Copolymers, resin compositions, and applications of resin compositions

Abstract

The application relates to the field of high polymer material preparation, in particular to a copolymer, a resin composition and application of the resin composition. The copolymer comprises a monofunctional phenol compound residue, an aromatic dicarboxylic acid or an acid halide residue thereof, a difunctional phenol compound residue and a multifunctional phenol resin residue. The resin composition composed of the copolymer and an epoxy resin has the characteristics of high heat resistance, low dielectricity, low warping and low moisture absorption, and can be used for sealing of electrical and electronic components or circuit substrates.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high polymer material preparation, in particular to a copolymer, a resin composition and application of the resin composition. BACKGROUND

[0002] The cured product of an epoxy resin composition which contains an epoxy resin and a curing agent as essential components exhibits excellent heat resistance and insulation, and is therefore widely used for various electronic device applications such as semiconductors and printed wiring boards. In the field of the electronic device applications, especially in the technical field of multilayer printed board insulating materials, the signal speedup and high frequency in various electronic devices are advancing in recent years. Along with the signal speedup and high frequency, it is gradually becoming difficult to maintain a sufficiently low dielectric constant (Dk) and obtain a low dielectric tangent (Df). Therefore, the related applications require low dielectric materials that can correspond to the above applications.

[0003] When a low dielectric resin is used as a curing agent for an epoxy resin, no polar groups such as hydroxyl groups are generated, and the dielectric properties of the cured product of the epoxy resin can be greatly improved. Based on the above characteristics, low dielectric resins and epoxy resin compositions are widely used in semiconductor substrates, CCL substrate materials, BT substrates, and ABF film materials. However, due to the technical trend of high frequency, miniaturization, and thinning of electronic components, higher heat resistance, lower dielectric properties, and better curing shrinkage properties are required for multilayer printed board insulating materials, and the low dielectric resins that have been commercialized so far are difficult to meet the above technical requirements, so there is an urgent need in the industry to develop low dielectric resins with better performance and related application materials. SUMMARY

[0004] In view of the shortcomings of the prior art described above, the purpose of the present application is to provide a copolymer, a resin composition and application of the resin composition, for obtaining a resin composition with high heat resistance, low dielectric, low warpage, and low moisture absorption, thereby solving the problems in the prior art.

[0005] To achieve the above-mentioned object and other related objects, the present application is obtained by the following technical scheme.

[0006] In one aspect, the present application provides a copolymer, which comprises a monofunctional phenolic compound residue, an aromatic dicarboxylic acid or its acid halide residue, a difunctional phenolic compound residue, and a multifunctional phenolic resin residue.

[0007] The second aspect of the present application provides a preparation method of the aforementioned copolymer of the present application, which comprises mixing and reacting a monofunctional phenolic compound, an aromatic dicarboxylic acid or its acid halide, a difunctional phenolic compound, and a multifunctional phenolic resin.

[0008] The third aspect of the present application provides a resin composition comprising the aforementioned copolymer and an epoxy resin.

[0009] The fourth aspect of the present application provides the use of the aforementioned copolymer and / or resin composition in a cured product, a semiconductor sealant, a prepreg, a circuit substrate, a laminated film.

[0010] Compared with the prior art, the present application has the following advantages:

[0011] The resin composition of the copolymer and the epoxy resin has excellent properties of high heat resistance, lower dielectric, lower warpage, and low moisture absorption. Therefore, the resin composition of the present application can be used for sealing of electrical and electronic components or circuit substrates. DETAILED DESCRIPTION

[0012] The applicant of the present application found through experiments that copolymerization of a dicarboxylic acid or acid halide, a monofunctional phenol, and a difunctional phenol and a polyfunctional phenol produces no active hydrogen and has a lower dielectric loss tangent. On this basis, the present application was completed.

[0013]

Copolymer

[0014] The present application provides a copolymer comprising a monofunctional phenol compound residue, an aromatic dicarboxylic acid or acid halide residue, a difunctional phenol compound residue, and a polyfunctional phenol resin residue. Further, the copolymer has a monofunctional phenol compound residue at the terminal.

[0015] In the copolymer provided by the present application, the monomer corresponding to the monofunctional phenol compound residue is a monofunctional phenol compound. Optionally, the monofunctional phenol compound is selected from one or more of phenol, 1-naphthol, and 2-naphthol. Preferably, the monofunctional phenol compound is 1-naphthol.

