A high thixotropic ink oil for photovoltaic paste and its preparation method

Abstract

The present invention relates to the field of glass paste, and specifically relates to a novel high thixotropic ink oil for photovoltaic paste and a preparation method thereof. The components of a novel high thixotropic ink oil for photovoltaic paste include: an environmentally friendly solvent, a water-soluble acrylic resin B7, a water-soluble acrylic resin B12, a dispersant, a thickener, a wetting agent, and an antifoaming agent. This ink oil has the advantages of high thixotropy, environmental protection, high adhesion, high reflectivity, etc., can be widely used in photovoltaic glass paste, and is well applicable to printing different types of glass, such as float glass, embossed glass, etc.

Description

Technical Field

[0001] The present invention relates to the fields of new materials and glass pastes, and specifically relates to a high thixotropic ink oil for photovoltaic pastes and a preparation method thereof. Background Art

[0002] Photovoltaic power generation is a technology that directly converts light energy into electrical energy by using the photovoltaic effect at the semiconductor interface. Its system structure has no mechanical moving parts, is pollution-free, noiseless, has a long working life, and also has the unique advantage of a modular structure, making it suitable for power production of any scale, from large central power plants to small private residential power supplies. Photovoltaic glass paste, as a raw material for photovoltaic power generation components, has an important impact on the efficiency of photovoltaic power generation.

[0003] Photovoltaic power generation mainly consists of three major parts: solar panels (crystalline silicon modules), controllers, and inverters. The solar panels are composed of crystalline silicon modules, and the efficiency of photovoltaic power generation mainly depends on the conversion efficiency of crystalline silicon modules to convert solar energy into electrical energy. Experimental studies have found that: the glass paste used for crystalline silicon modules has a greater impact on its light reflectivity and adhesion and other properties, and it is relatively difficult to achieve both high adhesion and high reflectivity at the same time. Often, when obtaining a high reflectivity, the adhesion is relatively low, and when obtaining high adhesion, the reflectivity will decrease. Therefore, in order to simultaneously improve the light conversion efficiency and service life of crystalline silicon modules, it is of great significance to develop a photovoltaic glass paste with both high reflectivity and high adhesion.

[0004] In the case of the same glass powder, the ink oil has a certain impact on the printability, reflectivity, adhesion and other properties of the glass paste. Therefore, the performance of the ink oil also affects the utilization rate of photovoltaic power generation. Summary of the Invention

[0005] To solve the above problems, the present invention discloses a high thixotropic ink oil for photovoltaic pastes and a preparation method thereof, and prepares an ink oil with high thixotropy, high water washing performance, high homogenization and high transfer and transmission properties.

[0006] A high thixotropic ink oil for photovoltaic pastes contains the following components by weight percentage:

[0007] Environmental protection solvent: 85 - 90%; Water-soluble acrylic resin B7: 2 - 8%; Water-soluble acrylic resin B12: 4 - 14%; Dispersant: 0.2 - 5%; Thickener: 0.2 - 6%; Wetting agent: 0.2 - 2%; Defoamer 0.01 - 0.05%.

[0008] Preferably, the water-soluble acrylic resin B7 refers to a water-soluble acrylic resin with a weight-average molecular weight of 65,000 to 75,000 Mw; the water-soluble acrylic resin B12 refers to a water-soluble acrylic resin with a weight-average molecular weight of 115,000 to 125,000 Mw.

[0009] Preferably, the water-soluble acrylic resin comprises the following components in parts by weight:

[0010] Methyl methacrylate: 30 - 70 parts; butyl acrylate: 19 - 59 parts; 2-hydroxyethyl methacrylate: 1 - 19 parts; acrylic acid: 1 - 5 parts; initiator: 0.1 - 2 parts; chain transfer agent: 0.1 - 1; solvent: 100 - 120 parts.

[0011] Preferably, the environmental protection solvent is diethylene glycol butyl ether, diethylene glycol butyl ether acetate, dipropylene glycol methyl ether, and / or propylene glycol ethyl ether acetate.

[0012] Preferably, the thickening agent is methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, or ethyl cellulose.

[0013] Preferably, the dispersant is TEGO Dispers 750W, TEGO Dispers 755W, or TEGO Dispers 757W.

[0014] Preferably, the wetting agent is LD8375, LD91083, or LD8270.

[0015] Preferably, the defoaming agent is P-06, P-09, P-20, BYK-024, or BYK-054.

