A hyperbranched active ester curing agent containing double bonds and an interlayer film containing the active ester curing agent

Abstract

The present invention belongs to the technical field of IC packaging materials, and relates to a hyperbranched active ester curing agent containing double bonds and an interlayer film containing the active ester curing agent. The structural formula of the hyperbranched active ester curing agent containing double bonds is shown in Formula I: #imgabs0# Formula I; the hyperbranched active ester curing agent containing double bonds contains more branched structures, has better fluidity, can improve its film-forming performance, and provides more active ester group equivalents; at the same time, through the free radical polymerization reaction of the double bonds therein, the crosslinking density is further increased. After acting together with the crosslinking reaction of the non-hyperbranched active ester curing agent and epoxy resin, the glass transition temperature of the interlayer film can be increased, its coefficient of thermal expansion can be reduced, and its thermodynamic properties can be improved; in addition, the hyperbranched rigid skeleton structure can introduce nanoscale micropores into the curing system, thereby improving the dielectric properties of the interlayer film.

Description

Technical Field

[0001] The present invention belongs to the technical field of IC packaging materials, and relates to a hyperbranched active ester curing agent containing double bonds and a build-up film containing the active ester curing agent. Background Art

[0002] As a key core material in advanced packaging technology, the build-up film is crucial for improving the performance of electronic packaging. Currently, the mainstream raw materials for build-up films include epoxy resins, phenolic resins, cyanate esters, active esters, etc. Among them, the thermosetting resin system composed of active esters and epoxy resins does not generate additional hydroxyl groups (-OH) during the reaction process, and has the characteristics of low dielectric loss and low water absorption, meeting the requirements of the new generation of build-up films for electrical properties.

[0003] In addition, the active ester plus epoxy resin system also exhibits excellent film-forming ability, good heat resistance characteristics, and excellent chemical stability. With the continuous development of today's electronic technology, the chip packaging process is developing towards smaller line widths and pitches, and at the same time, the chip size is also increasing year by year. Facing such a development trend, advanced packaging puts forward higher standards for build-up film materials, especially the improvement of the glass transition temperature (Tg) and the reduction of its coefficient of thermal expansion (CTE) are particularly important. A high Tg value can ensure that the material still maintains sufficient mechanical strength at a higher temperature; while a low CTE helps to reduce the problem of board warping caused by the thermal expansion difference between different materials due to temperature changes, thereby improving the reliability of the entire packaging structure.

[0004] Existing resin systems mostly exhibit problems such as a relatively low glass transition temperature (Tg), a relatively high coefficient of thermal expansion (CTE), and poor thermal stability. Therefore, improving the glass transition temperature of the build-up film and reducing its coefficient of thermal expansion have become one of the key research points in the current field. Summary of the Invention

[0005] In view of the above problems existing in the prior art, the present invention provides a hyperbranched active ester curing agent containing double bonds and a build-up film containing the active ester curing agent. The present invention uses hyperbranched active esters as curing agents, combines non-hyperbranched active ester curing agents and epoxy resins, and obtains a build-up film with high Tg, low CTE, and low dielectric constant, ensuring the use performance of the build-up film in the field of integrated circuit packaging.

[0006] To achieve the above object, the present invention provides a hyperbranched active ester curing agent containing double bonds, and its structural formula is shown in Formula I:

[0007] Formula I;

[0008] Among them, R is selected from one or more of substituted or unsubstituted C1-C10 linear alkyl groups, substituted or unsubstituted C1-C10 branched alkyl groups, and substituted or unsubstituted C3-C10 cycloalkyl groups; preferably a substituted or unsubstituted C1-C3 linear alkyl group;

[0009] X is selected from one or more of substituted or unsubstituted benzene rings, substituted or unsubstituted naphthalene rings, substituted or unsubstituted biphenyls, substituted or unsubstituted alicyclic hydrocarbons, substituted or unsubstituted naphthalene ethers, substituted or unsubstituted bisphenol A, substituted or unsubstituted dicyclopentadiene, and substituted or unsubstituted 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide group (DOPO);

[0010] n is from 1 to 10, preferably from 1 to 5.