[0016] In the copolymer provided by the present application, the monomer corresponding to the aromatic dicarboxylic acid or acid halide residue is an aromatic dicarboxylic acid or acid halide. Optionally, the aromatic dicarboxylic acid or acid halide is selected from one or more of phthaloyl dichloride, isophthaloyl dichloride, terephthaloyl dichloride, phthalic acid, isophthalic acid, and terephthalic acid. Preferably, the aromatic dicarboxylic acid or acid halide is selected from isophthaloyl dichloride or isophthalic acid.

[0017] In the copolymer provided by the present application, the monomer corresponding to the polyfunctional phenol resin residue is a polyfunctional phenol resin. Optionally, the polyfunctional phenol resin has the following structural formula: wherein A is selected from the group consisting of arylene, G is selected from the group consisting of alkylene or a bond, E is selected from the group consisting of arylene or cycloalkylene, and n is a number of repeating units selected from the group consisting of 0-10. In some embodiments, the arylene group has a number of carbon atoms selected from the group consisting of 6-12, for example 6, 10, 12; the alkylene group has a number of carbon atoms selected from the group consisting of 1-3, for example 1, 2, 3; and the cycloalkylene group has a number of carbon atoms selected from the group consisting of 10-20, for example 10, 15, 20. By way of illustration, an arylene group having a number of carbon atoms selected from the group consisting of 6-12 can be represented by C6-C12 arylene.

[0018] Optionally, A is selected from the group consisting of C6-C12 arylene. Further optionally, A is selected from the group consisting of phenylene or naphthylene.

[0019] Optionally, G is selected from the group consisting of C1-C3 alkylene or a bond. Further optionally, G is selected from the group consisting of methylene, or G is selected from the group consisting of a bond, and when G is selected from the group consisting of a bond, the polyfunctional phenolic resin is

[0020] Optionally, E is selected from the group consisting of C6-C12 arylene or C10-C20 cycloalkylene. Further optionally, E is selected from the group consisting of phenylene, naphthylene, biphenylene, or wherein, represents a point of attachment, and m is an integer selected from the group consisting of 0-1.

[0021] Optionally, n is selected from the group consisting of 0-9, 0-8, 0-7, 0-6, 0-5, 0-4, 0-3, 0-2.5, 0-2, etc. Preferably, n is selected from the group consisting of 0-5.

[0022] In some embodiments of the present application, the polyfunctional phenolic resin is selected from the group consisting of aralkyl type phenolic resin, biphenyl aralkyl type phenolic resin, dicyclopentadiene type phenolic resin.

[0023] In one optional embodiment, the polyfunctional phenolic resin is an aralkyl type phenolic resin. Specifically: in the structural formula wherein A is selected from the group consisting of phenylene or naphthylene, E is selected from the group consisting of phenylene or naphthylene, G is selected from the group consisting of methylene, and n is a number of repeating units having an average value selected from the group consisting of 0-10, the polyfunctional phenolic resin is an aralkyl type phenolic resin. Further, n has an average value selected from the group consisting of 0-5; still further, n is a number selected from the group consisting of 0-2.5, optionally including n is 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5. Preferably, the hydroxyl equivalent weight is selected from the group consisting of 145-300; more preferably, the hydroxyl equivalent weight is selected from the group consisting of 145-250 g / eq; by way of illustration, the polyfunctional phenolic resin is, for example A is selected from phenylene, E is selected from phenylene, G is selected from methylene, and the average value of n is 0.5; A is selected from phenylene, E is selected from phenylene, G is selected from methylene, and the average value of n is 0.7; A is selected from phenylene, E is selected from phenylene, G is selected from methylene, and the average value of n is 0.9; A is selected from phenylene, E is selected from phenylene, G is selected from methylene, and the average value of n is 1.1.

[0024] In another optional embodiment, the polyfunctional phenolic resin is a biphenyl aryl phenolic resin. Specifically: in the structural formula In this context, A is selected from phenylene or naphthylene, E is selected from biphenylene, and G is selected from methylene. When n is a repeating unit and its average value is between 0 and 10, the polyfunctional phenolic resin is a biphenyl aryl phenolic resin. Further, the average value of n is between 0 and 6; even further, n is between 0 and 2.5, including n = 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5. The biphenyl group includes... The methylene group includes The naphthyl group includes E is preferably Preferably, the hydroxyl equivalent is 183-400; more preferably, the hydroxyl equivalent is 183-350 g / eq; polyfunctional phenolic resins, for example: A is selected from phenylene, G is selected from methylene, and E is selected from... The average value of n is 0.1; A is selected from phenylene, G is selected from methylene, and E is selected from... The average value of n is 0.2; A is selected from phenylene, G is selected from methylene, and E is selected from... The average value of n is 1.0; A is selected from phenylene, G is selected from methylene, and E is selected from... The average value of n is 1.2; A is selected from phenylene, G is selected from methylene, and E is selected from... The average value of n is 1.5; A is selected from phenylene, G is selected from methylene, and E is selected from... The average value of n is 2.0.

