Thermocuring silk-screen printing ink and application thereof

Abstract

The invention provides thermocuring silk-screen printing ink and application thereof. The thermocuring silk-screen printing ink comprises main agent printing ink and a curing agent, the main agent ink comprises benzene-ring-free epoxy resin and a first filler; the curing agent is a resin system containing carboxylic acid groups; the molar ratio of epoxy groups in the benzene-ring-free epoxy resin to carboxylic acid groups in the resin system containing the carboxylic acid groups is (2-1): (1-2). The thermocuring silk-screen printing ink is rapidly cured to form a solid coating at proper temperature and time, and has excellent UV resistance, heat resistance and silk-screen printing effect after being cured.

Description

Technical Field

[0001] The invention relates to the technical field of photovoltaic ink compositions, and in particular to a thermal curing silk screen ink and application thereof. Background Art

[0002] The new generation of insulating glue used in the double-glass field is expected to be transparent and UV-resistant, which can also be used as protective glue on the front of the component. At present, the performance evaluation of insulating glue is mainly measured from the aspects of light transmittance, viscosity, full-plate coating warping, UV resistance, hardness, adhesion, etc. However, the UV resistance of insulating glue has always been poor, especially under high temperature conditions, it is easy to turn yellow, and the yellowing resistance is weak. At the same time, in order to meet the current requirements of fast silk screen printing of insulating glue, higher requirements are put forward for insulating glue. Therefore, how to improve the UV resistance of insulating glue and meet the requirements of fast silk screen printing is an important problem we need to solve. Summary of the invention

[0003] The present invention aims to solve one of the technical problems in the prior art at least to a certain extent. To this end, one object of the present invention is to provide a heat curing screen printing ink and its application.

[0004] In a first aspect of the present invention, the present invention provides a heat-curable screen printing ink. According to an embodiment of the present invention, the heat-curable screen printing ink comprises: a base ink and a curing agent; The main ink comprises a benzene ring-free epoxy resin and a first filler; The curing agent is a resin system containing a carboxylic acid group; The molar ratio of the epoxy group in the benzene ring-free epoxy resin to the carboxylic acid group in the resin system containing the carboxylic acid group is (2-1): (1-2).

[0005] According to the thermosetting screen printing ink of the above embodiment of the present invention, the use of a benzene ring-free epoxy resin and a resin system containing a carboxylic acid group can improve the UV resistance of the ink and avoid yellowing of the ink. Although the use of a benzene ring-free epoxy resin and a resin system containing a carboxylic acid group improves the UV resistance of the ink, its screen printing effect is not good. The main reason is that the acrylic resin containing a carboxylic acid group generally has a large molecular weight and is soluble in a volatile solvent. After the solvent evaporates, the resin is solid, which causes the scraper to scrape back and forth quickly across the screen during the fast screen printing process, causing the quick-drying solvent to evaporate, the solvent content to decrease, and the viscosity of the resin solution containing the carboxylic acid group to increase rapidly, causing the coating printing parameters to change and not match the original screen printing process. A more serious phenomenon is the precipitation of solid resin, which blocks the screen. In view of this, the inventors have found that by controlling the molar ratio of the epoxy groups in the benzene ring-free epoxy resin to the carboxylic acid groups in the resin system containing carboxylic acid groups to be (2-1): (1-2), such as 2:1, 1:1, 1:2, etc., or a range between any two of the above values, the thermosetting screen printing ink can be quickly cured to form a solid coating at a suitable temperature and time without causing an excess of a certain component, resulting in an incompletely cured coating, stickiness, and insufficient hardness.

[0006] In some embodiments of the present invention, the number average molecular weight of the resin containing carboxylic acid groups in the resin system containing carboxylic acid groups is 1000-5000 g / mol. For example, the molecular weight is 1000 g / mol, 2000 g / mol, 3000 g / mol, 4000 g / mol, 5000 g / mol, etc., or the range between any two values ​​of the above. The inventors have found that by controlling the number average molecular weight of the resin containing carboxylic acid groups in the resin system containing carboxylic acid groups within the above range, the resin containing carboxylic acid groups exists in the form of liquid resin or semi-solid resin, which can enable the ink to achieve rapid screen printing, and the resin with the above molecular weight has good compatibility, further improving the screen printing effect of the ink.

