the present invention has a specific structure, and the orange peel additive contains fluorine and methoxy groups. The F atom has a low surface tension, which can form a large surface tension difference with the atoms in the orange peel paint system to promote the formation of a strong three-dimensional surface effect on the paint film. Moreover, the methoxy group in the orange peel additive helps to improve the crosslinking density of the product and enhance the adhesion. The combined action of the orange peel additive and other components can not only enhance the three-dimensional sense and orange peel effect of the paint film, but also improve the adhesion and impact performance of the orange peel paint.

[0062] (2) The preparation method of the present invention is simple, the process operation is easy to implement, and it is convenient for large-scale production and application. Description of the Drawings

[0063] Figure 1 They are the orange peel effect diagrams of grade A, grade B, grade C, and grade D. Detailed Embodiments

[0064] In order to make those skilled in the art more clearly understand the technical solution described in the present invention, the following examples are listed for illustration. It should be noted that the following examples do not limit the protection scope required by the present invention.

[0065] Unless otherwise specified, the raw materials, reagents, or devices used in the following examples can be obtained from conventional commercial channels or can be obtained by existing known methods.

[0066] Example 1

[0067] A waterborne two-component orange peel paint is composed of component A and component B;

[0068] By weight percentage, component A consists of the following components: 13% water, 57% water-based resin (Songwei UR-1246), 8% cosolvent (5% propylene glycol methyl ether and 3% butyl acetate), 0.6% dispersant (Matsuo 8840W), 21% filler (18% titanium dioxide and 3% carbon black powder), 0.1% defoamer (BYK CF-1536), 0.2% orange peel additive, and 0.1% water-based thickener (Shanghai Shenzhu SN-9722);

[0069] Component B is 100% water-based polyurethane curing agent (Asahi Kasei MHG-80B);

[0070] The mass ratio of component A to component B is 8:1.

[0071] The structural formula of the orange peel additive is:

[0072]

[0073] The reaction equation of the orange peel additive is:

[0074]

[0075] The preparation method of the water-based two-component orange peel paint includes the following steps:

[0076] (1) Pre-dispersion of the slurry: Add water, cosolvent (35% of all the cosolvent), and defoamer into the reaction kettle, stir for 15 min, and control the rotation speed at 1200 r / min; add the dispersant, stir for 5 min, and the rotation speed is 500 r / min; then add the filler and disperse it at high speed for 10 min, and control the rotation speed at 2000 r / min; finally, add the grinding beads, the rotation speed is 3200 r / min, and grind the filler fineness to 50 μm to obtain the slurry;

[0077] (2) Paint adjustment: Blend the slurry obtained in step (1) with the water-based resin, control the rotation speed at 700 r / min to prevent demulsification, stir for 30 min, and then add the remaining all cosolvent, orange peel additive, and mix and stir; finally, use the water-based thickener to adjust the system to a viscosity of KU = 75 (measured by Stormer viscometer) to obtain component A; Component A and component B constitute the orange peel paint.

[0078] Among them, the preparation method of the orange peel additive includes the following steps:

[0079] (1) Add 0.6 mol of perfluorobutanol, 1 mol of acrylic monomer, and 9 g of sodium aluminate into cyclohexane, introduce nitrogen, heat to 120 °C and stir for 18 h, and naturally cool to room temperature of 25 °C to obtain an intermediate product;

[0080] (2) React the 100 g of intermediate product obtained in step (1), 48 g of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (catalyst 2), and 100 g of trimethoxyhydrosilane at 55 °C to obtain a water-based orange peel additive.

[0081] Example 2

[0082] The difference between Example 2 and Example 1 is only that the water-based resin in Example 2 is Wanhua 2043, and the water-based polyurethane curing agent is Duonaide TPA-100, and the others are the same as in Example 1.

[0083] Example 3

[0084] The difference between Example 3 and Example 1 is only that the water-based resin selected in Example 3 is Tongde 3AH56W, the defoaming agent is BASF 2240, and the water-based polyurethane curing agent is Wanhua Chemical 161, and the others are the same as in Example 1.

[0085] Example 4

[0086] The difference between Example 4 and Example 1 is only that the fillers added in Example 4 are titanium dioxide, barium sulfate, and talc powder, and the mass ratio of the three is 10:10:1, and the others are the same as in Example 1.

[0087] Comparative Example 1

[0088] The difference between Comparative Example 1 and Example 1 is only that the orange peel additive in Comparative Example 1 is DH-8200 from Suzhou Qingtian New Materials Co., Ltd., which is a high molecular polysiloxane polymer, and the others are the same as in Example 1.

[0089] Comparative Example 2

[0090] The difference between Comparative Example 2 and Example 1 is that the orange peel additive in Comparative Example 2 is 1103 from Hongxin Chemical Industry, which is a silicone polymer, and the others are the same as in Example 1.

[0091] Comparative Example 3

[0092] The difference between Comparative Example 3 and Example 1 is that the orange peel additive in Comparative Example 3 is obtained by chemical reaction of p-fluorostyrene, acrylic monomer, and trimethoxyhydrosilane, and the others are the same as in Example 1.

[0093] Comparative Example 4

[0094] The difference between Comparative Example 4 and Example 1 is that the orange peel additive in Comparative Example 4 is obtained by chemical reaction of perfluorobutanol, 3,4-dihydroxycinnamic acid, and trimethoxyhydrosilane, and the others are the same as in Example 1.

[0095] Comparative Example 5

[0096] The difference between Comparative Example 5 and Example 1 is that in Comparative Example 5, the orange peel additive is obtained by chemical reaction using perfluorobutanol, acrylic monomer, and tetramethyldivinyldisiloxane, and the others are the same as in Example 1.

