Copolymer, resin composition and application of resin composition

Abstract

The invention relates to the field of preparation of high polymer materials, in particular to a copolymer, a resin composition and application of the resin composition. The copolymer includes a monofunctional phenol compound residue, an aromatic dicarboxylic acid or an acyl halide residue thereof, a bifunctional phenol compound residue, and a polyfunctional phenol resin residue. The resin composition composed of the copolymer and the epoxy resin has the characteristics of high heat resistance, low dielectric, low warpage 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 polymer material preparation, and in particular to a copolymer, a resin composition and the application of the resin composition. Background Art

[0002] The cured product of epoxy resin composition with epoxy resin and its curing agent as essential components shows excellent heat resistance and insulation, and is therefore widely used in various electronic device applications such as semiconductors and printed wiring boards. In the electronic device applications, especially in the technical field of multilayer printed substrate insulating materials, the high speed and high frequency of signals in various electronic devices are being promoted in recent years. Along with the high speed and high frequency of signals, it becomes difficult to maintain a sufficiently low dielectric constant (Dk) and obtain a low dielectric positive connection (Df). Therefore, related applications need to be able to correspond to the low dielectric material of the above applications.

[0003] When used as a curing agent for epoxy resin, low dielectric resin does not produce polar groups such as hydroxyl groups, and can significantly improve the dielectric properties of epoxy resin cured products. 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 technological trend of high frequency, miniaturization and thinning of electronic components, multi-layer printed substrate insulation materials also require higher heat resistance, lower dielectric properties and better curing shrinkage properties. The currently commercialized low dielectric resins are difficult to meet the above technical requirements. Therefore, the industry urgently needs to develop low dielectric resins with better performance and related application materials. Summary of the invention

[0004] In view of the above-mentioned shortcomings of the prior art, the purpose of the present application is to provide a copolymer, a resin composition and the application of the resin composition, so as to obtain a resin composition with high heat resistance, low dielectric, low warpage and low moisture absorption, so as to solve the problems in the prior art.

[0005] To achieve the above-mentioned purpose and other related purposes, the present application is obtained through the following technical solutions.

[0006] In one aspect, the present application provides a copolymer, which includes a monofunctional phenol compound residue, an aromatic dicarboxylic acid or an acyl halide residue thereof, a difunctional phenol compound residue, and a polyfunctional phenol resin residue.

[0007] The second aspect of the present application provides a method for preparing the aforementioned copolymer of the present application, the preparation method comprising: mixing and reacting a monofunctional phenol compound, an aromatic dicarboxylic acid or its acyl halide, a difunctional phenol compound, and a multifunctional phenol resin to obtain the copolymer.

[0008] A third aspect of the present application provides a resin composition, which includes the aforementioned copolymer of the present application and an epoxy resin.

[0009] The fourth aspect of the present application provides the use of the copolymer and / or resin composition as described above in the present invention in cured products, semiconductor seals, prepregs, circuit substrates, and laminated films.

[0010] Compared with the prior art, the beneficial effects of this application are:

[0011] The resin composition composed of the copolymer and epoxy resin of the present application 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 has found through experiments that the copolymerization of dicarboxylic acid or acyl halide, monophenol and dihydric phenol or polyhydric phenol does not produce active hydrogen and has a lower dielectric loss tangent. Based on this, the present application was completed.

[0013]

Copolymer

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

[0015] In the copolymer provided in 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 in the present application, the monomer corresponding to the aromatic dicarboxylic acid or its acyl halide residue is an aromatic dicarboxylic acid or its acyl halide. Optionally, 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. Preferably, the aromatic dicarboxylic acid or its acyl halide is selected from isophthaloyl chloride or isophthalic acid.