[0016] Another object of the present invention is to disclose a preparation method of the novel high-thixotropic ink oil for photovoltaic paste, and the preparation method comprises the following steps:

[0017] S1 Preparation of water-soluble acrylic resin: Methyl methacrylate, butyl acrylate, 2-hydroxyethyl methacrylate, and acrylic acid are sequentially added into a reaction kettle, then the solvent is added and stirred to dissolve and mix evenly, and then heated. An initiator and a chain transfer agent are added to the mixed solution for reaction. After the reaction is completed, a water-soluble acrylic resin is obtained; the obtained water-soluble acrylic resin is dried and ground to obtain fine granular water-soluble acrylic resin;

[0018] S2 Preparation of high-thixotropic ink oil: Weighed resin, solvent, thickening agent, dispersant, wetting agent, and defoaming agent are sequentially added into a heating and stirring container according to weight percentages, and then heated and stirred to obtain a uniform liquid, thus preparing the high-thixotropic ink oil.

[0019] Preferably, in the preparation step of the S1 water-soluble acrylic resin, the mass ratio of methyl methacrylate to the solvent is 1:(17-20).

[0020] Preferably, in the preparation step of the S1 water-soluble acrylic resin, the stirring speed is 300-500 rpm.

[0021] Preferably, in the preparation step of the S1 water-soluble acrylic resin, the heating temperature is 40-60 °C.

[0022] Preferably, in the preparation step of the S2 highly thixotropic ink oil, the required heating temperature is 55-65 °C.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] (1) In the highly thixotropic ink oil of the present invention, by adjusting the combination of resins with different molecular weights, the glass paste has good fluidity during dynamic movement and poor fluidity under static conditions, ensuring that the shape on the printing substrate can be maintained after printing and guaranteeing good printability.

[0025] (2) In the highly thixotropic ink oil of the present invention, through the mixed combination of high and low molecular weight resin contents, the ink can have high thixotropy at a relatively low viscosity state, enabling a high content of glass powder in the mixed paste, increasing the reflectivity, and thus improving the efficiency of photovoltaic power generation.

[0026] (3) In the raw material water-soluble acrylic resin of the highly thixotropic ink oil of the present invention, functional monomers containing hydroxyl (-OH) are selected to introduce hydroxyl groups; and functional monomers containing acylamino (-CONH2) are used to introduce hydrophilic groups such as acylamino groups to increase the water solubility of the ink. Then, by adding a certain proportion of hydrophilic co-solvent, the water solubility of the ink is further increased, improving the water washing performance of the ink, ensuring the rapid cleaning of defective glass products during a large number of printings, and simply and conveniently realizing the recycling of glass.

[0027] (4) In the highly thixotropic ink oil of the present invention, during the stirring process of the ink, the apparent viscosity of the ink will rapidly decrease, improving the homogenization and transfer and transmission properties of the ink, and greatly improving the stirring efficiency. Specific Embodiments

[0028] The following embodiments are provided to better further understand the present invention. They are not limited to the best embodiment, and do not constitute a limitation to the content and protection scope of the present invention. Any product that is the same as or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior art features falls within the protection scope of the present invention.

[0029] For those without specific experimental procedures or conditions indicated in the examples, the operations or conditions of the conventional experimental procedures described in the literature in this field can be followed. For reagents or instruments without the manufacturer indicated, they are all conventional reagent products that can be obtained through commercial purchase.

[0030] Example 1

[0031] A high thixotropic ink oil for photovoltaic paste, comprising the following components by mass percentage: environmental protection solvent: 75%; water-soluble acrylic resin B7: 2%; water-soluble acrylic resin B12: 4%; dispersant: 0.2%; thickener: 0.2%; wetting agent: 0.2%; defoaming agent: 0.01%.

[0032] A preparation method of a high thixotropic ink oil for photovoltaic paste, comprising the following steps:

[0033] S1 Preparation of water-soluble acrylic resin:

[0034] (1) Preparation of water-soluble acrylic resin B7: 30 parts by weight of methyl methacrylate, 19 parts of butyl acrylate, 1 part of 2-hydroxyethyl methacrylate and 1 part of acrylic acid were successively added to the reaction kettle, and then 100 parts by weight of solvent was added for stirring to dissolve and mix evenly. The stirring speed was 300 rpm, and then the temperature was heated to 40°C. Subsequently, 0.1 part of initiator and 0.1 part of chain transfer agent were added to the mixed solution for polymerization reaction. After the reaction ended, water-soluble acrylic resin B7 was obtained. The obtained water-soluble acrylic resin was dried and ground to obtain fine granular water-soluble acrylic resin B7, with a weight of 50 parts.