[0025] In another optional embodiment, the polyfunctional phenolic resin is a dicyclopentadiene-type phenolic resin. Specifically: in the structural formula when A is selected from phenylene or naphthylene, E is selected from represents a point of attachment, G is selected from a bond, n is an average number of repeat units, and m is an integer from 0 to 1. Preferably, m is 0. Preferably, the hydroxyl equivalent weight is from 160 to 250 g / eq, preferably, the hydroxyl equivalent weight is from 160 to 220 g / eq, preferably, the hydroxyl equivalent weight is from 160 to 200 g / eq. The multifunctional phenolic resin is, for example: A is selected from phenylene, G is selected from a bond, and E is selected from n is selected from 0; A is selected from phenylene, G is selected from a bond, and E is selected from n is selected from 0.5.

[0026] In the copolymer provided by the present application, the monomer corresponding to the residue of the difunctional phenolic compound is a difunctional phenolic compound. The difunctional phenolic compound is selected from phenolphthalein, a derivative of phenolphthalein, a dihydroxy-substituted diphenylfluorene, or a dihydroxy-substituted diphenylfluorene derivative.

[0027] Optionally, the difunctional phenolic compound is selected from phenolphthalein.

[0028] Optionally, the difunctional phenolic compound is selected from a derivative of phenolphthalein, the derivative of phenolphthalein having a structural formula of wherein X is selected from NR 6 ; R 6 is selected from phenyl; R 4 , R 5 are each independently selected from hydroxy-substituted phenyl. The hydroxy-substituted phenyl can be, for example, The R 4 , R 5 are preferably represents a point of attachment.

[0029] The present application does not specifically limit the point of attachment of the group, and it is explained that each of the positions can exist simultaneously or partially simultaneously or only a single specific point of attachment exists.

[0030] Optionally, the dihydroxy-substituted diphenylfluorene is, for example, 9,9-bis(4-hydroxyphenyl)fluorene (BPF).

[0031] Optionally, the dihydroxy-substituted diphenylfluorene derivative is selected from an alkyl-substituted dihydroxy-substituted diphenylfluorene, for example, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (BCF), 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene.

[0032] In the copolymers provided in this application, the ratio of the amount of hydroxyl groups in the difunctional phenolic compound plus the amount of hydroxyl groups in the polyfunctional phenolic resin plus the amount of hydroxyl groups in the monofunctional phenolic compound to the amount of carboxylic acid or acyl halide of the aromatic dicarboxylic acid or its acyl halide is 1:0.1-1:3. For example, the total amount of hydroxyl groups in the difunctional phenolic compound, polyfunctional phenolic resin, and monofunctional phenolic compound is 1, and the amount of carboxylic acid or acyl halide of the aromatic dicarboxylic acid or its acyl halide is 1.5. Any range characterized by combinations of the above end values ​​is also included, which will not be elaborated here.

[0033] In the copolymers provided in this application, the molar ratio of phenolic hydroxyl groups in the polyfunctional phenolic resin to the molar ratio of phenolic hydroxyl groups in the difunctional phenolic compound is 1:(0.1-3). Options include 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, and 1:3. Any range characterized by combinations of the above values ​​is also included, which will not be elaborated here.

[0034] [Preparation methods of copolymers]

[0035] The present invention also provides a method for preparing a copolymer, the method comprising: mixing and reacting a monofunctional phenolic compound, an aromatic dicarboxylic acid or its acyl halide, a difunctional phenolic compound, and a polyfunctional phenolic resin.

[0036] In the copolymer preparation method provided in this application, the ratio of the amount of hydroxyl groups in the difunctional phenol compound plus the amount of hydroxyl groups in the polyfunctional phenol resin plus the amount of hydroxyl groups in the monofunctional phenol compound to the amount of carboxylic acid or acyl halide of the aromatic dicarboxylic acid or its acyl halide is 1:0.1-1:3. For example, the total amount of hydroxyl groups in the difunctional phenol compound, polyfunctional phenol resin, and monofunctional phenol compound is 1, and the amount of carboxylic acid or acyl halide of the aromatic dicarboxylic acid or its acyl halide is 1.5. Any range characterized by combinations of the above-mentioned end values ​​is also included, which will not be elaborated here.