[0011] A hyperbranched active ester curing agent containing double bonds provided by the present invention has a relatively large number of branched structures in its structural formula. Compared with the linear active ester, it has better fluidity and can improve the film-forming property of the active ester system; using an alkyl end-capping in the hyperbranched active ester helps to improve the solubility of the hyperbranched active ester in the solvent, obtain a uniform solution system, and further improve its film-forming performance.

[0012] Preferably, the hyperbranched active ester curing agent containing double bonds is formed by the reaction of resveratrol, an X-group compound with hydroxyl groups at both ends, aromatic dicarbonyl chloride, and an acyl chloride compound containing an R group;

[0013] The resveratrol has the following structural formula: ;

[0014] The aromatic dicarbonyl chloride includes one or more of terephthaloyl chloride, phthaloyl chloride, and isophthaloyl chloride, and has the following structural formula: ;

[0015] The X-group compound with hydroxyl groups at both ends has the following structural formula: ;

[0016] The acyl chloride compound containing an R group has the following structural formula: .

[0017] Here, X and R correspond to X and R in Formula I respectively.

[0018] Specifically, as shown in Reaction Formula I:

[0019] Reaction Formula I.

[0020] Preferably, the molar ratio of resveratrol to the X-group compound with hydroxyl groups at both ends is 1:(2 - 10). More preferably 1:(3 - 5).

[0021] The present invention strictly controls the ratio of resveratrol and the compound of X group with hydroxyl groups at both ends in the reaction. If the proportion of resveratrol is too high, the degree of hyperbranched structure is too large, and the crosslinking reaction will be inhibited due to steric hindrance effect, reducing the crosslinking degree after the resin is thermoset. On the contrary, the degree of hyperbranched structure is too small, resulting in a decrease in the fluidity of the product, weakening the leveling ability, and reducing the introduction of nano-scale micropores, and the dielectric properties become poor.

[0022] Preferably, the molar ratio of the aromatic dicarboxylic acid dichloride and the acyl chloride compound containing R group is (1-5):1. More preferably, it is (2-3):1.

[0023] Preferably, the molar ratio of the total amount of the aromatic dicarboxylic acid dichloride and the acyl chloride compound containing R group to the total amount of resveratrol and the compound of X group with hydroxyl groups at both ends is 1:(1-5). More preferably, it is 1:(1.5-3).

[0024] The present invention also provides a preparation method of a hyperbranched active ester curing agent containing double bonds, which includes the following steps: dissolving resveratrol, the compound of X group with hydroxyl groups at both ends and a catalyst in a solvent, adding the aromatic dicarboxylic acid dichloride and the acyl chloride compound containing R group for a common reaction to obtain the hyperbranched active ester curing agent containing double bonds.

[0025] The present invention also provides a preparation method of a hyperbranched active ester curing agent containing double bonds, which includes the following steps: dissolving resveratrol, the compound of X group with hydroxyl groups at both ends and a catalyst in a solvent, adding the aromatic dicarboxylic acid dichloride for a first reaction, and then adding the acyl chloride compound containing R group for a second reaction to obtain the hyperbranched active ester curing agent containing double bonds.

[0026] In the preparation method of the hyperbranched active ester curing agent containing double bonds, preferably, the catalyst includes one or more of triethylamine, triethylenediamine, ethylene glycol bis(dimethylaminoethyl ether), tetraethylammonium bromide, and bis(morpholino)diethyl ether.

[0027] In the preparation method of the hyperbranched active ester curing agent containing double bonds, preferably, the molar amount of the catalyst is 1-5 times the total molar amount of the aromatic dicarboxylic acid dichloride and the acyl chloride compound containing R group.

[0028] In the preparation method of the hyperbranched active ester curing agent containing double bonds, preferably, both the aromatic dicarboxylic acid dichloride and the acyl chloride compound containing R group are diluted with a solvent to a concentration of 0.01-0.05 mol / ml before use.

