Hyperbranched active ester curing agent containing double bonds and layer-adding film containing active ester curing agent

Abstract

The invention belongs to the technical field of IC packaging materials, and relates to a hyperbranched active ester curing agent containing double bonds and a layer-adding film containing the active ester curing agent. The structural formula of the hyperbranched active ester curing agent containing the double bonds is as shown in a formula I: # imgabs0 # formula I; the double-bond-containing hyperbranched active ester curing agent contains more branched structures, has better flowability, can improve the film-forming property of the curing agent, and provides more active ester equivalent; meanwhile, through the free radical polymerization reaction of double bonds, the crosslinking density is further increased, and after the combined action with the crosslinking reaction of the non-hyperbranched active ester curing agent and the epoxy resin, the glass-transition temperature of the layer-adding film can be increased, the thermal expansion coefficient of the layer-adding film can be reduced, and the thermodynamic property of the layer-adding film can be improved; in addition, the hyperbranched rigid skeleton structure can introduce nanoscale micropores into a curing system, so that the dielectric property of the layer-adding film is improved.

Description

Technical Field

[0001] The 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, build-up films are crucial to improving the performance of electronic packaging. At present, mainstream build-up film raw materials include epoxy resin, phenolic resin, cyanate ester, active ester, etc. Among them, the thermosetting resin system composed of active ester and epoxy resin will not generate additional hydroxyl groups (-OH) during the reaction process, and has the characteristics of low dielectric loss and low water absorption, which meets the requirements of the new generation of build-up films for electrical performance.

[0003] In addition, the active ester plus epoxy resin system also exhibits excellent film-forming ability, good heat resistance and excellent chemical stability. With the continuous development of today's electronic technology, the chip packaging process is moving towards smaller line widths and line spacing, and the chip size is also expanding year by year. Faced with such a development trend, advanced packaging has put forward higher standards for build-up film materials, especially in terms of improving the glass transition temperature (Tg) and reducing its coefficient of thermal expansion (CTE). A high Tg value can ensure that the material can still maintain sufficient mechanical strength at higher temperatures; while a low CTE helps to reduce the problem of board bending caused by the difference in thermal expansion between different materials due to temperature changes, thereby improving the reliability of the entire packaging structure.

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

[0005] The present invention aims at the above problems existing in the prior art and 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 a hyperbranched active ester as a curing agent, combined with a non-hyperbranched active ester curing agent and an epoxy resin, to obtain a build-up film with high Tg, low CTE and low dielectric constant, thereby 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 double-bond-containing hyperbranched active ester curing agent, the structural formula of which is shown in Formula I:

[0007] Formula I;

[0008] Wherein, R is selected from one or more of substituted or unsubstituted C1-C10 straight chain alkyl, substituted or unsubstituted C1-C10 branched chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl; preferably, substituted or unsubstituted C1-C3 straight chain alkyl;

[0009] X is selected from one or more of a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted biphenyl, a substituted or unsubstituted alicyclic hydrocarbon, a substituted or unsubstituted naphthyl ether, a substituted or unsubstituted bisphenol A, a substituted or unsubstituted dicyclopentadiene, and a substituted or unsubstituted 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide group (DOPO);

[0010] n is 1-10, preferably 1-5.

[0011] The invention provides a double-bond-containing hyperbranched active ester curing agent, which contains more branched structures in its structural formula, has better fluidity than active esters with linear structures, and can improve the film-forming property of the active ester system; alkyl end-capping is used in the hyperbranched active ester, which helps to improve the solubility of the hyperbranched active ester in the solvent, obtain a uniform solution system, and further improve its film-forming property.

[0012] Preferably, the double-bond-containing hyperbranched active ester curing agent is prepared by reacting resveratrol, an X-group compound having hydroxyl groups at both ends, an aromatic dicarboxylic acid chloride, and an acyl chloride compound containing an R group;

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

[0014] The aromatic dicarboxylic acid 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 the R group has the following structural formula: .

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

[0018] The specific reaction is shown in reaction formula Ⅰ: Reaction formula Ⅰ.

[0019] Preferably, the molar ratio of resveratrol to the X-group compound having hydroxyl groups at both ends is 1:(2-10), and more preferably 1:(3-5).

[0020] The present invention strictly controls the ratio of resveratrol and the X group compound with hydroxyl groups at both ends in the reaction. If the ratio of resveratrol is too high, the hyperbranching degree is too large, which will inhibit the cross-linking reaction due to the steric effect and reduce the cross-linking degree of the resin after thermal curing; otherwise, the hyperbranching degree is too small, resulting in reduced product fluidity, weakened leveling ability, reduced introduction of nano-scale micropores, and poor dielectric properties.