[0037] In the copolymer preparation method provided in this application, the molar ratio of the hydroxyl groups in the polyfunctional phenolic resin to the hydroxyl groups in the difunctional phenolic compound is 1:(0.1-3). Options include 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, and 1:3. Any range characterized by combinations of the above values ​​is also included, which will not be elaborated here.

[0038] The ester group equivalent weight of the copolymer is 200-500 g / eq. It can be 200 g / eq, 250 g / eq, 300 g / eq, 400 g / eq, 450 g / eq, 500 g / eq. Any range characterized by a combination of the above endpoints is also included, and is not repeated here.

[0039] The number average molecular weight of the copolymer is 500-3000.

[0040] The number average molecular weight of the copolymer is 500-3000.

[0041] The copolymer can be prepared under alkaline conditions. For example:

[0042] Option 1: the multifunctional phenolic resin, difunctional phenolic compound, aromatic dicarboxylic acid or its acyl halide, monofunctional phenol are reacted under alkaline conditions.

[0043] Option 2: the aromatic dicarboxylic acid or its acyl halide is reacted with the monofunctional phenol under alkaline conditions to obtain a reactant, and then the reactant is reacted with the multifunctional phenolic resin, difunctional phenolic compound under alkaline conditions.

[0044] In both options, the alkaline conditions are, for example, one or more of sodium hydroxide, potassium hydroxide, triethylamine, pyridine, etc.

[0045]

Resin composition

[0046] The present application also provides a resin composition, which comprises the copolymer as described above and an epoxy resin.

[0047] The epoxy resin in the resin composition is selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, phosphorus-containing epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate type epoxy resin, aralkyl linear novolac epoxy resin, alicyclic epoxy resin, glycidyl amine type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, phosphorus atom-containing epoxy resin, etc.

[0048] The epoxy equivalent weight of the epoxy resin in the resin composition provided herein is selected from the range of 90 to 500 g / eq; optionally 90 g / eq, 150 g / eq, 200 g / eq, 250 g / eq, 300 g / eq, 350 g / eq, 400 g / eq, 450 g / eq, 500 g / eq. Any range characterized by combinations of the above-stated limits is also included, which will not be repeated here. Preferably, the epoxy equivalent weight is in the range of 200 to 300 g / eq.

[0049] The epoxy resin in the resin composition provided herein is optionally selected from the group consisting of: G' is a glycidyl ether, n' is a repeating unit having an average value of a number from 0 to 20 (wherein n' is preferably 3 to 10, more preferably 3 to 8), A' is selected from phenylene, B is selected from methylene or a bond, E' is selected from phenylene, biphenylene or

[0050] The ratio of the ester equivalent weight of the copolymer to the epoxy equivalent weight of the epoxy resin in the resin composition provided herein is in the range of 1 : 0.5 to 0.5: 1; preferably in the range of 1 : 0.9 to 0.9: 1; further preferably in the range of 1 : 0.95 to 0.95: 1 (the data is rounded, which is not limited to the specific values).

[0051] The resin composition provided herein further comprises a curing accelerator selected from one or more of the group consisting of pyridine-based, phosphorus-based curing accelerators, amine compounds, imidazole compounds, organic acid metal salts, Lewis acids, and amine complex salts.

[0052] Optionally, the phosphorus-based curing accelerator is selected from one or more of the group consisting of alkyl phosphines, primary phosphines such as phenyl phosphines, secondary phosphines such as dialkyl phosphines, diphenyl phosphines, tertiary phosphines such as trialkyl phosphines, triphenyl phosphines, phosphine compounds, and phosphonium salt compounds.

[0053] Optionally, the amine compound is selected from one or more of the group consisting of triethylamine, dimethylbenzylamine, triethylenediamine, tripropylamine, tributylamine, dimethylethanolamine, triethanolamine, 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, and the like.

[0054] Optionally, the imidazole compound is selected from one or more of 1-(2-cyanoethyl)-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dimethylolimidazole, 2-phenyl-4-methyl-5-methylolimidazole, 1-vinyl-2-methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, and the like.

[0055] The curing accelerator can be used alone or in combination of two or more.

[0056] In the resin composition provided by the present application, the equivalent ratio of the ester group of the copolymer to the equivalent of the curing accelerator is 100:0.1-100:1.5. Preferably, it is 100:0.1-100:1.

