Alkali-soluble photo / thermal dual-curing aliphatic polyester acrylate resin, preparation method and application thereof

Abstract

The application belongs to the technical field of solder resist ink resins, and particularly relates to an alkali-soluble photo / thermal dual-curing aliphatic polyester acrylate resin as well as a preparation method and application thereof. The application discloses an aliphatic polyester acrylate resin as shown in formula I. The preparation method of the aliphatic polyester acrylate resin is as follows: first, an intermediate product with an epoxy group at the end is prepared by reacting an aliphatic diepoxy compound with an aliphatic diacid; then, the obtained intermediate product is reacted with acrylic acid to obtain an intermediate product with an acrylate group at the end; finally, the obtained intermediate product is reacted with an aliphatic cyclic diacid anhydride to obtain a target product. The aliphatic polyester acrylate resin prepared by the method has excellent photo / thermal curing performance and alkali etching developing property, and since the resin does not contain an aromatic structure, the application of the resin in the preparation of solder resist ink can overcome the defect of poor yellowing resistance, so that the aliphatic polyester acrylate resin has a good application prospect in the field of low-yellowing solder resist ink.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of solder resist ink resins, and particularly relates to an alkali-soluble light / heat dual-curing aliphatic polyester acrylate resin as well as a preparation method and application thereof. BACKGROUND

[0002] Ultraviolet light curing technology is a curing technology that utilizes ultraviolet light to decompose a photoinitiator to generate free radicals, which in turn initiate the polymerization of double bonds in a prepolymer to form a crosslinked structure. Compared with traditional thermal curing, ultraviolet light curing does not require heating and can be completed within a few seconds to tens of seconds at room temperature, which can greatly shorten the production time and reduce energy consumption, and the system does not contain organic solvents, which is more convenient and environmentally friendly. Among them, epoxy acrylate is the most widely used and largest amount of light-cured oligomer, which has the characteristics of fast curing speed and low cost. The cured film made of it has the advantages of high rigidity, high hardness, high gloss, excellent chemical resistance and other advantages. However, due to the interaction between molecules, the viscosity and brittleness of the epoxy acrylate resin are large, so its application in the fields of electronics, aerospace and other fields is limited.

[0003] Solder resist ink is one of the key materials for making printed circuit boards (PCB), which is coated on the etched circuit board to form an insulating, heat-resistant, and adhesive protective film, which can prevent the circuit from breaking. In the tin immersion process, solder resist ink can also control the tin deposition area to prevent short circuits caused by dense solder joints. However, traditional screen printing solder resist ink has poor registration accuracy and resolution, and dry film solder resist ink has poor adhesion to the circuit board. Since the concept of alkali developing photosensitive solder resist ink was proposed in the late 1980s, some foreign institutions have conducted a lot of research and development. This solder resist ink mainly contains carboxylated epoxy acrylate resin and B component epoxy resin. After screen printing on the etched circuit board, the solvent is removed by pre-baking, and a light-cured latent image is obtained by mask exposure. After developing with dilute alkali solution, further curing at medium temperature can form a high-performance solder resist layer. This photoimageable solder resist ink has good registration accuracy and adhesion.

[0004] At present, the light / heat dual-curing resins used in alkali developing solder resist ink mostly contain aromatic ring structures, such as o-cresol formaldehyde epoxy acrylate resin, which is widely used in the field of solder resist ink. However, the aromatic structure contained therein has poor yellowing resistance, which limits its application in white solder resist ink. At the same time, although the addition of antioxidants and other additives can alleviate yellowing to some extent, it cannot fundamentally solve the problem of resin yellowing. Therefore, developing alkali developing solder resist ink resins with good yellowing resistance is one of the problems to be solved in the industry. SUMMARY

[0005] In order to overcome the above-mentioned deficiencies of the prior art, the present application provides an alkali-soluble light / heat dual-curing aliphatic polyester acrylate resin, which has excellent light / heat curing performance and alkali etching development property, and has a good application prospect in the field of solder resist ink, especially low-yellowing solder resist ink.