[0021] Preferably, the molar ratio of the aromatic dicarboxylic acid chloride to the acyl chloride compound containing an R group is (1-5):1. More preferably, it is (2-3):1.

[0022] Preferably, the molar ratio of the total amount of the aromatic dicarboxylic acid chloride and the acyl chloride compound containing the R group to the total amount of resveratrol and the X group compound with hydroxyl groups at both ends is 1:(1-5), and more preferably 1:(1.5-3).

[0023] The present invention also provides a method for preparing a hyperbranched active ester curing agent containing a double bond, comprising the following steps: dissolving resveratrol, an X group compound having hydroxyl groups at both ends, and a catalyst in a solvent, adding aromatic dicarboxylic acid chloride and an acyl chloride compound containing an R group to react together to obtain a hyperbranched active ester curing agent containing a double bond.

[0024] The present invention also provides a method for preparing a hyperbranched active ester curing agent containing a double bond, comprising the following steps: dissolving resveratrol, an X group compound having hydroxyl groups at both ends, and a catalyst in a solvent, adding aromatic dicarboxylic acid chloride to carry out a first reaction, and then adding an acyl chloride compound containing an R group to carry out a second reaction to obtain a hyperbranched active ester curing agent containing a double bond.

[0025] In the preparation method of the double-bond-containing hyperbranched active ester curing agent, preferably, the catalyst includes one or more of triethylamine, triethylenediamine, ethylene glycol bis(dimethylaminoethyl) ether, tetraethylammonium bromide, and bismorpholine diethyl ether.

[0026] In the preparation method of the double-bond-containing hyperbranched active ester curing agent, preferably, the molar amount of the catalyst is 1 to 5 times the total molar amount of the aromatic dicarboxylic acid chloride and the acyl chloride compound containing the R group.

[0027] In the preparation method of the double-bond-containing hyperbranched active ester curing agent, preferably, the aromatic dicarboxylic acid chloride and the acyl chloride compound containing an R group are both diluted with a solvent to a concentration of 0.01-0.05 mol / ml before use.

[0028] The solvent mentioned herein is not particularly limited, as long as it can dissolve the reaction raw materials, and can be listed as one or more of tetrahydrofuran, butanone, N,N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethylimidazolidin-2-one, 1,2-propylene glycol, methyl isobutyl ketone, methyl ethyl ketone, toluene, xylene, cyclohexanone, ethyl acetate, etc.

[0029] In the preparation method of the double-bond-containing hyperbranched active ester curing agent, preferably, the reaction conditions of the common reaction, the first reaction and the second reaction include reacting at 5-10° C. for 5-12 hours under an inert gas atmosphere. The reaction conditions of the common reaction, the first reaction and the second reaction may be the same or different.

[0030] Preferably, the inert gas atmosphere includes one or more of nitrogen, argon and helium, and more preferably nitrogen.

[0031] In the preparation method of the double-bond-containing hyperbranched active ester curing agent, preferably, 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.

[0032] Preferably, the purification treatment comprises: precipitating the reaction product in pure water and / or ethanol, and washing the solid product obtained after filtering with ethanol and / or methanol.

[0033] The present invention also provides a build-up film formula, comprising the above-mentioned double-bond-containing hyperbranched active ester curing agent.

[0034] Preferably, the build-up film formula comprises: 5 to 12 parts of a hyperbranched active ester curing agent containing double bonds, 25 to 50 parts of a non-hyperbranched active ester curing agent, 20 to 80 parts of an epoxy resin, 50 to 80 parts of an inorganic filler, 0.5 to 1.5 parts of a first catalyst and 0.1 to 1.0 parts of a second catalyst.

[0035] The hyperbranched structure in the hyperbranched active ester can provide more active ester equivalents than 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 build-up film, and works together with the crosslinking reaction of the non-hyperbranched active ester and the epoxy resin to increase the glass transition temperature of the build-up film, reduce its thermal expansion coefficient, and improve its thermodynamic properties. In order to ensure the high reaction rate of the hyperbranched active ester, the hyperbranched structure with a rigid skeleton is used, which can also increase the Tg and modulus of the build-up film, reduce the steric effect during the curing reaction, further ensure the crosslinking density, and introduce nano-scale micropores into the curing system to improve the dielectric properties of the build-up film.