[0057] In the resin composition provided by the present application, the reaction is preferably carried out in an organic solvent. Examples of the organic solvent used include one or more of ketone solvents, acetate solvents, carbitol solvents, aromatic hydrocarbon toluene, xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone. Among them, one or more of ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone; one or more of acetate solvents such as ethyl acetate, butyl acetate, cellulose acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. These can be used alone or two or more as a mixed solvent.

[0058] In the resin composition provided by the present application, the glass transition temperature of the resin composition is 185°C or higher. Test method: dynamic mechanical analysis (DMA) is used, and the DMA method specified in 2.4.24.4 of IPC-TM-650 is used for determination.

[0059] In the resin composition provided by the present application, the dielectric loss tangent Df is less than 0.007. The dielectric constant Dk is less than 3. Test method: GB / T 40564-2021 is used.

[0060] In the resin composition provided by the present application, the warpage deformation height is less than 150 μm. Test method: the temperature is in the range of room temperature to 260°C, and the plate deformation height (μm).

[0061] The resin composition provided by the present application has a moisture absorption rate of 0.2 to 0.5. Test method: cut the above obtained laminate into a size of 25 mm in width and 75 mm in length as a test piece, and place it in an atmosphere of 85°C / 85% RH for 168 hours, and measure the weight change before and after.

[0062]

Application

[0063] The present application also provides the use of the copolymer as described above and / or the resin composition as described above in a cured product, a semiconductor sealing material, a prepreg, a circuit substrate, a laminated film.

[0064]

Cured product

[0065] The present application also provides a cured product obtained by curing the resin composition as described above. The curing conditions are 100 to 180°C for 10 to 60 minutes, and 180 to 250°C for 1 to 5 hours.

[0066]

Semiconductor sealing material

[0067] The present application also provides a semiconductor sealing material using the resin composition as described above and an inorganic filler.

[0068] Examples of the inorganic filler in the semiconductor sealing material provided by the present application include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, and magnesium hydroxide. Among them, fused silica is particularly preferred because it can increase the filling rate of the inorganic filler. Here, the fused silica can be used in a pulverized form or a spherical form, but in order to increase the amount of the fused silica to be blended and suppress the increase in the melt viscosity of the molding material, it is preferred to mainly use spherical silica. In addition, in order to increase the amount of the spherical silica to be blended, it is preferred to appropriately adjust the particle size distribution of the spherical silica.

[0069]

Prepreg

[0070] The present application also provides a prepreg obtained by impregnating a reinforcing substrate with the resin composition as described above and then semi-curing it.

[0071] In the prepreg provided by the present application, the reinforcing substrate is selected from at least one of natural fibers, organic synthetic fibers, organic woven fabrics, and inorganic woven fabrics. Preferably, the reinforcing substrate is a glass fiber cloth, and among them, an open fiber cloth or a flat cloth is preferably used. The glass fiber cloth is preferably an E glass fiber cloth, an S glass fiber cloth, or a Q glass fiber cloth.

[0072]

Circuit substrate

[0073] The present application also provides a circuit substrate obtained by mixing the resin composition as described above with an organic solvent to obtain a varnish, and then forming the varnish and a copper foil into a plate shape under heating and pressure.

[0074]

Laminated film

[0075] The application also provides a laminated film, which is obtained by mixing the resin composition as described above with an organic solvent, coating the obtained substance on a substrate film, and drying.

[0076] The substrate film is selected from at least one of PET film, PP film, PE film, and PVC film.

[0077] The following specific examples illustrate the embodiments of the application, and those skilled in the art can easily understand other advantages and effects of the application from the disclosure of the specification.

[0078] Before further describing the specific embodiments of the application, it should be understood that the scope of protection of the application is not limited to the following specific embodiments; it should also be understood that the terms used in the embodiments of the application are for the purpose of describing the specific embodiments, and are not intended to limit the scope of protection of the application. The test methods in the following examples are not specified, and are generally carried out under conventional conditions, or under the conditions recommended by the manufacturers.

[0079] When the embodiments give numerical ranges, it should be understood that, unless otherwise stated in the application, both endpoints of each numerical range and any number between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the application have the same meaning as generally understood by those skilled in the art. In addition to the specific methods, devices, materials used in the examples, any method, device and material of the prior art similar or equivalent to those described in the examples of the application can also be used to implement the application according to the mastery of the prior art by those skilled in the art and the description of the application.

[0080] Test instruments and methods:

[0081] GPC instrument: Agilent 1260 Infinity II, chromatographic column KF801+KF802+KF803; conditions: THF flow rate 1 mL / min, 35℃. Standard, monodisperse polystyrene with known molecular weight was used.