[0029] The solvents mentioned in this article are not particularly limited, as long as they can dissolve the reaction raw materials. Examples include one or more of tetrahydrofuran, methyl ethyl ketone, N,N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethylimidazolidin-2-one, 1,2-propanediol, methyl isobutyl ketone, methyl ethyl ketone, toluene, xylene, cyclohexanone, ethyl acetate, etc.

[0030] In the preparation method of the hyperbranched active ester curing agent containing double bonds, preferably, the reaction conditions for the co-reaction, the first reaction, and the second reaction include reacting at 5-10°C for 5-12 h under an inert gas atmosphere. The reaction conditions for the co-reaction, the first reaction, and the second reaction can be the same or different.

[0031] Preferably, the inert gas atmosphere includes one or more of nitrogen, argon, and helium. More preferably, it is nitrogen.

[0032] In the preparation method of the hyperbranched active ester curing agent containing double bonds, preferably, after the co-reaction and the second reaction are completed, the reaction product is purified, and then dried at 50-60°C and stored for later use.

[0033] Preferably, the purification treatment includes: precipitating the reaction product in pure water and / or ethanol, and washing the solid product obtained after filtration with ethanol and / or methanol.

[0034] The present invention also provides a formulation for an interlayer film, including the above-mentioned hyperbranched active ester curing agent containing double bonds.

[0035] Preferably, the formulation for the interlayer film includes: 5-12 parts of the hyperbranched active ester curing agent containing double bonds, 25-50 parts of the non-hyperbranched active ester curing agent, 20-80 parts of epoxy resin, 50-80 parts of inorganic filler, 0.5-1.5 parts of the first catalyst, and 0.1-1.0 parts of the second catalyst.

[0036] The hyperbranched structure in the hyperbranched active ester can provide more active ester group equivalents than the conventional commercially available linear active esters. On this basis, the free radical polymerization reaction of the double bonds in the hyperbranched active ester further increases the crosslinking density of the interlayer film. Acting together with the crosslinking reaction of the non-hyperbranched active ester and the epoxy resin, it improves the glass transition temperature of the interlayer film, reduces its thermal expansion coefficient, and improves its thermodynamic properties. In order to ensure a high reaction rate of the hyperbranched active ester, using a hyperbranched structure with a rigid skeleton can also improve the Tg and modulus of the interlayer film, reduce the steric hindrance effect during the curing reaction, further ensure the crosslinking density, and at the same time introduce nanoscale micropores into the curing system to improve the dielectric properties of the interlayer film.

[0037] Preferably, the non - hyperbranched active ester curing agent includes one or more of bisphenol A - type active ester, bisphenol M - type active ester, bisphenol F - type active ester, dicyclopentadiene - type active ester, biphenyl - type active ester, naphthalene - type active ester, and phenolic aldehyde - type active ester.

[0038] Preferably, the epoxy resin includes one or more of naphthalene - ring - type epoxy resin, dicyclopentadiene - type epoxy resin, bisphenol - type epoxy resin, biphenyl - type epoxy resin, naphthol - type epoxy resin, linear phenolic - type epoxy resin, aralkyl - type phenolic epoxy resin, aralkyl - biphenyl - type phenolic epoxy resin, and naphthol - type phenolic epoxy resin.

[0039] Preferably, the first catalyst includes one or more of pyridine - type catalysts, imidazole - type catalysts, pyrimidine - type catalysts, and thiazole - type catalysts. Further preferably, the first catalyst includes one or more of 4 - dimethylaminopyridine, 1 - ethyl - 2 - methylimidazole, 1 - tert - butyl - 4 - methylimidazole, 1 - cyanoethyl - 2 - ethyl - 4 - methylimidazole, 2 - phenylimidazole, 2 - phenyl - 4,5 - dihydroxymethylimidazole, 2 - phenyl - 4 - methyl - 5 - hydroxymethylimidazole, 2 - ethyl - 4 - methylimidazole, 1,8 - diazabicyclo[5,4,0]undec - 7 - ene, and 2,4,6 - tris(dimethylaminomethyl)phenol. The first catalyst is used to catalyze the reaction between the active ester group and the epoxy group.