[0035] (2) Preparation of water-soluble acrylic resin B12: 50 parts by weight of methyl methacrylate, 40 parts of butyl acrylate, 1 part of 2-hydroxyethyl methacrylate and 1 part of acrylic acid were successively added to the reaction kettle, and then 100 parts by weight of solvent was added for stirring to dissolve and mix evenly. The stirring speed was 300 rpm, and then the temperature was heated to 40°C. Subsequently, 0.1 part of initiator and 0.1 part of chain transfer agent were added to the mixed solution for polymerization reaction. After the reaction ended, water-soluble acrylic resin B12 was obtained. The obtained water-soluble acrylic resin was dried and ground to obtain fine granular water-soluble acrylic resin B12, with a weight of 90 parts.

[0036] S2 Preparation of high thixotropic ink oil: 1500 parts by weight of environmental protection solvent, 40 parts of water-soluble acrylic resin B7, 80 parts of water-soluble acrylic resin B12, 4 parts of dispersant, 4 parts of thickener, 4 parts of wetting agent and 0.2 part of defoaming agent were placed in a heating and stirring container. The reaction temperature was heated to 55°C, and the reaction speed was 500 rpm. Then, heating and stirring were carried out to obtain a uniform liquid, and the high thixotropic ink oil was prepared.

[0037] Example 2

[0038] A high thixotropic ink oil for photovoltaic paste, comprising the following components by mass percentage: environmental protection solvent: 80%; water-soluble acrylic resin B7: 4%; water-soluble acrylic resin B12: 8%; dispersant: 1.0%; thickener: 1.0%; wetting agent: 0.6%; defoaming agent: 0.02%.

[0039] A preparation method of a high thixotropic ink oil for photovoltaic paste, comprising the following steps:

[0040] S1 Preparation of water-soluble acrylic resin:

[0041] (1) Preparation of water-soluble acrylic resin B7: Add 40 parts by weight of methyl methacrylate, 20 parts by weight of butyl acrylate, 10 parts by weight of hydroxyethyl methacrylate and 3 parts by weight of acrylic acid into a reaction kettle in sequence, then add 110 parts by weight of solvent and stir to dissolve and mix evenly. The stirring speed is 400 rpm, then heat the temperature to 50 °C, then add 1 part by weight of initiator and 1 part by weight of chain transfer agent into the mixed solution for polymerization reaction. After the reaction is completed, water-soluble acrylic resin B7 is obtained. Dry and grind the obtained water-soluble acrylic resin to obtain fine granular water-soluble acrylic resin B7, with a weight of 70 parts by weight.

[0042] (2) Preparation of water-soluble acrylic resin B12: Add 60 parts by weight of methyl methacrylate, 49 parts by weight of butyl acrylate, 10 parts by weight of hydroxyethyl methacrylate and 3 parts by weight of acrylic acid into a reaction kettle in sequence, then add 110 parts by weight of solvent and stir to dissolve and mix evenly. The stirring speed is 400 rpm, then heat the temperature to 50 °C, then add 1 part by weight of initiator and 1 part by weight of chain transfer agent into the mixed solution for polymerization reaction. After the reaction is completed, water-soluble acrylic resin B12 is obtained. Dry and grind the obtained water-soluble acrylic resin to obtain fine granular water-soluble acrylic resin B12, with a weight of 120 parts by weight.

[0043] S2 Preparation of high thixotropic ink oil: Place 1200 parts by weight of environmental protection solvent, 60 parts by weight of water-soluble acrylic resin B7, 120 parts by weight of water-soluble acrylic resin B12, 15 parts by weight of dispersant, 15 parts by weight of thickener, 9 parts by weight of wetting agent and 0.3 parts by weight of defoaming agent into a heating and stirring container, heat the reaction temperature to 60 °C, the reaction speed is 500 rpm, then carry out heating and stirring to obtain a uniform liquid, and prepare a high thixotropic ink oil.

[0044] Example 3

[0045] A high thixotropic ink oil for photovoltaic paste, comprising the following components in mass percentage: environmental protection solvent: 85%; water-soluble acrylic resin B7: 6%; water-soluble acrylic resin B12: 11%; dispersant: 2.0%; thickener: 2.0%; wetting agent: 1.0%; defoamer: 0.03%.