[0006] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is:

[0007] The present application provides an alkali-soluble light / heat dual-curing aliphatic polyester acrylate resin, the molecular structure of the polyester acrylate resin is shown in formula (I):

[0008]

[0009] In formula (I), R1 is derived from a corresponding aliphatic bis-epoxy compound, including (a) and mixtures thereof; R2 is derived from a corresponding aliphatic diacid, including and mixtures thereof, n=8-25; R3 is derived from a corresponding aliphatic cyclic diacid anhydride, including and mixtures thereof; R4 is derived from a corresponding unsaturated carboxylic acid, including H, CH3 and mixtures thereof; m is determined by the number average molecular weight of the resin, the number average molecular weight of the resin is Mn=5000-10000, and the acid value is 60-80 mgKOH / g.

[0010] Preferably, in the polyester acrylate resin shown in formula (I), R1 is selected from (a)+(e) or (d)+(e), more preferably (a)+(e), and the mass ratio of (a):(e) is preferably 9:1-8:2; R2 is selected from R3 is selected from R4 is selected from H.

[0011] More preferably, the polyester acrylate resin has the following structural formula:

[0012]

[0013] R1 is R`1 is with a molecular weight Mn=400-1000; R2 is selected from R3 is x1, x2 are determined by the number average molecular weight of the resin, x1:x2=10:1-4:1, and the number average molecular weight of the resin is 5500-9100.

[0014] The present application provides a preparation method of the alkali-soluble light / heat dual-curing aliphatic polyester acrylate resin of the first aspect, comprising the following steps:

[0015] S1, as shown in the following reaction formula, the aliphatic bis-epoxy compound, aliphatic diacid and ring-opening reaction catalyst is dissolved in a solvent under inert atmosphere, heated to acid value = 0, the end of the epoxy polyester intermediate product is prepared;

[0016] The reaction is a bis-epoxy compound and diacid by ring-opening addition reaction between epoxy and carboxyl group to generate the end of the epoxy polyester intermediate product;

[0017]

[0018] In the reaction formula, R1, R2 value is the same as in example 1 or 2; the molar ratio of y and x is 0.8:1-0.9:1; m is determined by the number average molecular weight of the product, the number average molecular weight of the product is M n = 4500-8500;

[0019] S2, as shown in the following reaction formula, in the product of S1, adding polymerization inhibitor and unsaturated carboxylic acid, and adding ring-opening reaction catalyst and solvent, continue to heat to epoxy value = 0, the end of the polyester intermediate product is prepared acrylic ester / methacrylate group;

[0020] The reaction is a bis-epoxy compound and diacid by ring-opening addition reaction between epoxy and carboxyl group to generate the end of the epoxy polyester intermediate product;

[0021]

[0022] In the reaction formula, R1, R2, R4 value is the same as in example 1 or 2; m is determined by the number average molecular weight of the product, the number average molecular weight of the product is M n = 4500-8500;

[0023] S3, in the intermediate product of S2, adding aliphatic cyclic dianhydride and solvent, heating to acid value = 60-80, the target product is obtained;

[0024] The reaction is a bis-epoxy compound and diacid by ring-opening addition reaction between epoxy and carboxyl group to generate the end of the epoxy polyester intermediate product;

[0025]

[0026] In the reaction formula, R1, R2, R3, R4, m value is the same as in example 1 or 2.

[0027] Preferably, in S1, the aliphatic bis-epoxy compound is selected from hydrogenated bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, 1,4-butanediol glycidyl ether, neopentyl glycol diglycidyl ether, 1,2-cyclohexanediol diglycidyl ether and mixture thereof.

[0028] More preferably, the aliphatic diepoxy compound is selected from the group consisting of hydrogenated bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, 1,2-cyclohexanediol diglycidyl ether and mixtures thereof.

[0029] More preferably, the aliphatic diepoxy compound is selected from the group consisting of polyethylene glycol diglycidyl ether and a mixture of hydrogenated bisphenol A epoxy resin, the mass ratio of the polyethylene glycol diglycidyl ether (such as polyethylene glycol 400 diglycidyl ether) to the hydrogenated bisphenol A epoxy resin (such as epoxy resin 1510) is 1:9 to 2:8.