[0017] In the copolymer provided in the present application, the monomer corresponding to the multifunctional phenol resin residue is a multifunctional phenol resin. Optionally, the structural formula of the multifunctional phenol resin is Wherein A is selected from arylene, G is selected from alkylene or connecting bond, E is selected from arylene or cycloalkylene, and n is a repeating unit, selected from a number of 0-10. In some embodiments, the number of carbon atoms in the arylene is 6-12, such as 6, 10, 12; the number of carbon atoms in the alkylene is 1-3, such as 1, 2, 3; the number of carbon atoms in the cycloalkylene is 10-20, such as 10, 15, 20. For example, the number of carbon atoms in the arylene group of 6-12 can be represented by a C6-C12 arylene group.

[0018] Optionally, A is selected from C6-C12 arylene groups. Further optionally, A is selected from phenylene groups or naphthylene groups.

[0019] Optionally, G is selected from C1-C3 alkylene or a connecting bond. Further optionally, G is selected from methylene, Or G is selected from a connecting bond. When G is selected from a connecting bond, the multifunctional phenol resin is

[0020] Optionally, E is selected from C6-C12 arylene or C10-C20 cycloalkylene. Further optionally, E is selected from phenylene, naphthylene, biphenylene or in, Indicates the connection position, m is an integer from 0 to 1.

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

[0022] In some embodiments of the present application, the multifunctional phenol resin is selected from aralkyl phenol-formaldehyde resin, biphenyl aralkyl phenol-formaldehyde resin, and dicyclopentadiene phenol-formaldehyde resin.

[0023] In an optional embodiment, the multifunctional phenol resin is an aralkyl phenolic resin. Specifically: in the structural formula In the embodiment, when A is selected from phenylene or naphthylene, E is selected from phenylene or naphthylene, G is selected from methylene, and n is a repeating unit with an average value of 0-10, the multifunctional phenol resin is an aralkyl type phenolic resin. Further, n has an average value of 0-5; further, n is a number of 0-2.5, and n can be 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 is 145-300; more preferably, the hydroxyl equivalent is 145-250 g / eq; as an example, the multifunctional phenol 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 multifunctional phenol resin is a biphenyl aralkyl type phenolic resin. Specifically: In the structural formula When A is selected from phenylene or naphthylene, E is selected from biphenylene, G is selected from methylene, When n is a repeating unit and the average value is 0-10, the multifunctional phenol resin is a biphenyl aralkyl type phenolic resin. Further, the average value of n is 0-6; further, n is 0-2.5, 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. The biphenyl includes The methylene group includes The naphthylene group includes The E is preferably Preferably, the hydroxyl equivalent is 183-400; more preferably, the hydroxyl equivalent is 183-350 g / eq; multifunctional phenol resins such as: 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 multifunctional phenol resin is a dicyclopentadiene phenolic resin. Specifically: in the structural formula When A is selected from phenylene or naphthylene, E is selected from Indicates the connection position, G is selected from the connecting bond, n is a repeating unit, and the average value is a number of 0-10, and the multifunctional phenol resin is a dicyclopentadiene type phenolic resin. Further, the average value of n is a number of 0-5. For example, n is 0, 0.5, 1.0, 1.1, 1.2, 1.5, 2.0, 2.2, 2.5, 2.7, 2.9, 3.0, 3.1, 10. m is an integer of 0-1. Preferably, m is 0. Preferably, the hydroxyl equivalent is 160-250g / eq, preferably, the hydroxyl equivalent is 160-220g / eq, preferably, the hydroxyl equivalent is 160-200g / eq. Multifunctional phenol resins are for example: A is selected from phenylene, G is selected from a connecting bond, and E is selected from n is selected from 0; A is selected from phenylene, G is selected from a connecting bond, and E is selected from n is selected from 0.5.

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

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

[0028] Optionally, the difunctional phenol compound is selected from a derivative of phenolphthalein, and the structural formula of the derivative of phenolphthalein is Wherein, X is selected from NR 6 ; R 6 Selected from phenyl; R 4 , R 5 Each is independently selected from hydroxy substituted phenyl. Wherein the hydroxy substituted phenyl can be, for example, The R 4 , R 5 Preferably Indicates the connection location.

[0029] The connection positions of the groups of the present invention are not specifically limited, which means that various positions may exist simultaneously or partially simultaneously or only a single specific connection position may exist.

