Color paste with high wettability and high covering power as well as preparation method and application of color paste

Abstract

The invention discloses a high-wettability and high-covering-power color paste, which is prepared from the following raw materials: polyester resin and toner, and the Mohs hardness of the toner is 2-5. The vacuum infusion resin and the color paste are mixed according to the proportion of 98: 2, so that the vacuum infusion product has a certain appearance color, the use of coatings (paint and gel coat) is reduced, and the cost of the vacuum infusion product is greatly reduced. According to the invention, zinc sulfide with Moh's hardness of 3, brightness of 98 and average particle size of 0.35 [mu] m is adopted as the toner, so that friction between the toner and the glass fiber can be reduced, and influence on physical properties of a final product is reduced. The bonding degree among the resin, the color paste and the glass fiber can be improved, so that the effect of providing certain coating appearance protection for the glass fiber reinforced plastic product without influencing the strength of the product is achieved.

Description

Technical Field

[0001] The present invention relates to the field of coating compositions, and particularly to a color paste with high wettability and high hiding power, a preparation method thereof, and an application thereof. Background Art

[0002] The vacuum infusion process is a process in which a reinforcing fiber material is pre-laid on a rigid mold, then auxiliary materials such as a vacuum bag are laid, the air in the system is evacuated, and the unsaturated resin is pressed into the fiber layer through a pre-laid pipeline by the pressure generated during the vacuum pumping process, so that the resin wets the fiber material. In the vacuum infusion process, white parts generally have problems of reduced product strength due to poor wettability of the white color paste, and the hiding power of the white color paste is insufficient, requiring a relatively high addition amount, which exacerbates the problem of reduced product strength. Therefore, it is crucial to develop a color paste that has little impact on the mechanical properties of the vacuum infusion resin and has high hiding power.

[0003] Chinese Patent Application CN102964791A discloses an unsaturated polyester glass fiber mat board and a preparation method thereof. A polyethylene film is laid on each of the upper and lower surfaces of the glass fiber mat, and they are driven by a chain belt to pass through a pair of rollers together. After extrusion, the resin paste on the upper and lower polyethylene films penetrates into the glass fiber mat under the action of pressure to obtain a sized mat sheet with films attached to the upper and lower surfaces, which does not involve the problem of resin penetration into glass fibers and is not applicable to the vacuum infusion process. Chinese Patent CN101747607B discloses a resin-based composite sanitary ware hardware and a preparation method thereof, which are prepared by high-pressure injection or pressing into a mold for curing. The metal mold of the sanitary ware hardware product is evacuated to make the produced sanitary ware hardware product dense and pore-free, which does not involve the problem of resin wetting of glass fibers in a vacuum state and is not applicable to the vacuum infusion process. Summary of the Invention

[0004] In order to develop a color paste that has little impact on the mechanical properties of the vacuum infusion resin and has high hiding power, the first aspect of the present invention provides a color paste with high wettability and high hiding power, and the preparation raw materials include a polyester resin and a color powder, and the Mohs hardness of the color powder is 2-5.

[0005] As an embodiment, the Mohs hardness of the color powder is 3.

[0006] As an embodiment, the preparation raw materials include 30-40% of the polyester resin and 60-70% of the color powder by weight percentage, and the sum of the weight percentages of the polyester resin and the color powder is 100%.

[0007] As an embodiment, the preparation raw materials include 39% of the polyester resin and 61% of the color powder by weight percentage, and the sum of the weight percentages of the polyester resin and the color powder is 100%.

[0008] As an implementation manner, the average particle size of the toner is 0.1 - 0.5 μm, and the light brightness L is 95 - 100.

[0009] As an implementation manner, the average particle size of the toner is 0.2 - 0.4 μm, and the light brightness L is 97 - 99.

[0010] As an implementation manner, the average particle size of the toner is 0.35 μm, and the light brightness L is 98.