[0030] Preferably, in S1, the aliphatic dibasic acid is selected from the group consisting of 1,4-cyclohexyl dicarboxylic acid, C4-C10 aliphatic dibasic acid and mixtures thereof.

[0031] More preferably, the aliphatic dibasic acid is selected from the group consisting of 1,4-cyclohexyl dicarboxylic acid.

[0032] Preferably, the ring-opening reaction catalyst in S1 is selected from the group consisting of tertiary amine, trihydrocarbyl phosphine and mixtures thereof, and the addition amount is 0.2% to 1% of the total mass of the reactants.

[0033] More preferably, the ring-opening reaction catalyst is selected from the group consisting of triethylamine, triphenyl phosphine and mixtures thereof, and more preferably triphenyl phosphine.

[0034] Preferably, the solvent in S1 is selected from at least one of ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol methyl ether propionate, dipropylene glycol methyl ether, propylene glycol methyl ether, mesitylene and tetramethylbenzene.

[0035] More preferably, the solvent is selected from diethylene glycol ethyl ether acetate.

[0036] Preferably, in S2, the unsaturated carboxylic acid is selected from the group consisting of acrylic acid, methacrylic acid and mixtures thereof, and the molar number of the added unsaturated carboxylic acid is 1.1 times the theoretically remaining epoxy group molar number in the system after S1 reaction, and the theoretically remaining epoxy group molar number in the system is calculated by subtracting the carboxyl group molar number contained in the dibasic acid from the epoxy group molar number contained in the diepoxy compound.

[0037] More preferably, the unsaturated carboxylic acid is selected from acrylic acid.

[0038] Preferably, in S2, the polymerization inhibitor is selected from 2,6-di-tert-butyl-p-cresol (BHT) and 4-methoxyphenol, and the addition amount of each polymerization inhibitor is 0.2% to 0.4% of the mass of the added unsaturated carboxylic acid in S2.

[0039] Preferably, the aliphatic cyclic dianhydride of S3 is selected from hexahydrophthalic anhydride, succinic anhydride and mixtures thereof, and the addition amount is determined according to the acid value of the final product system = 60-80 mgKOH / g, and the specific calculation formula is:

[0040]

[0041] More preferably, the aliphatic cyclic dianhydride is selected from hexahydrophthalic anhydride.

[0042] The third aspect of the present application provides the application of the alkali-soluble photo / thermal dual-curing aliphatic polyester acrylate resin of the first aspect in preparing solder resist ink.

[0043] The terminal acrylate group in the polyester acrylate resin molecule of the present application endows the polymer with photo-curing performance, the carboxyl side group endows the polymer with alkali-soluble and thermal curing performance (forms a thermal curing system with an additional multi-epoxy compound), and the structure does not contain aromatic structure, and the polyester acrylate resin can be applied in preparing solder resist ink to solve the problem of yellowing.

[0044] Compared with the prior art, the present application has the following beneficial effects:

[0045] The present application discloses an aliphatic polyester acrylate resin, the terminal acrylate group contained in the polyester acrylate resin endows the resin with photo-curing performance, and the carboxyl side group contained in the polyester acrylate resin endows the resin with alkali-soluble and thermal curing performance, so that the polyester acrylate resin belongs to an alkali-soluble photo / thermal dual-curing resin. The present application also discloses a preparation method of the aliphatic polyester acrylate resin, that is, first, an intermediate product with an epoxy group at the terminal is prepared by reacting an aliphatic di-epoxy compound and an aliphatic di-acid, then the obtained intermediate product is reacted with acrylic acid to obtain an intermediate product with an acrylate group at the terminal, and finally, the obtained intermediate product is reacted with an aliphatic cyclic dianhydride to obtain the target product. The aliphatic polyester acrylate resin prepared by the method of the present application has excellent photo / thermal curing performance and alkali etching developing property, and since the resin does not contain aromatic structure, the aliphatic polyester acrylate resin can overcome the defect of not being resistant to yellowing when applied in preparing solder resist ink, so that the aliphatic polyester acrylate resin has good application prospect in the field of low-yellowing solder resist ink. BRIEF DESCRIPTION OF DRAWINGS

[0046] Figure 1 is the GPC graph of the polyester intermediate product with an epoxy group at the terminal;

[0047] Figure 2 is the GPC graph of the polyester acrylate resin;

[0048] Figure 3 is the comparison graph of the polyester acrylate resin before and after the developing property test. DETAILED DESCRIPTION

[0049] The specific embodiments of the present invention will be further described below. It should be noted that these descriptions are for the purpose of aiding understanding the present invention, but do not constitute a limitation thereof. Furthermore, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0050] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the experimental materials used in the following embodiments are all available through conventional commercial channels.