[0030] Alternatively, a dihydroxy-substituted diphenylfluorene such as 9,9-bis(4-hydroxyphenyl)fluorene (BPF).

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

[0032] In the copolymer provided in the present application, the (amount of hydroxyl groups in the difunctional phenol compound plus the amount of hydroxyl groups in the multifunctional phenol resin plus the amount of hydroxyl groups in the monofunctional phenol compound): the amount of carboxylic acid of aromatic dicarboxylic acid or its acyl halide or the amount of carboxylic acid halide is 1:0.1-1:3. For example, the total amount of hydroxyl groups in the difunctional phenol compound, the multifunctional phenol resin and the monofunctional phenol compound is 1, and the amount of carboxylic acid of aromatic dicarboxylic acid or its acyl halide or the amount of carboxylic acid halide is 1.5. It also includes any range characterized by a combination of the above-mentioned end values, which will not be repeated here.

[0033] In the copolymer provided in the present application, the molar ratio of the phenolic hydroxyl group in the multifunctional phenol resin to the molar ratio of the phenolic hydroxyl group in the difunctional phenol compound is 1:(0.1-3). It can be selected as 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, 1:3. It also includes any range characterized by a combination of the above end values, which will not be repeated here.

[0034]

Preparation method of copolymer

[0035] The present invention also provides a method for preparing the copolymer, which comprises: mixing and reacting a monofunctional phenol compound, an aromatic dicarboxylic acid or its acyl halide, a difunctional phenol compound, and a multifunctional phenol resin to obtain the copolymer.

[0036] In the preparation method of the copolymer provided in the present application, the ratio of (the amount of hydroxyl groups in the difunctional phenol compound plus the amount of hydroxyl groups in the multifunctional phenol resin plus the amount of hydroxyl groups in the monofunctional phenol compound): the amount of carboxylic acid of the aromatic dicarboxylic acid or its acyl halide or the amount of acyl halide is 1:0.1-1:3. For example, the total amount of hydroxyl groups in the difunctional phenol compound, the multifunctional phenol resin and the monofunctional phenol compound is 1, and the amount of carboxylic acid of the aromatic dicarboxylic acid or its acyl halide or the amount of acyl halide is 1.5. It also includes any range characterized by a combination of the above-mentioned end values, which will not be repeated here.

[0037] In the preparation method of the copolymer provided in the present application, the molar ratio of the hydroxyl group in the multifunctional phenol resin to the molar ratio of the hydroxyl group in the difunctional phenol compound is 1:(0.1-3). It can be selected as 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, 1:3. It also includes any range characterized by a combination of the above end values, which will not be repeated here.

[0038] In the preparation method of the copolymer provided in the present application, the ester equivalent 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. It also includes any range characterized by a combination of the above end values, which will not be repeated here.

[0039] In the preparation method of the copolymer provided in the present application, the number average molecular weight of the copolymer is 500-3000.

[0040] In the preparation method of the copolymer provided in the present application, the weight average molecular weight of the copolymer is 1000-6000.

[0041] In the preparation method of the copolymer provided in the present application, the reaction can be carried out under alkaline conditions. For example:

[0042] Option 1: react a multifunctional phenol resin, a difunctional phenol compound, an aromatic dicarboxylic acid or its acyl halide, and a monofunctional phenol under alkaline conditions.

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

[0044] In both methods, the alkaline conditions include 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 in the present invention and an epoxy resin.

[0047] In the resin composition provided in the present application, the epoxy resin is selected from bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus-containing epoxy resin, o-cresol 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 phenolic 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] In the resin composition provided in the present application, the epoxy equivalent of the epoxy resin is selected to be 90-500 g / eq; it can be selected to be 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. It also includes any range characterized by a combination of the above end values, which will not be repeated here. Preferably, it is 200-300 g / eq.