[0011] During the experiment, the inventors found that if the hardness of the toner in the color paste added to the vacuum - introduced resin is too high, the bonding degree between the resin and the glass fiber will decrease due to friction during the curing and molding process of the vacuum - introduced resin, resulting in a significant decrease in the strength of the fiberglass product. If zinc sulfide with a Mohs hardness of 3 is used as the toner, while increasing the covering power of the vacuum - introduced resin, the influence of the toner on the mechanical properties of the vacuum - introduced resin product can be reduced. The reason may be that the friction between the low - hardness zinc sulfide and the glass fiber is small, which can reduce the influence on the mechanical properties. And zinc sulfide with a light brightness of 98 and a particle size of 35 μm has good dispersibility in the color paste, thus forming a color - uniform and good - covering - power color paste.

[0012] As an implementation manner, the oil absorption of the toner is 10 - 15 g / 100 g.

[0013] As an implementation manner, the oil absorption of the toner is 13 g / 100 g.

[0014] As an implementation manner, the toner is at least one of titanium dioxide or zinc sulfide.

[0015] As an implementation manner, the toner is zinc sulfide.

[0016] As an implementation manner, the viscosity of the polyester resin at 23 °C is 1000 - 1200 cst.

[0017] During the experiment, the inventors found that using a polyester resin with a viscosity of 1000 - 1200 cst can relatively avoid the decrease in the tensile and flexural properties of the vacuum - introduced resin. The possible reason is guessed to be that the polyester resin with a high viscosity has a good wrapping effect on the toner, and the movement resistance between the toners is large after forming the color paste. After being incorporated into the vacuum - introduced resin, it is not easy to contact with the glass fiber, reducing the friction between the toner and the glass fiber, and the bonding effect among the vacuum - introduced resin, the color paste, and the glass fiber is excellent. The inventors further found that when the viscosity of the polyester resin further increases, it will affect the dispersibility of the color paste in the vacuum - introduced resin and even increase the processing difficulty of the vacuum introduction.

[0018] As an embodiment, the raw materials for preparing the polyester resin include, by weight: 100 parts of terephthalic acid, 71 - 80 parts of ethylene glycol, 35 - 50 parts of adipic acid (CAS No.: 124 - 04 - 9), and 3.5 - 5.5 parts of benzoic acid.

[0019] As an embodiment, the raw materials for preparing the polyester resin include, by weight: 100 parts of terephthalic acid, 75 parts of ethylene glycol, 40 parts of adipic acid, and 4 parts of benzoic acid.

[0020] As an embodiment, the method for preparing the polyester resin includes the following steps:

[0021] S1 Mix terephthalic acid, ethylene glycol, and adipic acid, and raise the temperature to 180 - 220 °C for reaction;

[0022] S2 Remove the by - product impurities generated during the reaction through a fractionating column. When the acid value drops to 10 - 20 mg / KOH, raise the temperature to 250 - 270 °C and maintain a vacuum;

[0023] S3 Test the viscosity. When the viscosity reaches 5000 - 20000 cst, add benzoic acid and cool down to below 150 °C to obtain the polyester resin.

[0024] The second aspect of the present invention provides a method for preparing a color paste with high wettability and high hiding power, including the following step: Mix the polyester resin and color powder evenly to obtain the color paste.

[0025] The third aspect of the present invention provides an application of the color paste with high wettability and high hiding power, which is applied to the vacuum infusion resin.

[0026] As an embodiment, the weight ratio of the color paste to the vacuum infusion resin is (1 - 3):(97 - 99).

[0027] As an embodiment, the weight ratio of the color paste to the vacuum infusion resin is 2:98.

[0028] The inventor found during the experiment that introducing a modified color paste into the vacuum infusion resin and using a weight ratio of resin to color paste of 98:2 can endow the vacuum - infused product with a certain appearance color, reduce the use of coatings (paint, gel coat), and greatly reduce the cost of the vacuum - infused product. The reason is that the vacuum infusion resin needs to fully wet the glass fiber, so its viscosity is small and it is almost transparent. By introducing the color paste, the hiding power of the vacuum infusion resin for the glass fiber can be increased, thus having a certain color.