[0051] The molecular weight of the product was determined by GPC under the following conditions: an Agilent Technologies PL-GPC 50 gel permeation chromatograph was used, consisting of one Agilent PL 10μm MIXED-B gel column and two Agilent PL 5μm MIXED-D gel columns connected in series. Polystyrene (PS) was used as the standard. The refractive index detector was set at 40℃, THF was used as the mobile phase, and the flow rate was 1.0 mL / min. -1 .

[0052] Example 1: Synthesis of Polyester Acrylate Resin

[0053] S1. First, under a nitrogen atmosphere, 13.5g of epoxy resin 1510, 1.5g of polyethylene glycol 400 diglycidyl ether (PEG400DG), 10.45g of diethylene glycol ethyl ether acetate (DGMEA), and 5.9g of 1,4-cyclohexanedicarboxylic acid (CHDA) were added to the reactor. The mixture was heated to 120°C and stirred for 10 minutes. Then, 0.052g of triphenylphosphine (PPh3, 0.25wt%), a ring-opening catalyst, was added. The reaction was continued at 120°C for 6 hours until the acid value was 0, yielding a polyester intermediate with epoxy groups at the end. GPC analysis showed that the number average molecular weight of this product was approximately 7500. Figure 1 The reaction formula is as follows:

[0054]

[0055] In the formula: R1 is R`1 is Its molecular weight Mn = 400; R2 is selected from (x1+x2):y (molar ratio) = 1:0.9; x1:x2 = 10:1.

[0056] S2. Under a nitrogen atmosphere, 0.622 g of acrylic acid (AA) was added to the intermediate product of S1, along with one part of triphenylphosphine catalyst (0.052 g), 0.0012 g of 2,6-di-tert-butyl-p-cresol (BHT), 0.0012 g of 4-methoxyphenol (MEHQ), and 4 g of diethylene glycol ethyl ether acetate. After mixing, the mixture was stirred at 120 °C for 8 hours until the epoxy value reached 0, yielding a polyester intermediate with acrylate / methacrylate groups at the end. The reaction formula is as follows:

[0057]

[0058] In the formula: R1 is R`1 is Its molecular weight Mn = 400; R2 is selected from (x1+x2):y (molar ratio) = 1:0.9; x1:x2 = 10:1.

[0059] S3. Under nitrogen protection, the intermediate product of S2 was cooled to 100℃, and then 6.06g of hexahydrophthalic anhydride (HHPA) and 2g of diethylene glycol ethyl ether acetate were added. After mixing, the mixture was stirred at this temperature for 3 hours until the acid value reached 80mg KOH / g. After stopping the reaction, the polyester acrylate resin was obtained. GPC analysis showed that its number average molecular weight was approximately 9100. Figure 2 The reaction formula is as follows:

[0060]

[0061] In the formula: R1 is R`1 is Its molecular weight Mn = 400; R2 is selected from R3 is (x1+x2):y (molar ratio) = 1:0.9; x1:x2 = 10:1.

[0062] Examples 2-7 and Comparative Example 1: Synthesis of Polyester Acrylic Resin

[0063] The raw materials and reaction methods used in Examples 2-7 and Comparative Example 1 are the same as those in Example 1, except that the proportions of each reactant are different. The amounts of each reactant and the reaction results in Examples 1-7 and Comparative Example 1 are shown in Table 1.

[0064] Table 1. Synthesis of polyester acrylate resins in Examples 1-7 and Comparative Example 1

[0065]

[0066]

[0067] Experimental Example: Alkali-solubility and light / heat curing test of polyester acrylate resins

[0068] First, polyester acrylate resins obtained in Examples 1 to 7 and Comparative Example 1 were each coated on a glass slide using a 15 μm film coating bar, dried at 70°C, and then subjected to an alkali-solubility test in a 1% Na2CO3 solution at a temperature of 60°C, with magnetic stirring at 600 rpm during the test. The test results are shown in Table 2.