[0049] In the resin composition provided in the present application, optionally, the epoxy resin is, for example: G' is a glycidyl ether, n' is a repeating unit, the average value is 0-20 (wherein n' is preferably 3-10, more preferably 3-8), A' is selected from phenylene, B is selected from methylene or a linker, E' is selected from phenylene, biphenylene or

[0050] In the resin composition provided in the present application, the ratio of the ester equivalent of the copolymer to the epoxy equivalent of the epoxy resin is 1:0.5 to 0.5:1; preferably 1:0.9 to 0.9:1; further preferably 1:0.95 to 0.95:1 (the data are rounded off and are not limited to specific values).

[0051] In the resin composition provided in the present application, the resin composition also includes a curing accelerator, and the curing accelerator is selected from one or more of pyridines, 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 phosphine compounds such as primary phosphines such as alkyl phosphines and phenyl phosphine, secondary phosphines such as dialkyl phosphines and diphenyl phosphine, tertiary phosphines such as trialkyl phosphines and triphenyl phosphine, and phosphonium salt compounds.

[0053] Optionally, the amine compound is selected from one or more 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, etc.

[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-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-vinyl-2 1-methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methyl-imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole and the like.

[0055] The curing accelerators may be used alone or in combination of two or more.

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

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

[0058] In the resin composition provided in the present application, the glass transition temperature of the resin composition is above 185° C. Test method: Dynamic mechanical analysis (DMA) is used to perform the test according to the DMA method specified in 2.4.24.4 of IPC-TM-650.

[0059] In the resin composition provided in 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 adopted.

[0060] In the resin composition provided in the present application, the warpage height is less than 150 μm. Test method: Plate deformation height (μm) at a temperature ranging from room temperature to 260°C.

[0061] The resin composition provided in the present application has a moisture absorption rate of 0.2 to 0.5. Test method: Cut the laminate obtained above into a size of 25 mm wide and 75 mm long as a test piece, 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 invention also provides use of the copolymer and / or the resin composition of the present invention in a cured product, semiconductor sealing, prepreg, circuit substrate, or laminated film.

[0064]

Cured product

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

[0066]

Semiconductor sealing materials

[0067] The present application also provides a semiconductor sealing material, which adopts the resin composition and inorganic filler as mentioned above in the present application.

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

[0069]

Prepreg

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

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

[0072]

Circuit board

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

[0074]

Laminated film

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

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

[0077] The following is an explanation of the implementation of the present application by means of specific embodiments. People familiar with the art can easily understand other advantages and effects of the present application from the contents disclosed in this specification.

[0078] Before further describing the specific implementation methods of the present application, it should be understood that the scope of protection of the present application is not limited to the specific implementation methods described below; it should also be understood that the terms used in the examples of the present application are intended to describe specific implementation methods, rather than to limit the scope of protection of the present application. The test methods in the following examples that do not specify specific conditions are generally carried out under conventional conditions or under conditions recommended by the manufacturers.

[0079] When the embodiments give numerical ranges, it should be understood that, unless otherwise specified in the present application, the two endpoints of each numerical range and any numerical value between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the present application have the same meaning as those generally understood by those skilled in the art. In addition to the specific methods, equipment, and materials used in the embodiments, according to the grasp of the prior art by those skilled in the art and the record of the present application, any method, equipment, and material of the prior art similar or equivalent to the methods, equipment, and materials described in the embodiments of the present application can also be used to realize the present application.

[0080] Test instruments and methods:

[0081] GPC instrument: Agilent 1260 InfinityⅡ, chromatographic columns KF801+KF802+KF803; conditions: THF flow rate 1 mL / min, 35°C. Standard: monodisperse polystyrene with known molecular weight.