[0040] Preferably, the second catalyst is a peroxide - type catalyst, including one or more of dicumyl peroxide, benzoyl peroxide, cyclohexanone peroxide, tert - butyl peroxide, cumene hydroperoxide, and lauroyl peroxide. The second catalyst is used to catalyze the free - radical polymerization reaction of double bonds in the resin system.

[0041] Preferably, the inorganic filler includes one or more of silica, talcum powder, calcium carbonate, alumina, glass, cordierite, barium sulfate, barium carbonate, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, and zirconium phosphate.

[0042] Preferably, the interlayer film formulation further includes 1 - 5 parts of additives and 200 - 300 parts of solvents.

[0043] There is no particular limitation on the additives, and any additives that can be used in the interlayer film for functional modification can be used, such as one or more of leveling agents, defoaming agents, thickening agents, and homogenizing agents.

[0044] The present invention also provides a build-up film, which is prepared from the above build-up film formulation. The preparation method of the build-up film comprises the following steps: mixing the raw materials in the above build-up film formulation evenly to obtain a build-up film slurry, coating the slurry on a substrate, and drying to obtain the build-up film.

[0045] Preferably, the drying temperature is 60~130°C, and the drying time is 1~60 min.

[0046] The selection of the substrate is not particularly limited, and commonly used substrates in the art can be used, such as one or more of PET film, polyethylene film, polypropylene film, polyvinyl chloride film, etc.

[0047] The present invention also provides an application of the build-up film, and the application includes the application in integrated circuit packaging.

[0048] Compared with the prior art, the present invention has the following beneficial effects:

[0049] 1. In the hyperbranched active ester curing agent containing double bonds provided by the present invention, there are many branched structures, so that compared with the conventional linear active ester curing agent, it has better fluidity. Using an alkyl end-capping can improve the solubility of the hyperbranched active ester in the solvent and obtain a uniform solution system, jointly improving the film-forming performance of the hyperbranched active ester.

[0050] 2. In the hyperbranched active ester curing agent containing double bonds provided by the present invention, the hyperbranched structure can provide more active ester group equivalents than the linear active ester; on this basis, the free radical polymerization reaction of the double bonds in the hyperbranched active ester further increases the crosslinking density, and together with the crosslinking reaction of the non-hyperbranched active ester curing agent and epoxy resin, it improves the glass transition temperature of the build-up film, reduces the thermal expansion coefficient, and improves its thermodynamic properties.

[0051] 3. The hyperbranched active ester curing agent containing double bonds provided by the present invention designs a hyperbranched structure with a rigid backbone, which can itself improve the Tg and modulus of the build-up film, reduce the steric hindrance effect during the curing reaction, and further ensure the crosslinking density; at the same time, it can introduce nano-scale micropores into the curing system to improve the dielectric properties of the build-up film; in addition, one of the active ester raw materials is resveratrol, which is an extract from grape skins and is a bio-based material, helping to alleviate the current energy problem.

[0052] 4. In the build-up film formulation provided by the present invention, a hyperbranched active ester containing double bonds is introduced as a curing agent. Combining with a non-hyperbranched active ester curing agent and epoxy resin, a build-up film with a high Tg, a low CTE, and a low dielectric constant can be obtained, ensuring the use performance of the build-up film in the field of integrated circuit packaging. Detailed embodiments

[0053] The technical solution of the present invention will be further described below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to illustrate the present invention and are not used to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0054] The raw material information used in the following examples and comparative examples is as follows:

[0055] Non-hyperbranched active ester curing agent: HPC-8000-65T of DIC;

[0056] Naphthalene ring type epoxy resin: HP-6000 of DIC;

[0057] Dicyclopentadiene type epoxy resin: HP7200 of DIC;

[0058] Bisphenol A type epoxy resin: EPIKOTE 828EL of Mitsubishi Chemical;

[0059] Silica powder: SO-C2 of Yaduma, D50 = 0.5um;

[0060] Leveling agent: GRANDIC PC4100 of DIC;

[0061] Substrate: LUMIRROR R80 of Toray Industries, Inc.