[0007] In some embodiments of the present invention, the acid value of the resin containing carboxylic acid groups in the resin system containing carboxylic acid groups is 20mgKOH / g~250mgKOH / g. For example, the acid value of the resin is 20mgKOH / g, 50mgKOH / g, 100mgKOH / g, 200mgKOH / g, 250mgKOH / g, etc., or the range between any two values ​​of the above. The inventors found that the acid value of the resin containing carboxylic acid groups in the resin system containing carboxylic acid groups is within the above range, and can be reasonably matched with epoxy resin. The epoxy groups of epoxy resin are at the same level, which can ensure the density of cross-linking groups, so that the degree of curing will not be too low, and the mechanical properties of the coating can be made easier to control, and there will be no excessive epoxy in the coating, the coating will be hard, and there will be no excessive carboxylic acid resin, and the heat resistance of the coating will be insufficient.

[0008] In some embodiments of the present invention, the mass fraction of the resin containing carboxylic acid groups in the resin system containing carboxylic acid groups is 60-95%, and the mass fraction of the solvent is 5-40%. For example, the mass fraction of the resin containing carboxylic acid groups is 60%, 70%, 80%, 90%, 95%, etc., or a range between any two of the above values. The inventors have found that the mass fraction of the solvent in the resin system containing carboxylic acid groups is kept within the above range, so that the viscosity of the resin system containing carboxylic acid groups can be controlled within a reasonable range, and the solvent content can be controlled after being used in the coating system.

[0009] In some embodiments of the present invention, the carboxylic acid group-containing resin in the carboxylic acid group-containing resin system is formed by polymerizing an acid functional monomer and a non-acid functional monomer in the presence of a chain transfer agent. The inventors have found that the carboxylic acid group-containing resin in the carboxylic acid group-containing resin system is formed by polymerizing an acid functional monomer and a non-acid functional monomer in the presence of a chain transfer agent, which can reduce the polymerization degree of the resin and form a liquid resin, thereby improving the silk screen printing effect of the ink.

[0010] Preferably, the resin containing carboxylic acid groups has the general structural formula: , wherein MMA is a non-acid functional monomer; AA is an acid functional monomer; Z is a C4~C12 alkylthio group, a C4~C12 alkyl group, a phenyl group or a benzyl group; X is an isopropanoyl group, an acetic acid group, a 2-nitriloacetic acid group or a 2-aminoacetic acid group; n is the total polymerization degree of the acid functional monomer and the non-acid functional monomer, n=10~50, wherein the polymerization degree of the acid functional monomer is 2~10, and the polymerization degree of the non-acid functional monomer is 6~40.

[0011] In some embodiments of the present invention, the non-acid functional monomer includes at least one of methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, hexyl methacrylate, hexyl acrylate, decyl methacrylate, decyl acrylate, lauryl methacrylate, lauryl acrylate, tetrahydrofuran methacrylate, tetrahydrofuran acrylate, isobornyl methacrylate, isobornyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate and hydroxypropyl acrylate.

[0012] In some embodiments of the present invention, the acid functional monomer includes at least one of methacrylic acid and acrylic acid.

[0013] In some embodiments of the present invention, the chain transfer agent includes a thiol compound.

[0014] In some embodiments of the present invention, the resin system containing carboxylic acid groups further comprises a second filler. By adding a filler to the resin system containing carboxylic acid groups, the film-forming property of the ink can be improved.

[0015] In some embodiments of the present invention, based on the total mass of the resin system containing carboxylic acid groups, the mass of the second filler accounts for no more than 30%, thereby improving the film-forming property of the ink.

[0016] In some embodiments of the present invention, the second filler includes at least one of gas silica, silica powder, glass powder, barium sulfate, mica and phosphor.

[0017] In some embodiments of the present invention, the benzene ring-free epoxy resin includes at least one of hydrogenated bisphenol A epoxy resin, aliphatic glycidyl ether resin, ester ring epoxy resin, silicone epoxy resin and glycidyl amine resin.

[0018] In some embodiments of the present invention, the first filler includes at least one of aerosil, silica powder, glass powder, barium sulfate, mica and phosphor.

[0019] In some embodiments of the present invention, based on the total mass of the thermosetting screen printing ink, the mass proportion of the first filler is 0.5% to 30%, thereby improving the film-forming property of the ink.