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

[0083] Determination method of dielectric constant and dielectric loss tangent: GB / T 40564-2021

[0084] Warpage: Sheet deformation height (μm) at temperatures ranging from room temperature to 260°C

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

[0086] Synthesis Experiment

[0087] Copolymer Preparation Example

[0088] Preparation Example 1

[0089] Put the mixture into a flask equipped with a thermometer, dropping funnel, condenser, splitter and stirrer. (wherein A is selected from phenylene, E is selected from G is selected from methylene, hydroxyl equivalent 230g / eq, n is 2.23) (161g), (X is selected from NR 6 , R 6 Selected from phenyl, R 4 , R 5 Selected from p-hydroxy-substituted phenyl) (69g, 0.175mol), toluene (350g), nitrogen replacement, then add isophthaloyl chloride (242g, 1.2mol), nitrogen protection, add 1-naphthol (137g, 0.95mol), add 48% sodium hydroxide aqueous solution (sodium hydroxide 40g) dropwise at 40°C, and stir to react for 1 hour. After the reaction is completed, separate the liquid to remove the water layer, wash the organic layer with water to pH 7, remove the water layer, and distill under reduced pressure to remove the organic solvent to obtain resin X1 with a solid content of 65%. The ester equivalent of X1 is 259g / eq, Mn 1200, and Mw 2520.

[0090] Preparation Example 2

[0091] Put the mixture into a flask equipped with a thermometer, dropping funnel, condenser, splitter and stirrer. (wherein A is selected from phenylene, E is selected from G is selected from methylene, n is 2.23, hydroxyl equivalent 230g / eq)(69g), (X is selected from NR 6 , R 6 Selected from phenyl, R 4 , R 5Selected from p-hydroxy-substituted phenyl) (148g, 0.375mol), toluene (350g), nitrogen replacement, then add isophthaloyl chloride (242g, 1.2mol), nitrogen protection, add 1-naphthol (137g, 0.95mol), add 48% sodium hydroxide aqueous solution (sodium hydroxide 40g) dropwise at 40°C, and stir to react for 1 hour. After the reaction is completed, separate the liquid to remove the water layer, wash the organic layer with water to pH 7, remove the water layer, and distill under reduced pressure to remove the organic solvent to obtain resin X2 with a solid content of 65%.

[0092] Preparation Example 3

[0093] Put the mixture into a flask equipped with a thermometer, dropping funnel, condenser, splitter and stirrer. (wherein A is selected from phenylene, E is selected from G is selected from methylene, n is 2.23, hydroxyl equivalent is 230g / eq (161g), (X is selected from NR 6 , R 6 Selected from phenyl, R 4 , R 5 Selected from p-hydroxy-substituted phenyl) (128g, 0.325mol), toluene (350g), nitrogen replacement, then add isophthaloyl chloride (242g, 1.2mol), nitrogen protection, add 1-naphthol (94g, 0.65mol), add 48% sodium hydroxide aqueous solution (sodium hydroxide 40g, water 43g) dropwise at 40°C, and stir to react for 1 hour. After the reaction is completed, separate the liquid to remove the water layer, wash the organic layer with water to pH 7, remove the water layer, and distill under reduced pressure to remove the organic solvent to obtain resin X3 with a solid content of 65%.

[0094] Preparation Example 4

[0095] Put the mixture into a flask equipped with a thermometer, dropping funnel, condenser, splitter and stirrer. (wherein A is selected from phenylene, E is selected from G is selected from methylene, hydroxyl equivalent 230g / eq, n is 2.23) (161g), 9,9-bis (4-hydroxyphenyl) fluorene (61g, 0.175mol), toluene (350g), nitrogen replacement, then add isophthaloyl chloride (242g, 1.2mol), nitrogen protection, add 1-naphthol (137g, 0.95mol), add 48% sodium hydroxide aqueous solution (sodium hydroxide 40g, water 43g) dropwise at 40°C, stir and react for 1 hour. After the reaction is completed, separate the liquid to remove the water layer, wash the organic layer with water to pH 7, remove the water layer, and distill under reduced pressure to remove the organic solvent to obtain resin X4 with a solid content of 65%.