[0097] Performance Test

[0098] The waterborne two-component orange peel paints of Examples 1-4 and Comparative Examples 1-5 were subjected to performance tests. The specific test items and test methods are as follows:

[0099] Adhesion: Tested in accordance with GB / T 9286-1998;

[0100] Impact resistance (cm): Tested in accordance with GB / T1732-1993;

[0101] Film appearance: Visually inspected. According to the orange peel surface effect and the three-dimensional sense strength, the film appearance was divided into 4 grades. Grade A is excellent, Grade B is good, Grade C is average, and Grade D is poor.

[0102] The orange peel effects of Grade A, Grade B, Grade C, and Grade D are as Figure 1 shown. Among them, Figure 1 Figures (a), (b), (c), and (d) in

[0103] are the orange peel effect diagrams of Grade A, Grade B, Grade C, and Grade D, respectively.

[0104] Table 1: Performance test results of the waterborne two-component orange peel paints of Examples 1-4 and Comparative Examples 1-5

[0105]

[0106] It can be seen from Table 1 that the orange peel paint of the present invention has good adhesion, impact resistance, and good surface effect and three-dimensional sense.

[0107] Comparative Examples 1 and 2 used existing orange peel additives, making the adhesion and film appearance of Comparative Examples 1 and 2 significantly worse than those of Example 1.

[0108] For Comparative Example 3, the raw materials for preparing the orange peel additive are p-fluorostyrene, acrylic monomer, and trimethoxyhydro-silane. For Comparative Example 4, the raw materials for preparing the orange peel additive are perfluorobutanol, 3,4-dihydroxycinnamic acid, and trimethoxyhydro-silane. For Comparative Example 5, the raw materials for preparing the orange peel additive are perfluorobutanol, acrylic monomer, and tetramethyldivinyldisiloxane. As a result, the impact resistance and film appearance of Comparative Example 3 are worse than those of Example 1. The adhesion, impact resistance, and film appearance of Comparative Example 4 are worse than those of Example 1. The impact resistance, adhesion, and film appearance of Comparative Example 5 are all worse than those of Example 1. It shows that the present invention uses specific perfluorobutanol, acrylic monomer, and trimethoxyhydro-silane as raw materials to prepare the orange peel additive, which can better improve the adhesion, film appearance, and impact resistance of the orange peel paint after being applied to the orange peel paint.

[0109] In summary, the present invention uses specific perfluorobutanol, acrylic monomer, and trimethoxyhydro-silane as raw materials to prepare the orange peel additive. The three act synergistically, so that the prepared orange peel additive can better improve the adhesion and impact resistance of the orange peel paint after being applied to the orange peel paint, and can also improve the orange peel effect and three-dimensional sense of the paint film.

[0110] The above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. An orange peel pattern additive, characterized in that, The structural formula of the orange peel additive is as follows:

2. The preparation method of the orange peel pattern additive according to claim 1, characterized in that, It includes the following steps: Mix perfluorobutanol, acrylic monomer and trimethoxysilane, and react to obtain the orange peel additive.

3. The preparation method according to claim 2, characterized in that, It includes the following steps: (1) Mix the perfluorobutanol, acrylic monomer, first catalyst and solvent, and introduce nitrogen, heat and keep warm to obtain an intermediate product; (2) Mix the intermediate product obtained in step (1) with a second catalyst and trimethoxysilane, and react to obtain the orange peel additive.

4. The preparation method according to claim 3, characterized in that, In step (1), the molar ratio of the perfluorobutanol to the acrylic monomer is (0.45 - 0.9):1; and / or, the addition amount of the first catalyst accounts for 2.7 - 5.5% of the total mass of the perfluorobutanol and the acrylic monomer; and / or, the temperature for keeping warm is 90 - 130°C, and the time for keeping warm is 13 - 22 h; and / or, stirring is carried out during the process of keeping warm; and / or, in step (2), the mass ratio of the intermediate product to trimethoxysilane is 1:(0.7 - 2.2); and / or, the addition amount of the second catalyst accounts for 9 - 33% of the total mass of the intermediate product and trimethoxysilane; and / or, the reaction temperature is 35 - 65°C.

5. An orange peel paint, characterized in that, It includes the orange peel additive described in claim 1.

6. The orange-peel paint according to claim 5, characterized in that, It includes component A and component B; Component A includes waterborne resin, additives, fillers, and water; Component B includes a curing agent; The additives include the orange peel additive.

7. The orange peel paint according to claim 6, wherein The waterborne resin includes a hydroxyl acrylic dispersion; and / or, the fillers include at least one of titanium dioxide, barium sulfate, carbon black powder, talc powder, and iron black powder; and / or, the curing agent includes a polyurethane curing agent; and / or, the additives also include at least one of a dispersant, a co-solvent, an antifoaming agent, and a thickener; and / or, the mass ratio of component A to component B is (4.5 - 17.5):

1.

8. The orange peel paint according to claim 7, wherein, The additives also include a dispersant, a co-solvent, an antifoaming agent, and a thickener; and by weight percentage, component A includes 45 - 70% of waterborne resin, 0.45 - 1.1% of dispersant, 3.5 - 13% of co-solvent, 13 - 33% of fillers, 0.1 - 0.33% of antifoaming agent, 0.1 - 1.1% of orange peel additive, 0.1 - 1.1% of thickener, and 9 - 22% of water.

9. The preparation method of the orange peel paint according to any one of claims 5-8, characterized in that, It includes the following steps: Mix each raw material component of component A to obtain component A; Component A and component B constitute the orange peel paint.

10. Application of the orange peel additive described in claim 1 or the orange peel paint described in any one of claims 5 - 8 in the field of metal surface coating.

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