[0069] As can be seen from Table 2, the polyester acrylate resins of Examples 1 to 7 have good alkali-solubility, while Comparative Example 1, which has a molecular weight close to that of the resins of the other examples, has poor solubility in an aqueous sodium bicarbonate solution due to the absence of PEG400DG, and is not dissolved even after 20 minutes of immersion. It can be seen that the addition of an appropriate amount of PEG400DG is necessary in order to obtain good alkali-solubility. Also, as can be seen from a comparison of Examples 1, 4 and 7, as the content of PEG400DG in the resin increases, the alkali-solubility time of the resin decreases due to the good water-solubility of PEG. Also, as can be seen from a comparison of Examples 4, 5 and 6, the greater the acid value of the resin, i.e. the greater the number of carboxyl groups introduced, the better the alkali-solubility.

[0070] Table 2: Alkali-solubility test results of the resins of Examples 1 to 7 and Comparative Example 1

[0071]

[0072] Note: * not dissolved after 20 minutes.

[0073] Also, the polyester acrylate resins of Examples 1 to 7 were used to prepare white light / heat curable resins, and the light curability of the resins was further compared, as follows.

[0074] (1) The polyester acrylate resins obtained in Examples 1 to 7 were each combined with an active diluent (trimethylolpropane triacrylate, TMPTA), a curing agent (hydrogenated bisphenol A epoxy resin 1510), a photoinitiator (TPO, (2,4,6-trimethylbenzoyl) phenylphosphine oxide) and a solvent (diethylene glycol ethyl ether acetate, DGMEA) to form a light / heat curable compounded resin, and the proportions of the components are shown in Table 3.

[0075] Table 3: Formulation of light / heat curable compounded resins prepared from the polyester acrylate resins obtained in different examples

[0076]

[0077] (2) The prepared complex resin was uniformly coated on a glass slide, dried at 70°C for 30 min, and then exposed to UV light at 395 nm and 300 w for 10 s to obtain a photocured film. The photocured film was further heat cured at 120°C for 2 h and at 150°C for 1.5 h, and then cooled to room temperature to obtain a coating film sample.

[0078] (3) The hardness of the coating film sample after photocuring and heat curing was determined according to the pencil hardness method of GB / T 6739-1996, and the curing degree was determined by the gel content determination method. The test results are shown in Table 4.

[0079] As can be seen from the results in Table 4, the photocuring degree is related to the double bond content in the polyester acrylate resin. The photocuring degree is significantly improved after photocuring of the resin with a high double bond content. The curing degree and pencil hardness are significantly improved after heat curing at 150°C for 1.5 h than after heat curing at 120°C for 2 h. The above results show that the polyester acrylate resins of the present application have good photo / thermal dual curing performance.

[0080] Table 4 Photo / thermal curing performance test of the polyester acrylate resins of Examples 1-7

[0081]

[0082] Hardness 1: hardness after photocuring; G1: gel content after photocuring; Hardness 2: hardness after photocuring and heat curing at 120°C for 2 h; G2: gel content after photocuring and heat curing at 120°C for 2 h; Hardness 3: hardness after photocuring and heat curing at 150°C for 1.5 h; G3: gel content after photocuring and heat curing at 150°C for 1.5 h.

[0083] Finally, the polyester acrylate resins obtained in Examples 1-7 and Comparative Example 1 were prepared into photo / thermal curing resin white color paste, and a development test was performed, as follows:

[0084] (1) Preparation of white color paste: The complex resin was prepared according to the formulation in Table 3, and then titanium dioxide was added to prepare a white color paste, and the addition amount of titanium dioxide was 35 wt% of the complex resin. The specific preparation method was as follows: the complex resin, titanium dioxide and zirconium beads (2 mm, the addition amount was equal to the mass of the resin) were added to a grinding tank, ground for 1 h, and then filtered through a 400 mesh screen to obtain a white photo / thermal curing resin color paste (Examples 1-7).