[0062] Example 1

[0063] The preparation method of the hyperbranched active ester curing agent containing double bonds in this example includes the following steps:

[0064] (1) After 0.5 mol of resveratrol, 1.7 mol of 4,4'-dihydroxybiphenyl and 2.5 mol of triethylamine were fully dissolved in tetrahydrofuran, 80 ml of terephthaloyl chloride diluted with tetrahydrofuran (molar concentration: 0.01 mol / ml) and 40 ml of acetyl chloride diluted with tetrahydrofuran (molar concentration: 0.01 mol / ml) were added dropwise, and the reaction was carried out at 6 °C for 10 h under a nitrogen atmosphere;

[0065] (2) The reaction product was precipitated in a mixed system of water and ethanol (volume ratio of water to ethanol is 1:3), and the solid product obtained by filtration was washed with ethanol and dried in vacuo at 60 °C for later use.

[0066] The hyperbranched active ester curing agent containing double bonds has the following structural formula: where n = 2.9,

[0067] .

[0068] Example 2

[0069] The preparation method of the hyperbranched active ester curing agent containing double bonds in this example includes the following steps:

[0070] (1) After 0.8 mol of resveratrol, 4.0 mol of 1,5-dihydroxynaphthalene and 5.0 mol of triethylenediamine are fully dissolved in tetrahydrofuran, 75 ml of terephthaloyl chloride diluted with tetrahydrofuran (molar concentration: 0.02 mol / ml) is added dropwise, and the reaction is carried out at 6 °C for 10 h in a nitrogen atmosphere; then 25 ml of propionyl chloride diluted with tetrahydrofuran (molar concentration: 0.02 mol / ml) is added dropwise, and the reaction is carried out at 6 °C for 10 h in a nitrogen atmosphere;

[0071] (2) The reaction product is precipitated in a mixed system of water and ethanol (volume ratio of water to ethanol is 1:3), the solid product obtained by filtration is washed with methanol, and dried in vacuum at 60 °C for later use.

[0072] The above hyperbranched active ester curing agent containing double bonds has the following structural formula: where n = 2.9,

[0073] .

[0074] Example 3

[0075] The preparation method of the hyperbranched active ester curing agent containing double bonds in this example includes the following steps:

[0076] (1) After 0.5 mol of resveratrol, 1.7 mol of 4,4'-dihydroxybiphenyl and 2.5 mol of triethylamine are fully dissolved in tetrahydrofuran, 80 ml of terephthaloyl chloride diluted with tetrahydrofuran (molar concentration: 0.01 mol / ml) and 20 ml of acetyl chloride diluted with tetrahydrofuran (molar concentration: 0.01 mol / ml) are added dropwise, and the reaction is carried out at 6 °C for 10 h in a nitrogen atmosphere;

[0077] (2) The reaction product is precipitated in a mixed system of water and ethanol (volume ratio of water to ethanol is 1:3), the solid product obtained by filtration is washed with ethanol, and dried in vacuum at 60 °C for later use.

[0078] The above hyperbranched active ester curing agent containing double bonds has the following structural formula: where n = 5,

[0079] .

[0080] Application Example 1

[0081] This application example provides a laminated film, which is prepared by the following steps:

[0082] Take 8 parts of the hyperbranched active ester curing agent containing double bonds prepared in Example 1, 36 parts of non-hyperbranched active ester curing agent, 56 parts of naphthalene ring-type epoxy resin, 70 parts of silica powder, 1.0 part of 4-dimethylaminopyridine, 0.5 part of diisopropylbenzene peroxide and 3 parts of leveling agent, dissolve and mix them evenly in a solvent (160 ml of tetrahydrofuran and 90 ml of methyl ethyl ketone) to obtain an interlayer film slurry. Coat the slurry on a substrate and dry it at 80 °C for 10 min to obtain the interlayer film.