[0029] However, the inventor further found that if the hardness of the color powder in the color paste is relatively high, it will affect the bonding degree between the resin and the glass fiber, resulting in a decrease in the strength of the product. Using the color paste of the present application can improve the bonding degree among the resin, the color paste and the glass fiber, so as to provide an appearance protection for the FRP product with a certain coating while not affecting the strength of the product.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] (1) For the color paste with high wettability and high hiding power of the present invention, when the vacuum infusion resin and the color paste are mixed in a ratio of 98:2, it can endow the vacuum infusion product with a certain appearance color, reduce the use of coatings (paint, gel coat), and greatly reduce the cost of the vacuum infusion product.

[0032] (2) For the color paste with high wettability and high hiding power of the present invention, zinc sulfide with a Mohs hardness of 3, a brightness of 98, and an average particle size of 0.35 μm is used as the color powder, which can reduce the friction between the color powder and the glass fiber and reduce the influence on the physical properties of the final product.

[0033] (3) For the color paste with high wettability and high hiding power of the present invention, a polyester resin with a viscosity of 1000 - 1200 cst is used, which can maintain the tensile properties and flexural properties after the vacuum infusion resin is cured and formed.

[0034] (4) For the color paste with high wettability and high hiding power of the present invention, when the color paste of the present application is added to the vacuum infusion resin, it can improve the bonding degree among the resin, the color paste and the glass fiber, so as to achieve the effect of providing an appearance protection for the FRP product with a certain coating while not affecting the strength of the product.

[0035] (5) For the color paste with high wettability and high hiding power of the present invention, when added to the vacuum infusion resin, the tensile and flexural strengths of the vacuum-formed fiber-reinforced composite material decrease by < 5%, and the hiding power increases by > 15%. Description of the Drawings

[0036] Figure 1 Physical diagram of the plate prepared by the vacuum infusion resin prepared in Example 1 under the vacuum infusion process;

[0037] Figure 2 Physical diagram of the plate prepared by applying the color paste prepared in Example 2 to the vacuum infusion resin under the vacuum infusion process;

[0038] Figure 3 Physical diagram of the plate prepared by applying the color paste prepared in Example 3 to the vacuum infusion resin under the vacuum infusion process;

[0039] Figure 4The physical diagram of the board prepared by applying the color paste prepared in Example 4 to the vacuum infusion resin under the vacuum infusion process. Detailed implementation manners

[0040] Example 1

[0041] A vacuum infusion resin, model EL-4088H2, is purchased from Zhenjiang Liddell.

[0042] The preparation raw materials of the vacuum infusion resin include 100 parts by weight of terephthalic acid, 65 parts by weight of ethylene glycol, 30 parts by weight of adipic acid, and 2 parts by weight of benzoic acid.

[0043] The preparation method of the vacuum infusion resin includes the following steps:

[0044] S1 Mix terephthalic acid, ethylene glycol, and adipic acid, and raise the temperature to 200 °C for reaction;

[0045] S2 Remove the by-product impurities generated during the reaction through a fractionating column. When the acid value drops to 15 mg / KOH, raise the temperature to 260 °C and maintain vacuum;

[0046] S3 Test the viscosity. When the viscosity reaches 5000 - 8000 cst, add benzoic acid and cool down to below 150 °C to obtain the vacuum infusion resin.

[0047] Example 2

[0048] A color paste with high wettability and high hiding power includes 39% of polyester resin and 61% of color powder.

[0049] The color powder is zinc sulfide. The Mohs hardness of the color powder is 3, the average particle size is 0.35 μm, the light brightness L is 98, and the oil absorption is 13 g / 100 g. It is purchased from German Sahalieben, model Sahalieben zinc sulfide HD.

[0050] The viscosity of the polyester resin at 23 °C is 1000 - 1200 cst. The model is EL-P50 and it is purchased from Zhenjiang Liddell.

[0051] The preparation raw materials of the polyester resin include: 100 parts by weight of terephthalic acid, 75 parts by weight of ethylene glycol, 40 parts by weight of adipic acid, and 4 parts by weight of benzoic acid.

[0052] The preparation method of the polyester resin includes the following steps:

[0053] S1 Mix terephthalic acid, ethylene glycol, and adipic acid, and raise the temperature to 200 °C for reaction;

[0054] S2 Remove the by-product impurities generated during the reaction through a fractionating column. When the acid value drops to 15 mg / KOH, raise the temperature to 260 °C and maintain vacuum;

[0055] Test the viscosity at S3. When the viscosity reaches 5000 - 20000 cst, add benzoic acid and cool down to below 150 °C to obtain the polyester resin.