[0085] (2) Photocuring of white resin: The obtained white resin color paste was uniformly coated on a glass slide, dried at 70°C for 30 min, and then exposed to UV light at 395 nm and 300 w for 10 s to obtain a cured coating film.

[0086] (3) Development test: the thickness of the above-mentioned light-cured coating film was measured by a paint film thickness measuring instrument, and then the film was placed in a 1% Na2CO3 solution at a temperature of 60°C for alkali solubility test, magnetic stirring was carried out at 600 rpm during the test, and the test results are shown in Table 5 (alkali solubility before and after comparison chart). Figure 3

[0087] As can be seen from Table 5, the alkali solubility time is related to the molecular weight of the resin, the content of hydrophilic groups, the acid value, the thickness of the film and other factors. As can be seen from Examples 3, 7 and Comparative Example 1, in the case of smaller film thickness of Example 3 than Example 7, the alkali solubility time is prolonged, indicating that the alkali solubility is improved with the increase of PEG content in the resin; in Examples 4, 5 and 6, the dissolution of Example 6 is not good, which can be seen that the alkali solubility of the light-cured ink is decreased with the decrease of the acid value of the system; as can be seen from Examples 2 and 3, the alkali washing time of the light-sensitive resin with high molecular weight is longer after light curing.

[0088] Table 5 Development test results of white resin color paste prepared by different examples after light curing

[0089]

[0090] * Partial dissolution.

[0091] As can be seen from the above, the alkali-soluble light / heat dual-cured polyester acrylate resin prepared by the method of the present application has excellent light / heat curing performance and alkali etching development, and does not contain easily yellowing aromatic structure, thus having good application prospect in the field of solder resist ink, especially low-yellowing solder resist ink.

[0092] The above describes the embodiments of the present application in detail, but the present application is not limited to the described embodiments. For those skilled in the art, various changes, modifications, replacements and variations of the embodiments can be made without departing from the principles and spirits of the present application, and still fall within the protection scope of the present application.​

Claims

1. An alkali-soluble photo / thermal dual-curable aliphatic polyester acrylate resin characterized by, The molecular structure of the polyester acrylate resin is shown in formula (I): ； In formula (I), R1is derived from corresponding aliphatic bis-epoxide compounds, including (a) , (b) , (c) , (d) , (e) and mixtures thereof, n = 8-25; R2is derived from corresponding aliphatic diacids, including , and mixtures thereof; R3is derived from aliphatic cyclic diacid anhydride ; R4is derived from corresponding unsaturated carboxylic acid, including H, CH3and mixtures thereof; m is determined by the number average molecular weight of the resin, the number average molecular weight of the resin is Mn = 5000-10000, and the acid value is 60-80 mgKOH / g.

2. The alkali-soluble photo / thermal dual-curable aliphatic polyester acrylate resin according to claim 1, characterized by, In the polyester acrylate resins of formula (I), R1is selected from (a) + (e) or (d) + (e); R2is selected from ; R3is selected from ; and R4is selected from H.

3. The alkali-soluble photo / thermal dual-curable aliphatic polyester acrylate resin according to claim 2, characterized by, The polyester acrylate resin has the following structural formula: ； R1 is ; R`1 is , the molecular weight Mn=400~1000; R2 is selected from ; R3 is ; x1, x2 are determined by the number average molecular weight of the resin, x1:x2=10:1~4:1, the number average molecular weight of the resin is 5500~9100.