[0046] A preparation method of a high thixotropic ink oil for photovoltaic paste, comprising the following steps:

[0047] S1 Preparation of water-soluble acrylic resin:

[0048] (1) Preparation of water-soluble acrylic resin B7: Add 50 parts by weight of methyl methacrylate, 30 parts of butyl acrylate, 19 parts of 2-hydroxyethyl methacrylate and 5 parts of acrylic acid into the reaction kettle in sequence, then add 120 parts by weight of solvent for stirring to dissolve and mix evenly. The stirring speed is 500 rpm, then heat the temperature to 60 °C, and then add 2 parts of initiator and 2 parts of chain transfer agent into the mixed solution for polymerization reaction. After the reaction ends, water-soluble acrylic resin B7 is obtained. Dry and grind the obtained water-soluble acrylic resin to obtain fine granular water-soluble acrylic resin B7, with a weight of 100 parts by weight.

[0049] (2) Preparation of water-soluble acrylic resin B12: Add 70 parts by weight of methyl methacrylate, 59 parts of butyl acrylate, 19 parts of 2-hydroxyethyl methacrylate and 5 parts of acrylic acid into the reaction kettle in sequence, then add 120 parts by weight of solvent for stirring to dissolve and mix evenly. The stirring speed is 500 rpm, then heat the temperature to 60 °C, and then add 2 parts of initiator and 2 parts of chain transfer agent into the mixed solution for polymerization reaction. After the reaction ends, water-soluble acrylic resin B12 is obtained. Dry and grind the obtained water-soluble acrylic resin to obtain fine granular water-soluble acrylic resin B12, with a weight of 150 parts by weight.

[0050] S2 Preparation of high thixotropic ink oil: Place 992 parts by weight of environmental protection solvent, 70 parts of water-soluble acrylic resin B7, 128 parts of water-soluble acrylic resin B12, 23 parts of dispersant, 23 parts of thickener, 12 parts of wetting agent and 0.35 part of defoamer in a heating and stirring container, heat the reaction temperature to 65 °C, the reaction speed is 500 rpm, and then carry out heating and stirring to obtain a uniform liquid, thus preparing the high thixotropic ink oil.

[0051] Example 4

[0052] A high thixotropic ink oil for photovoltaic paste, comprising the following components by mass percentage: environmental protection solvent: 90%; water-soluble acrylic resin B7: 8%; water-soluble acrylic resin B12: 14%; dispersant: 5.0%; thickener: 6.0%; wetting agent: 2.0%; defoamer: 0.05%.

[0053] A preparation method of a high thixotropic ink oil for photovoltaic paste, comprising the following steps:

[0054] S1 The preparation of the water-soluble acrylic resin is the same as that in Example 3.

[0055] S2 Preparation of high thixotropic ink oil: Put 788 parts by weight of environmental protection solvent, 70 parts of water-soluble acrylic resin B7, 123 parts of water-soluble acrylic resin B12, 44 parts of dispersant, 53 parts of thickener, 18 parts of wetting agent and 0.44 parts of defoamer into a heating and stirring container, heat the reaction temperature to 65 °C, the rotation speed of the reaction is 500 rpm, and then carry out heating and stirring to obtain a uniform liquid, thus preparing the high thixotropic ink oil.

[0056] Comparative Example 1

[0057] Different from Example 3, the component ratios in this example are: water-soluble acrylic resin B7: 10%, thickener (ethyl cellulose): 6%; environmental protection solvent (diethylene glycol butyl ether): 56.5%; environmental protection solvent (diethylene glycol butyl ether acetate): 24%; dispersion aid (TEGO Dispers 750W): 2%; wetting agent (LD8270): 1.5%; defoamer (P-06): 0.01%, and the rest are the same as in Example 1.

[0058] Comparative Example 2

[0059] Different from Example 3, the component ratios in this example are: water-soluble acrylic resin B12: 10%, thickener (ethyl cellulose): 6%; environmental protection solvent (diethylene glycol butyl ether): 56.5%; environmental protection solvent (diethylene glycol butyl ether acetate): 24%; dispersion aid (TEGO Dispers 750W): 2%; wetting agent (LD8270): 1.5%; defoamer (P-06): 0.01%, and the rest are the same as in Example 1.

[0060] The water-based ink oils used in Comparative Examples 3 to 4 are all commercially available products:

[0061] Comparative Example 3 is selected from Yingde Xinlian Chemical Co., Ltd. Main components: resin 30%, solvent 65%, additives 5%.

[0062] Comparative Example 4 is selected from Nantong Zhonghe Chemical New Materials Co., Ltd. Main components: resin 35%, solvent 60%, additives 5%.

[0063] The ink oils of Examples 1-4 and Comparative Examples 1-4 were mixed with the same glass powder to form a glass paste for performance testing.