[0056] A method for preparing a color paste with high wettability and high hiding power, comprising the following steps: Mix the polyester resin and the color powder evenly to obtain the color paste.

[0057] An application of a color paste with high wettability and high hiding power, which is applied to the vacuum infusion resin.

[0058] The weight ratio of the color paste to the vacuum infusion resin is 2:98.

[0059] The vacuum infusion resin is the same as in Example 1.

[0060] Example 3

[0061] A color paste with high wettability and high hiding power, comprising 40% of polyester resin and 60% of color powder.

[0062] The color powder is titanium dioxide. Purchased from Changzhou Antai Chemical Industry, with the model number of B311 color powder.

[0063] The remaining implementation manners are the same as in Example 2.

[0064] Example 4

[0065] A color paste with high wettability and high hiding power, comprising 40% of polyester resin and 60% of color powder.

[0066] The color powder is titanium dioxide. Purchased from Longbai Group, with the model number of T895 color powder.

[0067] The remaining implementation manners are the same as in Example 2.

[0068] Example 5

[0069] A color paste with high wettability and high hiding power, comprising 40% of polyester resin and 60% of color powder.

[0070] The color powder includes color powder of model T895 (titanium dioxide), color powder of model B311 (titanium dioxide), and Sahalieben zinc sulfide HD, with a weight ratio of 20:20:20.

[0071] The T895 color powder is purchased from Longbai Group, the B311 color powder is purchased from Changzhou Antai Chemical Industry, and the Sahalieben zinc sulfide HD is purchased from Sahalieben, Germany.

[0072] Example 6

[0073] A color paste with high wettability and high hiding power, comprising 40% of polyester resin and 60% of color powder.

[0074] The toner is titanium dioxide. It is purchased from Longbai Group and the model is T895 toner.

[0075] The viscosity of the polyester resin at 23 °C is 800 - 1000 cst (excluding the point value of 1000 cst). The model is EL-PBC01 and it is purchased from Zhenjiang Lidel.

[0076] The raw materials for preparing the polyester resin include, by weight: 100 parts of terephthalic acid, 60 parts of ethylene glycol, 20 parts of adipic acid, and 1 part of benzoic acid.

[0077] The preparation method of the polyester resin includes the following steps:

[0078] S1 Mix terephthalic acid, ethylene glycol, and adipic acid, and raise the temperature to 200 °C for reaction;

[0079] S2 Remove the by-product impurities generated during the reaction through a fractionating column. When the acid value drops to 15 mg / KOH, raise the temperature to 260 °C and maintain vacuum;

[0080] S3 Test the viscosity. When the viscosity reaches 5000 - 20000 cst, add benzoic acid and cool down to below 150 °C to obtain the polyester resin.

[0081] The rest of the implementation manners are the same as those in Example 2.

[0082] Example 7

[0083] A toner with high wettability and high hiding power, including 40% of polyester resin and 60% of toner.

[0084] The toner is titanium dioxide. It is purchased from Longbai Group and the model is T895 toner.

[0085] The viscosity of the polyester resin at 23 °C is 700 - 800 cst (excluding the point value of 800 cst). The model is EL-P60 and it is purchased from Zhenjiang Lidel.

[0086] The raw materials for preparing the polyester resin include, by weight: 100 parts of terephthalic acid, 70 parts of ethylene glycol, 20 parts of adipic acid, and 3 parts of benzoic acid.

[0087] The preparation method of the polyester resin includes the following steps:

[0088] S1 Mix terephthalic acid, ethylene glycol, and adipic acid, and raise the temperature to 200 °C for reaction;

[0089] S2 Remove the by-product impurities generated during the reaction through a fractionating column. When the acid value drops to 15 mg / KOH, raise the temperature to 260 °C and maintain vacuum;

[0090] Test the viscosity at S3. When the viscosity reaches 5000 - 20000 cst, add benzoic acid and cool down to below 150 °C to obtain the polyester resin.

[0091] The remaining implementation manners are the same as those in Example 2.