[0082] Glass transition temperature Tg: determined by dynamic mechanical analysis (DMA) according to the DMA method specified in IPC-TM-650 2.4.24.4

[0083] Method for measuring dielectric constant and dielectric loss tangent: GB / T 40564-2021

[0084] Warpage: the temperature is in the range of room temperature to 260℃, and the deformation height (μm) of the plate

[0085] Hygroscopicity: The above obtained laminate was cut into a size of 25 mm in width and 75 mm in length, and used as a test piece. The weight change before and after the test piece was left in an atmosphere of 85°C / 85% RH for 168 hours was measured.

[0086] Synthesis experiment

[0087] Copolymer preparation example

[0088] Preparation Example 1

[0089] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a flow divider, and a stirrer were charged (wherein A is selected from the group consisting of phenylene, and E is selected from the group consisting of G is selected from the group consisting of methylene, and n is 2.23, and the hydroxyl equivalent weight is 230 g / eq) (69 g), (X is selected from the group consisting of NR 6 , R 6 is selected from the group consisting of phenyl, R 4 , R 5 is selected from the group consisting of p-hydroxy-substituted phenyl) (69 g, 0.175 mol), toluene (350 g), and nitrogen was replaced, followed by the addition of isophthaloyl chloride (242 g, 1.2 mol), and 1-naphthol (137 g, 0.95 mol) was added under nitrogen protection, and 48% sodium hydroxide aqueous solution (sodium hydroxide 40 g) was added dropwise at 40°C, and the reaction was stirred for 1 hour. After the completion of the reaction, the water layer was removed by liquid separation, the organic layer was washed with water until the pH was 7, the water layer was removed, and the organic solvent was removed by distillation under reduced pressure until the solid content was 65% of the resin X1. The ester equivalent weight of X1 was 259 g / eq, Mn was 1200, and Mw was 2520.

[0090] Preparation Example 2

[0091] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a flow divider, and a stirrer were charged (wherein A is selected from the group consisting of phenylene, and E is selected from the group consisting of G is selected from the group consisting of methylene, and n is 2.23, and the hydroxyl equivalent weight is 230 g / eq) (69 g), (X is selected from the group consisting of NR 6 , R 6 is selected from the group consisting of phenyl, R 4 , R 5Preparation Example 1

[0092] Preparation Example 2

[0093] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a flow divider, and a stirrer were charged (wherein A is selected from the group consisting of phenylene, E is selected from the group consisting of G is selected from the group consisting of methylene, n is 2.23, and the hydroxyl equivalent weight is 230 g / eq (161 g), (X is selected from the group consisting of NR 6 , R 6 is selected from the group consisting of phenyl, R 4 , R 5 is selected from the group consisting of p-hydroxy-substituted phenyl) (128 g, 0.325 mol), toluene (350 g), replaced with nitrogen, followed by the addition of isophthaloyl chloride (242 g, 1.2 mol), added with nitrogen protection, 1-naphthol (94 g, 0.65 mol), and 48% sodium hydroxide aqueous solution (sodium hydroxide 40 g, water 43 g) was added dropwise at 40°C, and the reaction was stirred for 1 hour. After the completion of the reaction, the aqueous layer was removed by liquid separation, the organic layer was washed with water until the pH became 7, the aqueous layer was removed, and the organic solvent was removed by distillation under reduced pressure until the solid content became 65% of the resin X3.

[0094] Preparation Example 3

[0095] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a flow divider, and a stirrer were charged (wherein A is selected from the group consisting of phenylene, E is selected from the group consisting of G is selected from the group consisting of methylene, the hydroxyl equivalent weight is 230 g / eq, and n is 2.23) (161 g), 9,9-bis(4-hydroxyphenyl)fluorene (61 g, 0.175 mol), toluene (350 g), replaced with nitrogen, followed by the addition of isophthaloyl chloride (242 g, 1.2 mol), added with nitrogen protection, 1-naphthol (137 g, 0.95 mol), and 48% sodium hydroxide aqueous solution (sodium hydroxide 40 g, water 43 g) was added dropwise at 40°C, and the reaction was stirred for 1 hour. After the completion of the reaction, the aqueous layer was removed by liquid separation, the organic layer was washed with water until the pH became 7, the aqueous layer was removed, and the organic solvent was removed by distillation under reduced pressure until the solid content became 65% of the resin X4.