[0096] Preparation Example 5

[0097] Put the mixture into a flask equipped with a thermometer, dropping funnel, condenser, splitter and stirrer. (wherein A is selected from phenylene, E is selected from G is selected from methylene, n is 2.23, hydroxyl equivalent 230g / eq) (161g), (X is selected from O, R 4 , R 5 Selected from p-hydroxy-substituted phenyl) (56g, 0.175mol), toluene (350g), nitrogen replacement, then add isophthaloyl chloride (242g, 1.2mol), nitrogen protection, add 1-naphthol (137g, 0.95mol), add 48% sodium hydroxide aqueous solution (sodium hydroxide 40g, water 43g) dropwise at 40°C, and stir to react for 1 hour. After the reaction is completed, separate the liquid to remove the water layer, wash the organic layer with water to pH 7, remove the water layer, and distill under reduced pressure to remove the organic solvent to obtain resin X5 with a solid content of 65%.

[0098] Preparation Example 6

[0099] Put the mixture into a flask equipped with a thermometer, dropping funnel, condenser, splitter and stirrer. (A is selected from phenylene, E is selected from G is selected from a connecting bond, n is 0.16) (hydroxyl equivalent 165g / eq) (116g), (X is selected from NR 6 , R 6 Selected from phenyl, R 4 , R 5 Selected from p-hydroxy-substituted phenyl) (69g, 0.175mol), toluene (350g), nitrogen replacement, then add isophthaloyl chloride (242g, 1.2mol), nitrogen protection, add 1-naphthol (137g, 0.95mol), 48% sodium hydroxide aqueous solution (sodium hydroxide 40g, water 43g) is added dropwise at 40°C, and stirred for reaction for 1 hour. After the reaction is completed, the water layer is separated and the organic layer is washed with water to pH 7, the water layer is removed, and the organic solvent is distilled off under reduced pressure to obtain resin X6 with a solid content of 65%.

[0100] Preparation of Comparative Example 1D1

[0101] Put the mixture into a flask equipped with a thermometer, dropping funnel, condenser, splitter and stirrer. (A is selected from phenylene, E is selected from G is selected from a connecting bond, n is 0.16) (hydroxyl equivalent 165g / eq) (173g), toluene (350g), nitrogen replacement, then add isophthaloyl chloride (242g, 1.2mol), nitrogen protection, add 1-naphthol (137g, 0.95mol), add 48% sodium hydroxide aqueous solution (sodium hydroxide 40g, water 43g) dropwise at 40°C, and stir to react for 1 hour. After the reaction is completed, separate the liquid to remove the water layer, wash the organic layer with water to pH 7, remove the water layer, and distill under reduced pressure to remove the organic solvent to obtain resin D1 with a solid content of 65%.

[0102] Preparation of Comparative Example 2D2

[0103] Put the mixture into a flask equipped with a thermometer, dropping funnel, condenser, splitter and stirrer. (X is selected from NR 6 , R 6 Selected from phenyl, R 4 , R 5 Selected from p-hydroxy-substituted phenyl) (207g, 0.525mol), toluene (350g), nitrogen replacement, then add isophthaloyl chloride (242g, 1.2mol), nitrogen protection, add 1-naphthol (137g, 0.95mol), add 48% sodium hydroxide aqueous solution (sodium hydroxide 40g, water 43g) dropwise at 40°C, stir and react for 1 hour. After the reaction is completed, separate the liquid to remove the water layer, wash the organic layer with water to pH 7, remove the water layer, and distill under reduced pressure to remove the organic solvent to obtain resin D2 with a solid content of 65%.

[0104] Comparative Example 3 D3 was prepared as a composition of D1 and D2 (D1:D2 = ester group equivalent ratio 1:1).

[0105] The amount of each raw material used in the copolymer preparation example is 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 compositions

[0112] Laminated board manufacturing conditions

[0113] Base material: Glass cloth "#2116" (210X280mm) manufactured by Nitto Boseki Co., Ltd.

[0114] Number of layers: 6

[0115] Pre-impregnation conditions: 160°C

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

[0117] Thickness after forming: 0.8mm

[0118] Solvent: MEK (methyl ethyl ketone)

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

[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 is 287g / eq, and softening point is 69°C.

[0121] The raw materials and amounts used in the preparation examples and comparative examples of epoxy resin compositions are shown in Table 3.