[0064] Test method: Referring to the corresponding national testing standards, the glass paste was screen-printed onto untempered embossed glass with a 250-mesh screen, and the wet film thickness was 20 ± 2 μm. Then, it was tempered at 710 °C for 100 s, and the performance of the glass paste after sintering was tested by different instruments. Test results: The test results are shown in the following table.

[0065]

[0066] From the above experimental results, it can be seen that the ink oils prepared in Examples 1-4 of the present invention have excellent reflectivity, covering property, good adhesion, good water washing property after tempering, and good compatibility between the ink oil and the glass powder. Among them, the combination of the two resins ensures the thixotropy and fluidity of the paste, and at the same time enables the glass paste to have a high solid content, improving the reflectivity; the synergistic effect of the dispersant and the wetting agent ensures the bonding at the interface between the paste and the glass, improving the adhesion of the paste; the addition of the thickening agent ensures that the viscosity of the paste is moderate, improving the storage stability of the paste. Among them, Example 3 has the best comprehensive performance and is the best example of the present invention.

[0067] By comparing Example 3 with Comparative Example 1 and Comparative Example 2, it can be seen that by matching two resins with different molecular weights, the thixotropy of the glass paste can be changed, and different printing effects and different solid contents can be obtained, thereby improving the reflectivity of the glass paste.

[0068] Obviously, the above examples are only for clear illustration and not for limitation of the implementation mode. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all implementation modes here. And the obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims

1. A high thixotropic ink oil for photovoltaic paste, characterized in that, Comprising components in the following weight percentages: Environmentally friendly solvent: 85 - 90%; Water-soluble acrylic resin B7: 2 - 8%; Water-soluble acrylic resin B12: 4 - 14%; Dispersant: 0.2 - 5%; Thickener: 0.2 - 6%; Wetting agent: 0.2 - 2%; Defoamer: 0.01 - 0.05%; The water-soluble acrylic resin B7 refers to a water-soluble acrylic resin with a weight average molecular weight of 65000 - 75000 Mw; The water-soluble acrylic resin B12 refers to a water-soluble acrylic resin with a weight average molecular weight of 115000 - 125000 Mw.

2. The high-thixotropic ink oil for photovoltaic paste according to claim 1, wherein The water-soluble acrylic resin comprises the following components in parts by weight: Methyl methacrylate: 30 - 70 parts; Butyl acrylate: 19 - 59 parts; 2-Hydroxyethyl methacrylate: 1 - 19 parts; Acrylic acid: 1 - 5 parts; Initiator: 0.1 - 2 parts; Chain transfer agent: 0.1 - 1; Solvent: 100 - 120 parts.

3. A high thixotropic ink oil for photovoltaic paste according to claim 1, characterized in that, The environmentally friendly solvent is diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether and / or propylene glycol monoethyl ether acetate.

4. A high thixotropic ink oil for photovoltaic paste according to claim 1, characterized in that, The thickener is methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose or ethyl cellulose.

5. The preparation method of a highly thixotropic ink oil for photovoltaic paste according to claim 1, characterized in that, Including the following steps: S1 Preparation of water-soluble acrylic resin: Add methyl methacrylate, butyl acrylate, 2-hydroxyethyl methacrylate and acrylic acid into the reaction kettle in sequence, then add the solvent and stir to dissolve and mix evenly, then heat, add the initiator and chain transfer agent into the mixed solution for reaction, and obtain the water-soluble acrylic resin after the reaction ends; Dry and grind the obtained water-soluble acrylic resin to obtain fine granular water-soluble acrylic resin; S2 Preparation of high thixotropic printing ink oil: Weigh the resin, solvent, thickener, dispersant, wetting agent and defoamer according to the weight percentages and add them into the heating and stirring container in sequence, then heat and stir to obtain a uniform liquid, and prepare the high thixotropic printing ink oil.

6. The preparation method of a high thixotropic ink oil for photovoltaic paste according to claim 5, characterized in that, In the S1 step of preparing water-soluble acrylic resin, the mass ratio of methyl methacrylate to the solvent is 1:(17 - 20).

7. The preparation method of a high thixotropic ink oil for photovoltaic paste according to claim 5, characterized in that, In the S1 step of preparing water-soluble acrylic resin, the stirring speed is 300 - 500 rpm.

8. The preparation method of a highly thixotropic ink oil for photovoltaic paste according to claim 5, characterized in that, In the S1 step of preparing water-soluble acrylic resin, the heating temperature is 40 - 60 °C.

9. The preparation method of a highly thixotropic ink oil for photovoltaic paste according to claim 5, characterized in that, In the S2 step of preparing high thixotropic printing ink oil, the heating temperature required is 55 - 65 °C.

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