[0020] In some embodiments of the present invention, the viscosity of the thermosetting screen printing ink is 5Pa·s to 30Pa·s. For example, the viscosity is 5Pa·s, 10Pa·s, 15Pa·s, 20Pa·s, 25Pa·s, 30Pa·s, etc., or a range between any two of the above values. The inventors have found that by controlling the viscosity of the thermosetting screen printing ink within the above range, the coating can prevent glue leakage on the screen printing screen during the screen printing process, the ink is applied in a good amount, and the printing is good. During the screen printing and curing process, a good shaping effect can be maintained.

[0021] In some embodiments of the present invention, the mass fraction of the solvent in the thermosetting screen printing ink is 2% to 20%. For example, the mass fraction is 2%, 5%, 10%, 15%, 20%, etc., or a range between any two of the above values. The inventors have found that the mass fraction of the solvent in the thermosetting screen printing ink is within the above range, which can adjust the viscosity of the system and adapt it to the client's screen printing process. The low amount of solvent allows the scraper to quickly scrape back and forth across the screen during the fast screen printing process, and a small amount of slow-drying solvent evaporates. After a small amount of high-boiling solvent evaporates, the viscosity of the coating changes little, matching the original screen printing process.

[0022] In some embodiments of the present invention, an auxiliary agent is also included. Further, the auxiliary agent includes at least one of a defoaming agent, a leveling agent and a dispersant.

[0023] In some embodiments of the present invention, based on the total mass of the thermosetting screen printing ink, the mass proportion of the auxiliary agent is 0.1% to 2%.

[0024] The present invention has at least the following technical effects: The thermosetting screen printing ink of the present invention does not contain a benzene ring, and the benzene ring-free epoxy resin and the carboxylic acid group-containing resin system cooperate with each other to work synergistically to improve the UV resistance and heat resistance of the ink. At the same time, the benzene ring-free epoxy resin and the carboxylic acid group-containing resin system used in the present invention have good compatibility and meet the performance requirements of the liquid resin, so that the ink has an excellent screen printing effect. In addition, the solvent mass fraction in the thermosetting screen printing ink is 2-20%, and such a small amount of solvent system can also reduce VOC emissions, which is more environmentally friendly and healthy. DETAILED DESCRIPTION

[0025] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. The present invention is described below with reference to specific embodiments. It should be noted that these embodiments are merely illustrative and do not limit the present invention in any way.

[0026] The preparation of the resin containing carboxylic acid groups of the present invention is as follows: The chemical structure of carboxylic acid resin is:

[0027] Wherein, n1 is the degree of polymerization of the methyl methacrylate monomer unit, n1=6-40; n2 is the degree of polymerization of the methacrylic acid monomer unit, n2=2-10.

[0028] The preparation method of the carboxylic acid resin of the above structure comprises: (1) 2.38 g of precursor, 0.2 g of azobisisocyanovaleric acid initiator, 6-40 g of methyl methacrylate, 1.44-7.2 g of acrylic acid, 0-20 g of acetone, and 0-20 g of DBE were mixed, and after nitrogen was passed to remove oxygen, the mixture was reacted at 80°C for 2 hours. The volatile solvent acetone was removed by vacuum to obtain a resin containing a carboxylic acid group.

[0029] The structural formula of the precursor is: ; Wherein, Z is an alkylthio group having four carbon atoms, and X is an isopropanoyl group; The preparation of the precursor is prior art, including but not limited to references FERGUSON CJ, HUGHES RJ, NGUYEN D, PHAM BTT, GILBERT RG, SERELIS AK, SUCH CH, HAWKETT BS. Ab initioemulsion polymerization by RAFT-controlled self-assembly [J]. Macromolecules, 2005, 38(6): 2191-2204.

[0030] In the above method, different monomers are selected and added according to the difference between the non-acid functional group monomer MMA and the acid functional group monomer AA to prepare resins containing different carboxylic acid groups.

[0031] Resin A containing carboxylic acid groups: (1) 2.38 g of precursor, 0.2 g of azobisisocyanovaleric acid initiator, 40 g of methyl methacrylate, 7.2 g of acrylic acid, 20 g of acetone, and 20 g of DBE were mixed, and after nitrogen was passed through to remove oxygen, the mixture was reacted at 80° C. for 2 hours, and the volatile solvent acetone was removed by vacuum to obtain resin A containing carboxylic acid groups. The number average molecular weight of the prepared resin A containing carboxylic acid groups was 5000 g / mol, and the acid value was 112 mgKOH / g.