[0096] Preparation Example 4

[0097] Into a flask equipped with a thermometer, dropping funnel, condenser, shunt, stirrer, was charged (wherein A is selected from phenylene, E is selected from G is selected from methylene, n is 2.23, hydroxyl equivalent weight 230 g / eq) (161 g), (X is selected from O, R 4 , R 5 is selected from p-hydroxy substituted phenyl) (56 g, 0.175 mol), toluene (350 g), replaced with nitrogen, then added isophthaloyl chloride (242 g, 1.2 mol), protected with nitrogen, added 1-naphthol (137 g, 0.95 mol), added 48% aqueous sodium hydroxide (sodium hydroxide 40 g, water 43 g) dropwise at 40°C, stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by liquid separation, the organic layer was washed with water until the pH was 7, the aqueous layer was removed, and the organic solvent was removed by distillation under reduced pressure to give a resin X5 having a solid content of 65%.

[0098] Preparation Example 6

[0099] Into a flask equipped with a thermometer, dropping funnel, condenser, shunt, stirrer, was charged (A is selected from phenylene, E is selected from G is selected from a bond, n is 0.16) (hydroxyl equivalent weight 165 g / eq) (116 g), (X is selected from NR 6 , R 6 is selected from phenyl, R 4 , R 5 is selected from p-hydroxy substituted phenyl) (69 g, 0.175 mol), toluene (350 g), replaced with nitrogen, then added isophthaloyl chloride (242 g, 1.2 mol), protected with nitrogen, added 1-naphthol (137 g, 0.95 mol), added 48% aqueous sodium hydroxide (sodium hydroxide 40 g, water 43 g) dropwise at 40°C, stirred for 1 hour. After completion of the reaction, the aqueous layer was removed by liquid separation, the organic layer was washed with water until the pH was 7, the aqueous layer was removed, and the organic solvent was removed by distillation under reduced pressure to give a resin X6 having a solid content of 65%.

[0100] Preparation Comparative Example 1D1

[0101] Into a flask equipped with a thermometer, dropping funnel, condenser, shunt, stirrer, was charged (A is selected from phenylene, E is selected from G is selected from a bond, n is 0.16) (hydroxyl equivalent 165 g / eq) (173 g), toluene (350 g), nitrogen substitution, then adding isophthaloyl chloride (242 g, 1.2 mol), nitrogen protection, adding 1-naphthol (137 g, 0.95 mol), 40°C dropwise adding 48% sodium hydroxide aqueous solution (sodium hydroxide 40 g, water 43 g), stirring for 1 hour. After the reaction is completed, the water layer is removed by liquid separation, the organic layer is washed with water until the pH is 7, the water layer is removed, and the organic solvent is removed by distillation under reduced pressure to a resin D1 with a solid content of 65%.

[0102] Preparation of Comparative Example 2D2

[0103] In a flask equipped with a thermometer, a dropping funnel, a condenser, a flow divider, and a stirrer, was placed (X is selected from NR 6 , R 6 is selected from phenyl, R 4 , R 5 is selected from p-hydroxy-substituted phenyl) (207 g, 0.525 mol), toluene (350 g), nitrogen substitution, then adding isophthaloyl chloride (242 g, 1.2 mol), nitrogen protection, adding 1-naphthol (137 g, 0.95 mol), 40°C dropwise adding 48% sodium hydroxide aqueous solution (sodium hydroxide 40 g, water 43 g), stirring for 1 hour. After the reaction is completed, the water layer is removed by liquid separation, the organic layer is washed with water until the pH is 7, the water layer is removed, and the organic solvent is removed by distillation under reduced pressure to a resin D2 with a solid content of 65%.

[0104] Preparation of Comparative Example 3D3 is a composition of D1 and D2 (D1:D2 = ester equivalent ratio 1:1).

[0105] The amounts of each raw material in the copolymer preparation example are shown in Table 1.

[0106] Table 1

[0107]

[0108] The copolymer parameters are shown in Table 2.

[0109] Table 2

[0110]

[0111] Preparation and performance evaluation of epoxy resin composition

[0112] Laminated board manufacturing conditions

[0113] Substrate: glass cloth " # 2116 " (210 X 280 mm) manufactured by Nitto Boseki Co., Ltd.

[0114] Number of layers: 6

[0115] Pre-impregnation conditions: 160°C

[0116] Curing conditions: at 200°C, 40 kg / cm 2 for 1.5 hours

[0117] Molded plate thickness: 0.8 mm

[0118] Solvent: MEK (methyl ethyl ketone)

[0119] Curing accelerator: DMAP (N,N-dimethylamino pyridine)

[0120] Epoxy resin: G' is a glycidyl ether, A' is selected from phenylene, B is selected from methylene, and E' is selected from biphenylene n' is 4.38. Epoxy equivalent weight 287 g / eq, softening point 69°C.