[0036] 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 type active ester.

[0037] 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.

[0038] Preferably, the first catalyst includes one or more of pyridine catalysts, imidazole catalysts, pyrimidine catalysts, and thiazole 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-diazacyclo[5,4,0]undecene-7, and 2,4,6-tris(dimethylaminomethyl)phenol. The first catalyst is used to catalyze the reaction of active ester groups with epoxy groups.

[0039] Preferably, the second catalyst is a peroxidation catalyst, including one or more of dicumyl peroxide, dibenzoyl 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.

[0040] Preferably, the inorganic filler includes one or more of silicon dioxide, talc, calcium carbonate, aluminum oxide, 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.

[0041] Preferably, the build-up film formula further comprises 1 to 5 parts of an auxiliary agent and 200 to 300 parts of a solvent.

[0042] The auxiliary agent is not particularly limited, and any auxiliary agent that can be used in the build-up film to improve its function can be used, and can be listed as one or more of a leveling agent, a defoaming agent, a thickener, and a leveling agent.

[0043] The present invention also provides a build-up film, which is prepared from the above build-up film formula. The preparation method of the build-up film comprises the following steps: uniformly mixing the raw materials in the above build-up film formula to obtain a build-up film slurry, coating the slurry on a substrate, and drying to obtain a build-up film.

[0044] Preferably, the drying temperature is 60-130° C., and the drying time is 1-60 min.

[0045] The selection of the substrate is not particularly limited, and any substrate commonly used in the art can be used, which can be one or more of PET film, polyethylene film, polypropylene film, polyvinyl chloride film, etc.

[0046] The present invention also provides an application of a build-up layer film, wherein the application includes application in integrated circuit packaging.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] 1. The hyperbranched active ester curing agent containing double bonds provided by the present invention has a relatively large number of branched structures, so that it has better fluidity than conventional linear active ester curing agents. The use of alkyl end-capping can improve the solubility of the hyperbranched active ester in the solvent, obtain a uniform solution system, and jointly improve the film-forming performance of the hyperbranched active ester.

[0049] 2. In a hyperbranched active ester curing agent containing double bonds provided by the present invention, the hyperbranched structure can provide more active ester group equivalents than 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, and works together with the crosslinking reaction of the non-hyperbranched active ester curing agent and the epoxy resin to increase the glass transition temperature of the build-up film, reduce the thermal expansion coefficient, and improve its thermodynamic properties.

[0050] 3. The present invention provides a double-bond-containing hyperbranched active ester curing agent, which is designed with a hyperbranched structure with a rigid skeleton, which can improve the Tg and modulus of the build-up film, reduce the steric effect during the curing reaction, and further ensure the cross-linking 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 skin and a bio-based material, which helps to alleviate the current energy problem.

[0051] 4. In a build-up film formula provided by the present invention, a hyperbranched active ester containing double bonds is introduced as a curing agent. Combined with a non-hyperbranched active ester curing agent and an epoxy resin, a build-up film with a higher Tg, a lower CTE and a lower dielectric constant can be obtained, thereby ensuring the performance of the build-up film in the field of integrated circuit packaging. DETAILED DESCRIPTION

[0052] The technical solution of the present invention is 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 intended 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 claims attached to this application.

[0053] The raw materials used in the following examples and comparative examples are as follows:

[0054] Non-hyperbranched active ester curing agent: DIC's HPC-8000-65T;

[0055] Naphthalene ring epoxy resin: DIC's HP-6000;

[0056] Dicyclopentadiene epoxy resin: DIC's HP7200;

[0057] Bisphenol A epoxy resin: EPIKOTE 828EL from Mitsubishi Chemical;

[0058] Silica powder: SO-C2 from Yaduma, D50=0.5um;

[0059] Leveling agent: DIC's GRANDIC PC4100;

[0060] Substrate: LUMIRROR R80 from Toray.

[0061] Example 1

[0062] The preparation method of the double-bond-containing hyperbranched active ester curing agent of this embodiment comprises the following steps:

[0063] (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 (molar concentration of 0.01 mol / ml) diluted with tetrahydrofuran and 40 ml of acetyl chloride (molar concentration of 0.01 mol / ml) diluted with tetrahydrofuran are added dropwise, and the mixture is reacted at 6°C in a nitrogen atmosphere for 10 h;

[0064] (2) The reaction product was precipitated in a mixture of water and ethanol (the volume ratio of water to ethanol was 1:3). The solid product obtained after filtration was washed with ethanol, dried under vacuum at 60°C and stored for later use.