[0092] Example 8

[0093] A color paste with high wettability and high hiding power, comprising 40% of polyester resin and 60% of color powder.

[0094] The color powder is titanium dioxide. Purchased from Shandong Jinhai Titanium Industry, with the model of 6618 white powder.

[0095] The remaining implementation manners are the same as those in Example 2.

[0096] Example 9

[0097] A color paste with high wettability and high hiding power, comprising 40% of polyester resin and 60% of color powder.

[0098] The color powder is titanium dioxide. Purchased from CITIC Titanium Industry, with the model of CR211 white powder. The remaining implementation manners are the same as those in Example 2.

[0099] Performance test

[0100] 1. Tensile strength: GB / T 1447 - 2005

[0101] 2. Tensile elastic modulus: GB / T 1447 - 2005

[0102] 3. Elongation at break: GB / T 1447 - 2005

[0103] 4. Flexural strength: GB / T 1449 - 2005

[0104] 5. Flexural elastic modulus: GB / T 1449 - 2005

[0105] 6. Color paste hiding power: GB / T 23981.2 - 2023

[0106] 7. Chromaticity parameters: GB / T 11186.1 - 1989

[0107] The performance test results are shown in Table 1 below.

[0108] Table 1

[0109]

[0110]

[0111] Example 2 is the best example. Example 3 has a relatively small impact on physical properties, but both the hiding power and chromaticity parameters are poor;

[0112] Example 4 has good hiding power and chromaticity parameters, but has a greater impact on the physical properties of the final fiberglass products.

[0113] Apply the color pastes of Examples 2-4 to the vacuum infusion resin. After mixing, under vacuum conditions, add 1.5 wt% of V388 curing agent, infiltrate 7 layers of composite felt, and prepare a plate with a size of 25×30 cm. The vacuum infusion resin of Example 1 is used to make a plate under the same conditions. The physical picture of Example 1 is shown in Figure 1 , and the physical pictures of Examples 2-4 are shown in Figures 2 - 4 .

Claims

1. A color paste with high wettability and high hiding power, characterized in that: The preparation raw materials include polyester resin and color powder, and the Mohs hardness of the color powder is 2-5.

2. The color paste with high wettability and high hiding power according to claim 1, characterized in that: The raw materials include 30-40% polyester resin and 60-70% toner in weight percentage, and the sum of the weight percentages of the polyester resin and the toner is 100%.

3. The color paste with high wettability and high hiding power according to claim 1, characterized in that: The toner has an average particle size of 0.1-0.5 μm and a brightness L of 95-100.

4. The color paste with high wettability and high hiding power according to claim 1, characterized in that: The oil absorption of the toner is 10-15 g / 100 g.

5. The color paste with high wettability and high hiding power according to claim 1, characterized in that: The viscosity of the polyester resin at 23° C. is 1000-1200 cst.

6. The color paste with high wettability and high hiding power according to claim 1, characterized in that: The raw materials for preparing the polyester resin include, by weight: 100 parts of terephthalic acid, 71-80 parts of ethylene glycol, 35-50 parts of adipic acid, and 3.5-5.5 parts of benzoic acid.

7. The color paste with high wettability and high hiding power according to claim 6, characterized in that: The preparation method of the polyester resin comprises the following steps: S1: terephthalic acid, ethylene glycol and adipic acid are mixed and heated to 180-220°C for reaction; The by-product impurities produced during the S2 reaction are removed through a fractionation column. When the acid value drops to 10-20 mg / KOH, the temperature is raised to 250-270°C and vacuum is maintained; S3 tests the viscosity. When the viscosity reaches 5000-20000 cst, benzoic acid is added and the temperature is lowered to below 150°C to obtain polyester resin.

8. A method for preparing a color paste with high wettability and high hiding power according to any one of claims 1 to 7, characterized in that: The following steps are involved: The polyester resin and the color powder are mixed evenly to obtain a color paste.

9. An application of the color paste with high wettability and high hiding power according to any one of claims 1 to 7, characterized in that: Used for vacuum infusion of resins.

10. The use of the color paste with high wettability and high hiding power according to claim 9, characterized in that: The weight ratio of the color paste to the vacuum-introduced resin is (1-3): (97-99).

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