[0083] Application Example 2

[0084] This application example provides an interlayer film, which is prepared by the following steps:

[0085] Take 5 parts of the hyperbranched active ester curing agent containing double bonds prepared in Example 2, 41 parts of non-hyperbranched active ester curing agent, 54 parts of dicyclopentadiene-type epoxy resin, 70 parts of silica powder, 0.8 part of 1-ethyl-2-methylimidazole, 0.6 part of benzoyl peroxide and 3 parts of leveling agent, dissolve and mix them evenly in a solvent (170 ml of tetrahydrofuran and 80 ml of N-methylpyrrolidone) to obtain an interlayer film slurry. Coat the slurry on a substrate and dry it at 80 °C for 10 min to obtain the interlayer film.

[0086] Application Example 3

[0087] This application example provides an interlayer film, which is prepared by the following steps:

[0088] Take 10 parts of the hyperbranched active ester curing agent containing double bonds prepared in Example 3, 32 parts of non-hyperbranched active ester curing agent, 58 parts of bisphenol A-type epoxy resin, 70 parts of silica powder, 1.2 parts of 1-tert-butyl-4-methylimidazole, 0.8 part of tert-butyl peroxide and 3 parts of leveling agent, dissolve and mix them evenly in a solvent (150 ml of tetrahydrofuran and 100 ml of methyl ethyl ketone) to obtain an interlayer film slurry. Coat the slurry on a substrate and dry it at 80 °C for 10 min to obtain the interlayer film.

[0089] Application Comparative Example 1

[0090] This application comparative example provides an interlayer film, which is prepared by the following steps:

[0091] Take 15 parts of the hyperbranched active ester curing agent containing double bonds prepared in Example 1, 29 parts of non-hyperbranched active ester curing agent, 56 parts of naphthalene ring-type epoxy resin, 70 parts of silica powder, 1.0 part of 4-dimethylaminopyridine, 0.5 part of diisopropylbenzene peroxide and 3 parts of leveling agent, dissolve and mix them evenly in a solvent (160 ml of tetrahydrofuran and 90 ml of methyl ethyl ketone) to obtain an interlayer film slurry. Coat the slurry on a substrate and dry it at 80 °C for 10 min to obtain the interlayer film.

[0092] Application Comparative Example 2

[0093] The difference between this application comparative example and Application Example 1 is that the hyperbranched active ester curing agent containing double bonds is not added to the interlayer film material, and the rest is the same as in Example 1.

[0094] The preparation method of the interlayer film in this comparative example includes the following steps: Take 44 parts of non-hyperbranched active ester curing agent, 56 parts of naphthalene ring type epoxy resin, 70 parts of silica powder, 1.0 part of 4-dimethylaminopyridine, 0.5 part of dicumyl peroxide and 3 parts of leveling agent, dissolve and mix them evenly in a solvent (160 ml of tetrahydrofuran and 90 ml of methyl ethyl ketone) to obtain an interlayer film slurry, coat the slurry on a substrate, and dry it at 80 °C for 10 min to obtain the interlayer film.

[0095] The raw material components of the interlayer films in the above Application Example and Application Comparative Example are set as shown in Table 1.

[0096] Table 1 Raw material component settings of the interlayer films in the Application Example and Application Comparative Example

[0097] 。

[0098] Perform thermodynamic performance and dielectric performance tests on the obtained interlayer films of the above Application Example and Application Comparative Example. The specific test methods are as follows:

[0099] 1. Coefficient of thermal expansion: Cure the obtained interlayer film at 190 °C for 90 min, then peel off the substrate to obtain a test specimen; Cut the test specimen into test pieces with a width of 2 mm and a length of 17 mm, and use a thermomechanical analysis device to perform tests in the tensile mode. The preloading force is 0.02 N, the temperature rise range is 25 °C to 260 °C, and the temperature rise rate is 5 °C / min to perform thermomechanical analysis to obtain the coefficient of thermal expansion in the range of 25 °C to 150 °C;