[0065] The above double-bond-containing hyperbranched active ester curing agent has the following structural formula: wherein n=2.9,

[0066] .

[0067] Example 2

[0068] The preparation method of the double-bond-containing hyperbranched active ester curing agent of this embodiment comprises the following steps:

[0069] (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 (molar concentration of 0.02 mol / ml) diluted with tetrahydrofuran is added dropwise, and the mixture is reacted at 6°C for 10 h in a nitrogen atmosphere; then 25 ml of propionyl chloride (molar concentration of 0.02 mol / ml) diluted with tetrahydrofuran is added dropwise, and the mixture is reacted at 6°C for 10 h in a nitrogen atmosphere;

[0070] (2) The reaction product was precipitated in a mixture of water and ethanol (the volume ratio of water to ethanol was 1:3). The solid product obtained after filtration was washed with methanol, dried under vacuum at 60°C and stored for later use.

[0071] The above double-bond-containing hyperbranched active ester curing agent has the following structural formula: wherein n=2.9,

[0072] .

[0073] Example 3

[0074] The preparation method of the double-bond-containing hyperbranched active ester curing agent of this embodiment comprises the following steps:

[0075] (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 (molar concentration of 0.01 mol / ml) diluted with tetrahydrofuran and 20 ml of acetyl chloride (molar concentration of 0.01 mol / ml) diluted with tetrahydrofuran are added dropwise, and the mixture is reacted at 6°C in a nitrogen atmosphere for 10 h;

[0076] (2) The reaction product was precipitated in a mixture of water and ethanol (the volume ratio of water to ethanol was 1:3). The solid product obtained after filtration was washed with ethanol, dried under vacuum at 60°C and stored for later use.

[0077] The above double-bond-containing hyperbranched active ester curing agent has the following structural formula: wherein n=5,

[0078] .

[0079] Application Example 1

[0080] This application embodiment provides a build-up film, which is prepared by the following steps:

[0081] Take 8 parts of the double-bond-containing hyperbranched active ester curing agent prepared in Example 1, 36 parts of non-hyperbranched active ester curing agent, 56 parts of naphthalene ring epoxy resin, 70 parts of silicon powder, 1.0 part of 4-dimethylaminopyridine, 0.5 diisopropylbenzene peroxide and 3 parts of leveling agent, dissolve and mix evenly in a solvent (160ml of tetrahydrofuran and 90ml of methyl ethyl ketone) to obtain a build-up film slurry, apply the slurry on a substrate, and dry at 80°C for 10 minutes to obtain the build-up film.

[0082] Application Example 2

[0083] This application embodiment provides a build-up film, which is prepared by the following steps:

[0084] Take 5 parts of the double-bond-containing hyperbranched active ester curing agent prepared in Example 2, 41 parts of non-hyperbranched active ester curing agent, 54 parts of dicyclopentadiene epoxy resin, 70 parts of silicon powder, 0.8 parts of 1-ethyl-2-methylimidazole, 0.6 parts of dibenzoyl peroxide and 3 parts of leveling agent, dissolve and mix evenly in a solvent (170 ml of tetrahydrofuran and 80 ml of N-methylpyrrolidone) to obtain a build-up film slurry, apply the slurry on a substrate, and dry at 80° C. for 10 min to obtain the build-up film.

[0085] Application Example 3

[0086] This application embodiment provides a build-up film, which is prepared by the following steps:

[0087] Take 10 parts of the double-bond hyperbranched active ester curing agent prepared in Example 3, 32 parts of non-hyperbranched active ester curing agent, 58 parts of bisphenol A epoxy resin, 70 parts of silicon powder, 1.2 parts of 1-tert-butyl-4-methylimidazole, 0.8 parts of tert-butyl peroxide and 3 parts of leveling agent, dissolve and mix evenly in a solvent (150 ml of tetrahydrofuran and 100 ml of methyl ethyl ketone) to obtain a build-up film slurry, apply the slurry on a substrate, and dry at 80° C. for 10 minutes to obtain the build-up film.