[0032] Resin B containing carboxylic acid groups: The main difference in the preparation process of resin B containing carboxylic acid groups and resin A containing carboxylic acid groups is that the MMA used is n-butyl acrylate and hydroxyethyl acrylate, and the AA used is acrylic acid. The number average molecular weight of the prepared resin B containing carboxylic acid groups is 3500 g / mol, and the acid value is 56 mgKOH / g.

[0033] Resin C containing carboxylic acid groups: The main difference in the preparation process of resin C containing carboxylic acid groups and resin A containing carboxylic acid groups is that the MMA used is ethyl acrylate, and the AA used is acrylic acid. The number average molecular weight of the prepared resin C containing carboxylic acid groups is 1000 g / mol, and the acid value is 20 mgKOH / g.

[0034] Resin D containing carboxylic acid groups: The main differences in the preparation process of resin D containing carboxylic acid groups and resin A containing carboxylic acid groups are: the MMA used is methyl methacrylate and hydroxyethyl acrylate, the AA used is methacrylic acid, and the number average molecular weight of the prepared resin D containing carboxylic acid groups is 2500g / mol, and the acid value is 250mgKOH / g.

[0035] The molecular structure of the resin was determined by NMR and MALDI-TOF, using DMSO-d6 as a deuterated reagent.

[0036] Example 1

[0037] The composition of the heat curing screen printing ink in this embodiment is: (1) Main agent: Benzene ring-free epoxy resin: hydrogenated bisphenol A epoxy resin DER331 (Dow), 100 parts by weight; First filler: 25 parts by weight of barium sulfate, 3 parts by weight of gas silicon R106 (Evonik); (2) Curing agent: resin system A containing carboxylic acid groups, the added solvent is DBE, the mass fraction of the resin is 70%, the resin system A containing carboxylic acid groups adopts the above-mentioned resin A containing carboxylic acid groups, and the curing agent is 80 parts by weight; The molar ratio of hydrogenated bisphenol A epoxy resin DER331 to the carboxylic acid group in the resin system containing carboxylic acid groups is 1:2

[0038] (3) Additives: Defoaming agent: BYK065 1 part by weight.

[0039] The above materials were ground separately and stirred before use. The viscosity of the prepared thermosetting screen printing ink was 25 Pa·s, and the mass fraction of the solvent in the thermosetting screen printing ink was 10%.

[0040] Example 2

[0041] The difference between Example 2 and Example 1 is: The weight parts of the curing agent used in Example 2 are different from those in Example 1. Example 2 uses 40 parts by weight of the resin system A containing carboxylic acid groups, so that the molar ratio of hydrogenated bisphenol A type epoxy resin DER331 (Dow) to the carboxylic acid groups in the resin system A containing carboxylic acid groups is 1:1.

[0042] The above materials were ground separately and stirred before use. The viscosity of the prepared thermosetting screen printing ink was 22 Pa·s, and the mass fraction of the solvent in the thermosetting screen printing ink was 7%.

[0043] Example 3

[0044] The difference between Example 3 and Example 1 is: The weight parts of the curing agent used in Example 3 are different from those in Example 1. Example 3 uses 20 parts by weight of the resin system A containing carboxylic acid groups, so that the molar ratio of hydrogenated bisphenol A type epoxy resin DER331 (Dow) to the carboxylic acid groups in the resin system A containing carboxylic acid groups is 2:1.

[0045] The above materials were ground separately and stirred before use. The viscosity of the prepared thermosetting screen printing ink was 18 Pa·s, and the mass fraction of the solvent in the thermosetting screen printing ink was 4%.

[0046] Example 4

[0047] The difference between Example 4 and Example 1 is as follows: The carboxylic acid group-containing resin in the carboxylic acid group-containing resin system used in Example 4 is the carboxylic acid group-containing resin B prepared above.

[0048] The above materials were ground separately and stirred before use. The viscosity of the prepared thermosetting screen printing ink was 15 Pa·s, and the mass fraction of the solvent in the thermosetting screen printing ink was 4%.

[0049] Example 5

[0050] The difference between Example 5 and Example 1 is: The carboxylic acid group-containing resin in the carboxylic acid group-containing resin system used in Example 5 is the carboxylic acid group-containing resin C prepared above.

[0051] The above materials were ground separately and stirred before use. The viscosity of the prepared thermosetting screen printing ink was 10 Pa·s, and the mass fraction of the solvent in the thermosetting screen printing ink was 2%.