[0122] Table 3

[0123]

[0124]

[0125] The performance test data of the embodiments and comparative examples of the epoxy resin composition are shown in Table 4.

[0126] Table 4

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

[0128] The copolymer, resin composition and application of the resin composition proposed in this application have been described through preferred embodiments. It is obvious that relevant technical personnel can modify or appropriately change and combine the process methods described herein without departing from the content, spirit and scope of this application to implement the technology of this application. It should be particularly pointed out that all similar substitutions and modifications are obvious to those skilled in the art, and they will be deemed to be included in the spirit, scope and content of this application.

Claims

1. A copolymer, characterized in that The copolymer includes a monofunctional phenol compound residue, an aromatic dicarboxylic acid or an acyl halide residue thereof, a difunctional phenol compound residue, and a polyfunctional phenol resin residue.

2. The copolymer according to claim 1, characterized in that Also includes any one or more of the following features: a1) the monomer corresponding to the monofunctional phenol compound residue is a monofunctional phenol compound, and the monofunctional phenol 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, and 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; a3) The monomer corresponding to the multifunctional phenol resin residue is a multifunctional phenol resin, and the structural formula of the multifunctional phenol resin is A is selected from an arylene group, G is selected from an alkylene group or a connecting bond, E is selected from an arylene group or a cycloalkylene group, and n is a repeating unit selected from a number of 0-10.

3. The copolymer according to claim 2, characterized in that Also includes any one or more of the following features: a31) A is selected from C6-C12 arylene; a32) G is selected from C1-C3 alkylene or a linking bond; a33) E is selected from a C6-C12 arylene group or a C10-C20 cycloalkylene group.

4. The copolymer according to claim 3, characterized in that Also includes any one or more of the following features: a311) A is selected from phenylene or naphthylene; a321) G is selected from methylene, a322) G is selected from a connecting bond; a331)E is selected from phenylene, naphthylene, biphenylene or in, Indicates the connection position, m is an integer from 0 to 1.

5. The copolymer according to claim 2, characterized in that Also includes any 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 of 0-10, the multifunctional phenol resin is an aralkyl type phenolic resin; b2) when A is selected from phenylene or naphthylene, E is selected from biphenylene, G is selected from methylene, When n is a repeating unit and the average value is a number of 0-10, the multifunctional phenol resin is a biphenyl aralkyl type phenolic resin; b3) when A is selected from phenylene or naphthylene, E is selected from When G is selected from a connecting bond, n is a repeating unit and the average value is a number of 0-10, the multifunctional phenol resin is a dicyclopentadiene phenolic resin.

6. The copolymer according to claim 1, characterized in that The monomer corresponding to the difunctional phenol compound residue is a difunctional phenol compound, and the difunctional phenol compound is selected from phenolphthalein, a derivative of phenolphthalein, dihydroxy-substituted diphenylfluorene or a dihydroxy-substituted diphenylfluorene derivative.

7. The copolymer according to claim 6, characterized in that Also includes any one or more of the following features: d1) The structural formula of the phenolphthalein derivative is Wherein, X is selected from NR 6 ; R 6 Selected from phenyl; R 4 , R 5 Each independently selected from hydroxy-substituted phenyl; d2) the dihydroxy-substituted diphenylfluorene is 9,9-bis(4-hydroxyphenyl)fluorene; d3) The dihydroxy-substituted diphenylfluorene derivative is an alkyl-substituted dihydroxy-substituted diphenylfluorene.

8. A method for preparing a copolymer according to any one of claims 1 to 7, characterized in that: The preparation method comprises: mixing and reacting a monofunctional phenol compound, an aromatic dicarboxylic acid or its acyl halide, a difunctional phenol compound and a multifunctional phenol resin.

9. A resin composition, characterized in that The resin composition comprises the copolymer according to any one of claims 1 to 7 and an epoxy resin.

10. Use of the copolymer according to any one of claims 1 to 7 and / or the resin composition according to claim 9 in cured products, semiconductor encapsulation, prepregs, circuit boards, and laminated films.

Images