4. The method of producing the alkali-soluble photo / thermal dual-curable aliphatic polyester acrylate resin according to claim 1, characterized by, The method comprises the following steps: S1, as shown in the following reaction formula, dissolve the aliphatic bis-epoxy compound, aliphatic dibasic acid and ring-opening reaction catalyst in a solvent under inert atmosphere, heat to react until the acid value = 0, and obtain the polyester intermediate product with terminal epoxy group; ； In the reaction formula, R1is derived from a corresponding aliphatic bis-epoxide, including (a) , (b) , (c) , (d) , (e) and mixtures thereof, n = 8-25; R2is derived from a corresponding aliphatic diacid, including , and mixtures thereof; the molar ratio of y to x is 0.8:1 to 0.9:1; m is determined by the number average molecular weight of the product, which is M n = 4500-8500. S2, as shown in the following reaction formula, add the polymerization inhibitor and unsaturated carboxylic acid to the intermediate product of S1, and supplement the ring-opening reaction catalyst and solvent, continue to heat to react until the epoxy value = 0, and obtain the polyester intermediate product with terminal acrylate / methacrylate group; ； In the reaction formula, R1is derived from a corresponding aliphatic bis-epoxide, including (a) , (b) , (c) , (d) , (e) and mixtures thereof, n = 8-25; R2is derived from a corresponding aliphatic diacid, including , and mixtures thereof; R4is derived from a corresponding unsaturated carboxylic acid, including H, CH3and mixtures thereof; m is determined by the number average molecular weight of the product, which is M n = 4500-8500; S3, add the aliphatic cyclic dianhydride and solvent to the intermediate product of S2, heat to react until the acid value = 60-80, and obtain the target product; ； In the reaction formula, R1 is derived from corresponding aliphatic bis-epoxide compounds, including (a) , (b) , (c) , (d) , (e) and mixtures thereof, n = 8-25; R2 is derived from corresponding aliphatic diacids, including , and mixtures thereof; R3 is derived from aliphatic cyclic diacid anhydride ; R4 is derived from corresponding unsaturated carboxylic acid, including H, CH3 and mixtures thereof; m is determined by the number average molecular weight of the resin, the number average molecular weight of the resin is Mn = 5000-10000, and the acid value is 60-80 mgKOH / g.

5. The method of producing an alkali-soluble photo / thermal dual-curable aliphatic polyester acrylate resin according to claim 4, characterized by, In S1, the aliphatic bis-epoxy compound is selected from hydrogenated bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, 1,4-butanediol glycidyl ether, neopentyl glycol diglycidyl ether, 1,2-cyclohexanediol diglycidyl ether and mixtures thereof; and the aliphatic dibasic acid is selected from 1,4-cyclohexyl dicarboxylic acid, C4-C10 aliphatic dibasic acid and mixtures thereof.

6. The method of producing an alkali-soluble photo / thermal dual-curable aliphatic polyester acrylate resin according to claim 4, characterized by, The ring-opening reaction catalyst in S1 is selected from tertiary amine, trihydrocarbyl phosphine and mixtures thereof, and the addition amount is 0.2%-1% of the total mass of the reactants.

7. The method of producing an alkali-soluble photo / thermal dual-curable aliphatic polyester acrylate resin according to claim 4, characterized by, The solvent in S1 is selected from at least one of ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol diethyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol methyl ether propionate, dipropylene glycol methyl ether, propylene glycol methyl ether, mesitylene and tetramethylbenzene.

8. The method of producing an alkali-soluble photo / thermal dual-curable aliphatic polyester acrylate resin according to claim 4, characterized by, In S2, the unsaturated carboxylic acid is selected from acrylic acid, methacrylic acid and mixtures thereof, and the molar number of the added unsaturated carboxylic acid is 1.1 times the theoretical residual epoxy group molar number in the system after the reaction in S1, and the theoretical residual epoxy group molar number in the system is calculated by subtracting the carboxyl molar number contained in the dibasic acid from the epoxy group molar number contained in the bis-epoxy compound; and the polymerization inhibitor is selected from 2,6-di-tert-butyl-p-cresol (BHT) and 4-methoxyphenol, and the addition amount of each polymerization inhibitor is 0.2%-0.4% of the mass of the added unsaturated carboxylic acid in S2.

9. The method of producing an alkali-soluble photo / thermal dual-curable aliphatic polyester acrylate resin according to claim 4, characterized by, The aliphatic cyclic diacid anhydride of S3 is selected from hexahydrophthalic anhydride, succinic anhydride and mixtures thereof, and the amount of addition is such that the acid value of the final product system = 60-80 mg KOH / g, the specific calculation formula being: .

10. Use of the alkali-soluble photo / thermal dual-curing aliphatic polyester acrylate resin according to any one of claims 1-3 in preparing solder resist ink.

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