[0088] Application Comparative Example 1

[0089] This comparative example provides a build-up film, which is prepared by the following steps:

[0090] Take 15 parts of the double-bond hyperbranched active ester curing agent prepared in Example 1, 29 parts of non-hyperbranched active ester curing agent, 56 parts of naphthalene ring epoxy resin, 70 parts of silicon powder, 1.0 part of 4-dimethylaminopyridine, 0.5 diisopropylbenzene peroxide and 3 parts of leveling agent, dissolve and mix evenly in a solvent (160ml of tetrahydrofuran and 90ml of methyl ethyl ketone) to obtain a build-up film slurry, apply the slurry on a substrate, and dry at 80°C for 10 minutes to obtain the build-up film.

[0091] Application Comparative Example 2

[0092] The difference between this comparative application example and application example 1 is that no hyperbranched active ester curing agent containing double bonds is added to the build-up film material, and the rest is the same as example 1.

[0093] The preparation method of the build-up film in this comparative example includes the following steps: dissolving 44 parts of a non-hyperbranched active ester curing agent, 56 parts of a naphthalene ring epoxy resin, 70 parts of silicon powder, 1.0 part of 4-dimethylaminopyridine, 0.5 parts of diisopropylbenzene peroxide and 3 parts of a leveling agent in a solvent (160 ml of tetrahydrofuran and 90 ml of methyl ethyl ketone) and mixing them evenly to obtain a build-up film slurry, coating the slurry on a substrate, and drying at 80°C for 10 minutes to obtain the build-up film.

[0094] The raw material components of the build-up films of the above-mentioned application examples and application comparison examples are set as shown in Table 1.

[0095] Table 1. Raw material composition of the build-up film in the application examples and comparative examples

[0096] .

[0097] The thermodynamic properties and dielectric properties of the build-up films obtained from the above application examples and the application comparison examples were tested, and the specific test methods are as follows:

[0098] 1. Thermal expansion coefficient: The obtained build-up film was cured at 190°C for 90 minutes, and then the substrate was peeled off to obtain a test sample; the test sample was cut into a test piece with a width of 2 mm and a length of 17 mm, and a thermomechanical analysis device was used to test in the pull-up mode, with a preload force of 0.02N, a temperature rise range of 25°C~260°C, and a temperature rise rate of 5°C / min. The thermal mechanical analysis was performed to obtain the thermal expansion coefficient in the range of 25°C to 150°C;

[0099] 2. Glass transition temperature: The obtained build-up film was cured at 190°C for 90 minutes, and then the substrate was peeled off to obtain a test sample; the test sample was cut into a test piece with a width of 6 mm and a length of 15 mm, and tested using a dynamic thermomechanical analysis device in tensile mode. The test conditions were set to a vibration frequency of 1 Hz, an amplitude of 15 μm, a heating rate of 5°C / min, and a heating range of 25°C~260°C to obtain the glass transition temperature Tg;

[0100] 3. Dielectric constant: The obtained build-up film was cured at 190°C for 90 minutes, and then the substrate was peeled off to obtain a test sample; the test sample was cut into a test piece of 51mm×69mm, and after being stored at 23±(1~5)°C and 50±5% relative humidity for 16 hours, the dielectric constant of the test piece was measured using the stripline method at a measurement frequency of 10GHz and a measurement temperature of 22~24°C;

[0101] 4. Loss factor: The obtained build-up film was cured at 190°C for 90 minutes, and then the substrate was peeled off to obtain a test sample; the test sample was cut into a test piece of 80 mm × 80 mm, and after being stored at 23±(1~5)°C and 50±5% relative humidity for 16 hours, the loss factor of the test piece was measured using the resonant cavity method at a measurement frequency of 10 GHz and a measurement temperature of 22~24°C;

[0102] The specific test results are shown in Table 2.

[0103] Table 2 Performance test data of examples and comparative examples

[0104] .

[0105] As shown in Table 2, it can be seen from Application Examples 1 to 3 that the hyperbranched active ester curing agent prepared in a proportion within the scope of the technical solution of the present invention is used in combination with a non-hyperbranched active ester curing agent and different types of epoxy resins to prepare a build-up film, which exhibits excellent thermodynamic properties and dielectric properties after being applied to a packaging carrier, thereby ensuring the use performance of the build-up film in the field of integrated circuit packaging; while in Application Comparative Example 1, an excessive amount of hyperbranched active ester curing agent is used, and the steric hindrance effect is obvious, so that part of the active ester groups cannot be added to the reaction, resulting in a decrease in the degree of crosslinking, and the phenomenon of Tg and CTE degradation occurs; in Application Comparative Example 2, no hyperbranched active ester curing agent is added, the fluidity of the system is reduced, the leveling performance deteriorates, the resulting build-up film system is uneven, and the thermodynamic properties and dielectric properties are poor.