[0100] 2. Glass transition temperature: Cure the obtained interlayer film at 190 °C for 90 min, then peel off the substrate to obtain a test specimen; Cut the test specimen into test pieces with a width of 6 mm and a length of 15 mm, and use a dynamic thermomechanical analysis device to perform tests in the tensile mode measurement mode. Set the test conditions: the vibration frequency is 1 Hz, the amplitude is 15 μm, the temperature rise rate is 5 °C / min, and the temperature rise range is 25 °C to 260 °C to obtain the glass transition temperature Tg;

[0101] 3. Dielectric Constant: The obtained additional layer film was cured at 190 °C for 90 min, and then the substrate was peeled off to obtain a test specimen; the test specimen was cut into a test piece of 51 mm × 69 mm, and after being stored for 16 h under the conditions of 23 ± (1 - 5) °C and 50 ± 5% relative humidity, the dielectric constant of the test piece was measured by the strip line method under the conditions of a measurement frequency of 10 GHz and a measurement temperature of 22 - 24 °C;

[0102] 4. Loss Factor: The obtained additional layer film was cured at 190 °C for 90 min, and then the substrate was peeled off to obtain a test specimen; the test specimen was cut into a test piece of 80 mm × 80 mm, and after being stored for 16 h under the conditions of 23 ± (1 - 5) °C and 50 ± 5% relative humidity, the loss factor of the test piece was measured by the resonant cavity method under the conditions of a measurement frequency of 10 GHz and a measurement temperature of 22 - 24 °C;

[0103] The specific test results are shown in Table 2.

[0104] Table 2 Performance Detection Data of Examples and Comparative Examples

[0105] 。

[0106] As shown in Table 2, it can be seen from Application Examples 1 - 3 that the hyperbranched active ester curing agent prepared by using the ratio within the technical solution scope of the present invention, combined with a non - hyperbranched active ester curing agent and different types of epoxy resins to prepare an additional layer film, shows excellent thermodynamic and dielectric properties after being applied to the encapsulation carrier board, ensuring the service performance of the additional layer film in the field of integrated circuit packaging; while in Comparative Example 1, an excessive amount of hyperbranched active ester curing agent was used, and the steric hindrance effect was obvious, resulting in some active ester groups being unable to participate in the reaction, leading to a decrease in cross - linking degree and the phenomenon of deterioration of Tg and CTE; in Comparative Example 2, no hyperbranched active ester curing agent was added, the fluidity of the system decreased, the leveling performance became poor, the obtained additional layer film system was uneven, and both the thermodynamic and dielectric properties were poor.

[0107] All aspects, embodiments, and features of the present invention should be considered illustrative in all respects and do not limit the present invention. The scope of the present invention is only defined by the claims. Without departing from the spirit and scope of the claimed invention, those skilled in the art will be aware of other embodiments, modifications, and uses.

[0108] In the preparation method of the present invention, the order of each step is not limited to the listed order. For those of ordinary skill in the art, without creative efforts, the changes in the sequence of each step are also within the protection scope of the present invention. In addition, two or more steps or actions can be carried out simultaneously.

[0109] Finally, it should be noted that the specific embodiments described herein are merely illustrative of the present invention and do not limit the implementation manners of the present invention. Those skilled in the art to which the present invention pertains can make various modifications or supplements to the described specific embodiments or use similar ways to replace them. It is not necessary and impossible to list all implementation manners here. And these obvious changes or variations derived from the essence of the present invention still fall within the protection scope of the present invention. Interpreting them as any additional limitation is contrary to the spirit of the present invention.

Claims

1. A hyperbranched active ester curing agent containing double bonds, characterized in that, Its structural formula is shown in Formula I: Formula I; Wherein, R is selected from C1-C3 linear alkyl groups; X is a biphenyl group or a naphthyl group; n is from 1 to 10; The hyperbranched active ester curing agent containing double bonds is formed by the reaction of resveratrol, a compound with X groups having hydroxyl groups at both ends, aromatic dicarboxylic acid dichloride, and an acyl chloride compound containing an R group; The aromatic dicarboxylic acid dichloride includes one or more of terephthaloyl chloride, phthaloyl chloride, and isophthaloyl chloride; The molar ratio of resveratrol to the compound with X groups having hydroxyl groups at both ends is 1:(2-10).