[0052] Example 6

[0053] The difference between Example 6 and Example 1 is: The carboxylic acid group-containing resin in the carboxylic acid group-containing resin system used in Example 6 is the carboxylic acid group-containing resin D prepared above.

[0054] The above materials were ground separately and stirred before use. The viscosity of the prepared thermosetting screen printing ink was 8 Pa·s, and the mass fraction of the solvent in the thermosetting screen printing ink was 9%.

[0055] Example 7

[0056] The difference between Example 7 and Example 1 is: The benzene ring-free epoxy resin used in Example 7 is ester ring epoxy resin (2,3-epoxycyclopentyl) ether.

[0057] The above materials were ground separately and stirred before use. The viscosity of the prepared thermosetting screen printing ink was 5 Pa·s, and the mass fraction of the solvent in the thermosetting screen printing ink was 8%.

[0058] Example 8

[0059] The difference between Example 8 and Example 1 is that the benzene ring-free epoxy resin used in Example 8 is trimethylolpropane triglycidyl ether resin.

[0060] The above materials were ground separately and stirred before use. The viscosity of the prepared thermosetting screen printing ink was 10 Pa·s, and the mass fraction of the solvent in the thermosetting screen printing ink was 5%.

[0061] Comparative Example 1

[0062] The difference between Comparative Example 1 and Example 1 is that Comparative Example 1 does not use a curing agent, but only uses a main agent and an auxiliary agent, and the epoxy resin used in Comparative Example 1 is bisphenol A epoxy resin E54.

[0063] The above materials were ground separately and stirred before use. The viscosity of the prepared ink was 38 Pa·s, and the mass fraction of the solvent in the thermosetting screen printing ink was 12%.

[0064] Comparative Example 2

[0065] The difference between Comparative Example 2 and Example 1 is: The weight parts of the curing agent used in Comparative Example 2 are different from those in Example 1. Comparative Example 2 uses 100 parts by weight of the resin system A containing carboxylic acid groups, so that the molar ratio of hydrogenated bisphenol A type epoxy resin DER331 (Dow) to the carboxylic acid groups in the resin system A containing carboxylic acid groups is 1:2.5.

[0066] The above materials were ground separately and stirred before use. The viscosity of the prepared thermosetting screen printing ink was 35 Pa·s, and the mass fraction of the solvent in the thermosetting screen printing ink was 14%.

[0067] Comparative Example 3

[0068] The difference between Comparative Example 3 and Example 1 is: The weight parts of the curing agent used in Comparative Example 3 are different from those in Example 1. Comparative Example 3 uses 16 parts by weight of the resin system A containing carboxylic acid groups, so that the molar ratio of hydrogenated bisphenol A type epoxy resin DER331 (Dow) to the carboxylic acid groups in the resin system A containing carboxylic acid groups is 2.5:1.

[0069] The above materials were ground separately and stirred before use. The viscosity of the prepared thermosetting screen printing ink was 10 Pa·s, and the mass fraction of the solvent in the thermosetting screen printing ink was 3%.

[0070] The properties of the heat-curable screen printing inks prepared in the examples and comparative examples were measured, and the specific method is as follows: Hardness: Tested according to GB / T6739-2006.

[0071] Yellowing index: tested according to GB2409-80.

[0072] Peel strength with EVA: Peel strength test is carried out according to GB / T2790.

[0073] Wet heat test: After the adhesive is printed and completely cured, the materials are laminated in the order of glass / adhesive film / battery / adhesive film / glass. A simulated laminated small component is made and placed in an environmental test chamber. According to the provisions of IEC 61215-2005, accelerated aging is carried out in a temperature and humidity chamber at 85℃±2℃ and humidity (85±5)%RH. The yellowing index (△YI) and peel strength of the sample after aging for 1000h are recorded.

[0074] UV aging test: After the glue is printed and fully cured, it is laminated in the order of glass / film / battery / film / glass. A simulated laminated small component is made and placed in an environmental test chamber. Test conditions: temperature (60±5)C, UV radiation in the range of 280nm~400nm reaches 120kWh / m 2 (The UV radiation with a wavelength of 280nm to 320nm accounts for 3% to 10% of the total UV radiation). The yellowing index test is performed on the laminate after UV120 test at a light intensity of 400-700lux.

[0075] Screen printing performance: The coating is printed on the surface of the battery cell substrate with a 200-mesh screen. After printing, the surface is smooth without missing prints, bubbles, wire drawing, burrs, or overflow.

[0076] The performance test results of the heat curing screen printing inks obtained in the examples and comparative examples are shown in Table 1.