[0106] The various aspects, embodiments, and features of the present invention should be considered to be illustrative in all aspects and not limiting of the present invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.

[0107] In the preparation method of the present invention, the order of each step is not limited to the order listed. For those skilled in the art, without creative work, the order of each step is also within the protection scope of the present invention. In addition, two or more steps or actions can be performed simultaneously.

[0108] Finally, it should be noted that the specific embodiments described herein are merely examples of the present invention, and are not intended to limit the implementation methods of the present invention. A person skilled in the art of the present invention may make various modifications or supplements to the specific embodiments described, or replace them in a similar manner. It is not necessary and impossible to provide all examples of all implementation methods here. However, these obvious changes or modifications derived from the essential spirit of the present invention still fall within the scope of protection of the present invention, and interpreting them as any additional limitation is contrary to the spirit of the present invention.

Claims

1. A double-bond-containing hyperbranched active ester curing agent, characterized in that: Its structural formula is shown in Formula I: Formula I; Wherein, R is selected from one or more of substituted or unsubstituted C1-C10 straight chain alkyl, substituted or unsubstituted C1-C10 branched chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl; X is selected from one or more of a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted biphenyl, a substituted or unsubstituted alicyclic hydrocarbon, a substituted or unsubstituted naphthyl ether, a substituted or unsubstituted bisphenol A, a substituted or unsubstituted dicyclopentadiene, and a substituted or unsubstituted 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide group; n is 1~10.

2. A double-bond-containing hyperbranched active ester curing agent according to claim 1, characterized in that: The double-bond-containing hyperbranched active ester curing agent is prepared by reacting resveratrol, an X-group compound having hydroxyl groups at both ends, an aromatic dicarboxylic acid chloride and an acyl chloride compound containing an R group; The aromatic dicarboxylic acid chloride includes one or more of terephthaloyl chloride, phthaloyl chloride and isophthaloyl chloride.

3. A double-bond-containing hyperbranched active ester curing agent according to claim 2, characterized in that: The molar ratio of resveratrol to the X-group compound with hydroxyl groups at both ends is 1:(2-10); and / or, the molar ratio of the aromatic dicarboxylic acid chloride to the acyl chloride compound containing an R group is (1-5):1; And / or, the molar ratio of the total amount of the aromatic dicarboxylic acid chloride and the acyl chloride compound containing the R group to the total amount of resveratrol and the X group compound having hydroxyl groups at both ends is 1:(1-5).

4. A method for preparing a double-bond-containing hyperbranched active ester curing agent as claimed in claim 1, characterized in that: The preparation method comprises the following steps: dissolving resveratrol, an X group compound with hydroxyl groups at both ends and a catalyst in a solvent, adding aromatic dicarboxylic acid chloride and an acyl chloride compound containing an R group to react together to obtain a hyperbranched active ester curing agent containing a double bond.

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

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(morpholine)diethylether; And / or, the molar amount of the catalyst is 1 to 5 times the total molar amount of the aromatic dicarboxylic acid chloride and the acyl chloride compound containing the R group; And / or, the aromatic dicarboxylic acid chloride and the acyl chloride compound containing an R group are diluted with a solvent to a concentration of 0.01-0.05 mol / ml before use.

7. A build-up film formulation, characterized in that: The build-up film formula includes a double-bond-containing hyperbranched active ester curing agent as described in claims 1 to 3, and the build-up film formula includes: 5 to 12 parts of a double-bond-containing hyperbranched active ester curing agent, 25 to 50 parts of a non-hyperbranched active ester curing agent, 20 to 80 parts of an epoxy resin, 50 to 80 parts of an inorganic filler, 0.5 to 1.5 parts of a first catalyst, and 0.1 to 1.0 parts of a second catalyst.

8. A build-up film formulation 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 a pyridine catalyst, an imidazole catalyst, a pyrimidine catalyst, and a thiazole catalyst; And / or, the second catalyst is a peroxide catalyst; And / or, the inorganic filler includes one or more of silicon dioxide, talc, calcium carbonate, aluminum oxide, 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 the build-up film formula according to claim 7, characterized in that: The method for preparing the build-up film comprises the following steps: uniformly mixing the raw materials in the above-mentioned build-up film formula to obtain a build-up film slurry, coating the slurry on a substrate, and drying to obtain the build-up film.

10. Use of the build-up layer film according to claim 9 in integrated circuit packaging.

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