[0121] The amounts of each raw material used in the preparation of the epoxy resin composition in the Examples and Comparative Examples are shown in Table 3.

[0122] Table 3

[0123]

[0124]

[0125] The performance test data of the Examples and Comparative Examples of the epoxy resin composition are shown in Table 4.

[0126] Table 4

[0127] Tg, °C Df Dk Warpage Moisture absorption Example 1 191 0.00572 2.87 less than 150 μm 0.2 Example 2 189 0.00536 2.89 less than 150 μm 0.2 Example 3 192 0.00563 2.88 less than 150 μm 0.2 Example 4 185 0.00591 2.91 less than 150 μm 0.4 Example 5 186 0.00588 2.90 less than 150 μm 0.3 Example 6 185 0.00694 2.96 less than 150 μm 0.5 Comparative Example 1 179 0.01056 2.94 350-500 μm 0.8 Comparative Example 2 185 0.00710 2.91 350-500 μm 0.7 Comparative Example 3 182 0.00709 2.90 350-500 μm 0.6

[0128] A copolymer, a resin composition, and the use of the resin composition according to the present application have been described by way of preferred embodiments, and it is obvious to those skilled in the art that the process described herein can be modified or appropriately changed and combined without departing from the content, spirit, and scope of the present application, to realize the technology of the present application. It is particularly pointed out that all similar substitutions and modifications are obvious to those skilled in the art, and they are considered to be included in the spirit, scope, and content of the present application.

Claims

1. A copolymer, characterized in that, The copolymer comprises monofunctional phenolic compound residues, aromatic dicarboxylic acids or their acyl halide residues, difunctional phenolic compound residues, and polyfunctional phenolic resin residues; The monomer corresponding to the residue of the difunctional phenolic compound is a difunctional phenolic compound, and the difunctional phenolic compound is selected from phenolphthalein derivatives; The structural formula of the phenolphthalein derivative is as follows: Where X is selected from NR 6 ;R 6 Selected from phenyl; R 4 R 5 Each is independently selected from hydroxylated phenyl groups; The monomer corresponding to the polyfunctional phenolic resin residue is a polyfunctional phenolic resin, and the structural formula of the polyfunctional phenolic resin is as follows: n is a repeating element, selected from numbers between 0 and 10. A is selected from C6-C12 aryl groups; G is selected from C1-C3 alkylene groups; E is selected from C6-C12 aryl groups.

2. The copolymer according to claim 1, characterized in that, It also includes one or more of the following features: a1) The monomer corresponding to the monofunctional phenolic compound residue is a monofunctional phenolic compound, and the monofunctional phenolic compound is selected from one or more of phenol, 1-naphthol, and 2-naphthol; a2) The monomer corresponding to the aromatic dicarboxylic acid or its acyl halide residue is an aromatic dicarboxylic acid or its acyl halide, wherein the aromatic dicarboxylic acid or its acyl halide is selected from one or more of phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, phthalic acid, isophthalic acid, and terephthalic acid.

3. The copolymer according to claim 1, characterized in that, It also includes one or more of the following features: a311)A is selected from phenylene or naphthylene; a321)G is selected from methylene, a331)E is selected from phenylene, naphthylene, and biphenylene, wherein, Indicates the connection location.

4. The copolymer according to claim 1, characterized in that, It also includes one or more of the following features: b1) When A is selected from phenylene or naphthylene, E is selected from phenylene or naphthylene, G is selected from methylene, n is a repeating unit, and the average value is a number from 0 to 10, the polyfunctional phenolic resin is an aralkyl-type phenolic resin. b2) When A is selected from phenylene or naphthylene, E is selected from biphenylene, and G is selected from methylene, When n is a repeating unit and the average value is a number between 0 and 10, the polyfunctional phenolic resin is a biphenyl aryl phenolic resin.

5. A method for preparing the copolymer according to any one of claims 1 to 4, characterized in that, The preparation method includes: The product is obtained by mixing and reacting monofunctional phenolic compounds, aromatic dicarboxylic acids or their acyl halides, difunctional phenolic compounds, and polyfunctional phenolic resins.

6. A resin composition, characterized in that, The resin composition comprises the copolymer and epoxy resin as described in any one of claims 1 to 4.

7. The use of the copolymer according to any one of claims 1-4 and / or the resin composition according to claim 6 in cured products, semiconductor sealants, prepregs, circuit boards, and multilayer films.

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