[0077] Table 1

[0078] As shown in Table 1, the molar ratio of the epoxy group in the benzene ring-free epoxy resin to the carboxylic acid group in the resin system containing the carboxylic acid group is (2-1): (1-2). The benzene ring-free epoxy resin and the resin curing agent containing the carboxylic acid group are fully cured, thereby improving the overall performance of the coating. The benzene ring-free epoxy resin and the resin system containing the carboxylic acid group have good compatibility and meet the performance requirements of the liquid resin, so that the ink has an excellent screen printing effect.

[0079] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A heat curing screen printing ink, characterized in that: Including main ink and curing agent; The main ink comprises a benzene ring-free epoxy resin and a first filler; The curing agent is a resin system containing a carboxylic acid group; The molar ratio of the epoxy group in the benzene ring-free epoxy resin to the carboxylic acid group in the resin system containing the carboxylic acid group is (2-1): (1-2).

2. The heat curing screen printing ink according to claim 1, characterized in that: The number average molecular weight of the resin containing carboxylic acid groups in the resin system containing carboxylic acid groups is 1000-5000 g / mol; And / or, the acid value of the resin containing carboxylic acid groups in the resin system containing carboxylic acid groups is 20 mgKOH / g to 250 mgKOH / g; And / or, the mass fraction of the resin containing carboxylic acid groups in the resin system containing carboxylic acid groups is 60-95%.

3. The heat curing screen printing ink according to claim 1 or 2, characterized in that: The carboxylic acid group-containing resin in the carboxylic acid group-containing resin system is formed by polymerizing an acid functional group monomer and a non-acid functional group monomer in the presence of a chain transfer agent; Preferably, the resin containing carboxylic acid groups has the general structural formula: Wherein, MMA is a non-acid functional monomer; AA is an acid functional monomer; Z is C4~C12 alkylthio, C4~C12 alkyl, phenyl or benzyl; X is isopropanoyl, acetyl, 2-nitroacetyl or 2-aminoacetyl; n is the total polymerization degree of the acid functional group monomer and the non-acid functional group monomer, n=10-50, wherein the polymerization degree of the acid functional group monomer is 2-10, and the polymerization degree of the non-acid functional group monomer is 6-40.

4. The heat curing screen printing ink according to claim 3, characterized in that: The non-acid functional group monomer includes at least one of methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, hexyl methacrylate, hexyl acrylate, decyl methacrylate, decyl acrylate, lauryl methacrylate, lauryl acrylate, tetrahydrofuran methacrylate, tetrahydrofuran acrylate, isobornyl methacrylate, isobornyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate and hydroxypropyl acrylate; And / or, the acid functional monomer comprises at least one of methacrylic acid and acrylic acid.

5. The heat curing screen printing ink according to claim 1 or 2, characterized in that: The resin system containing carboxylic acid groups further includes a second filler; and / or, based on the total mass of the resin system containing carboxylic acid groups, the mass proportion of the second filler is no more than 30%; And / or, the second filler includes at least one of aerosil, silica powder, glass powder, barium sulfate, mica and phosphor.

6. The heat curing screen printing ink according to claim 1 or 2, characterized in that: The benzene ring-free epoxy resin includes at least one of hydrogenated bisphenol A type epoxy resin, aliphatic glycidyl ether resin, ester ring epoxy resin, silicone epoxy resin and glycidyl amine resin.

7. The heat curing screen printing ink according to claim 1 or 2, characterized in that: The first filler comprises at least one of gas silica, silica powder, glass powder, barium sulfate, mica and phosphor; And / or, based on the total mass of the thermosetting screen printing ink, the mass proportion of the first filler is 0.5% to 30%.

8. The heat curing screen printing ink according to claim 1 or 2, characterized in that: The viscosity of the thermosetting screen printing ink is 5 Pa·s to 30 Pa·s; And / or, the mass fraction of the solvent in the thermosetting screen printing ink is 2% to 20%.

9. The heat curing screen printing ink according to claim 1 or 2, characterized in that: It also includes adjuvants; And / or, based on the total mass of the thermosetting screen printing ink, the mass proportion of the auxiliary agent is 0.1% to 2%; And / or, the auxiliary agent includes at least one of a defoaming agent, a leveling agent and a dispersant.

10. Use of the thermosetting silk screen printing ink according to any one of claims 1 to 9 in photovoltaic modules.

Images