2. The hyperbranched active ester curing agent containing double bonds according to claim 1, characterized in that The molar ratio of the aromatic dicarboxylic acid dichloride to the acyl chloride compound containing an R group is (1-5):

1.

3. The hyperbranched active ester curing agent containing double bonds according to claim 1, characterized in that, The molar ratio of the total amount of the aromatic dicarboxylic acid dichloride and the acyl chloride compound containing an R group to the total amount of resveratrol and the compound with X groups having hydroxyl groups at both ends is 1:(1-5).

4. A preparation method of a hyperbranched active ester curing agent containing double bonds as described in claim 1, characterized in that, The preparation method includes the following steps: dissolving resveratrol, the compound with X groups having hydroxyl groups at both ends, and a catalyst in a solvent, and adding the aromatic dicarboxylic acid dichloride and the acyl chloride compound containing an R group for a common reaction to obtain a hyperbranched active ester curing agent containing double bonds.

5. A preparation method of a hyperbranched active ester curing agent containing double bonds as described in claim 1, characterized in that, The preparation method includes the following steps: dissolving resveratrol, the compound with X groups having hydroxyl groups at both ends, and a catalyst in a solvent, adding the aromatic dicarboxylic acid dichloride for a first reaction, and then adding the acyl chloride compound containing an R group for a second reaction to obtain a hyperbranched active ester curing agent containing double bonds.

6. The preparation method according to claim 4 or 5, characterized in that, The catalyst includes one or more of triethylamine, triethylenediamine, ethylene glycol bis(dimethylaminoethyl ether), tetraethylammonium bromide, and bis(morpholino)diethyl ether; And / or, the molar amount of the catalyst is 1-5 times the total molar amount of the aromatic dicarboxylic acid dichloride and the acyl chloride compound containing an R group; And / or, before use, both the aromatic dicarboxylic acid dichloride and the acyl chloride compound containing an R group are diluted with a solvent to a concentration of 0.01-0.05 mol / ml; And / or, the reaction conditions for the common reaction, the first reaction, and the second reaction include reacting at 5-10°C for 5-12 h under an inert gas atmosphere; And / or, after the common reaction and the second reaction are completed, the reaction product is purified and then dried at 50-60°C and stored for later use.

7. A formulation for an additional layer film, characterized in that, The formulation of the interlayer film includes a hyperbranched active ester curing agent containing double bonds as described in Claim 1 or 2. The formulation of the interlayer film includes: 5-12 parts of the hyperbranched active ester curing agent containing double bonds, 25-50 parts of a non-hyperbranched active ester curing agent, 20-80 parts of epoxy resin, 50-80 parts of inorganic filler, 0.5-1.5 parts of a first catalyst, and 0.1-1.0 parts of a second catalyst.

8. A formulation of an additional layer film according to claim 7, characterized in that, The non-hyperbranched active ester curing agent includes one or more of bisphenol A type active ester, bisphenol M type active ester, bisphenol F type active ester, dicyclopentadiene type active ester, biphenyl type active ester, naphthalene type active ester, and phenolic type active ester; And / or, the epoxy resin includes one or more of naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, linear phenolic type epoxy resin, aralkyl type phenolic epoxy resin, aralkyl biphenyl type phenolic epoxy resin, and naphthol type phenolic epoxy resin; And / or, the first catalyst includes one or more of pyridine catalysts, imidazole catalysts, pyrimidine catalysts, and thiazole catalysts; And / or, the second catalyst is a peroxide catalyst; And / or, the inorganic filler includes one or more of silica, talcum powder, calcium carbonate, alumina, glass, cordierite, barium sulfate, barium carbonate, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, and zirconium phosphate.

9. A build-up film prepared from a build-up film formulation as described in claim 7, characterized in that, The method for preparing the interlayer film includes the following steps: mixing the raw materials in the above interlayer film formulation evenly to obtain an interlayer film slurry, coating the slurry on a substrate, and drying to obtain the interlayer film.

10. An application of an interlayer film as described in claim 9 in integrated circuit packaging.

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