A low dielectric resin, resin composition and application thereof

Abstract

The present application relates to the field of polymer materials technology, and in particular to a low dielectric resin, a resin composition, and applications thereof. The resin comprises a structure represented by formula (1): #imgabs0#n is a repeating unit selected from a number of 1-10; m is an integer of 1-2. The resin, resin composition, and resin mixture of the present application have excellent properties of low dielectric properties, resistance to moisture and heat, and toughness. Therefore, the resin, resin composition, and resin mixture of the present application can be used in laminates of printed circuit boards for various electrical devices.

Description

Technical Field

[0001] The present application relates to the technical field of polymer materials, and in particular to a low dielectric resin, a resin composition and applications thereof. Background Art

[0002] As electronic devices continue to evolve toward miniaturization, high performance, and high reliability, printed circuit boards (PCBs), an essential component of these devices, are subject to increasingly stringent material selection and performance requirements. To improve signal transmission speeds and adapt to diverse operating environments, the laminates used in PCBs for various electrical devices require materials with low dielectric properties, moisture and heat resistance, and toughness. Summary of the Invention

[0003] In view of the shortcomings of the prior art described above, the purpose of this application is to provide a low dielectric resin, a resin composition and its application, which is used to obtain a resin, a resin composition or a resin mixture with low dielectric properties, moisture and heat resistance, and toughness, so as to solve the problems in the prior art.

[0004] To achieve the above-mentioned objectives and other related purposes, this application is obtained through the following technical solutions.

[0005] On the one hand, the present application provides a resin, which comprises a structure represented by formula (1):

[0006]

[0007] n is a repeating unit, a number selected from 1-10;

[0008] m is an integer of 1-2.

[0009] The second aspect of the present application provides a resin composition, which comprises a structure represented by formula (1-1) and a structure represented by formula (1-2).

[0010]

[0011] n is a repeating unit, and is a number selected from 1-10.

[0012] The third aspect of the present application provides a resin mixture, which comprises the resin of the structure represented by the aforementioned formula (1) or the aforementioned resin composition and at least one other resin, wherein the other resin is selected from resins that react with the resin of the structure represented by the formula (1) or the resin composition.

[0013] A fourth aspect of the present application provides the use of the resin, resin composition and / or resin mixture as described above in the present invention in prepregs, circuit substrates, and laminated films.

[0014] Compared with the prior art, the present invention has the following advantages:

[0015] The resin, resin composition, and resin mixture of the present application have excellent properties such as low dielectric properties, moisture and heat resistance, and toughness. Therefore, the resin, resin composition, and resin mixture of the present application can be used in laminates of printed wiring boards for various electrical devices. DETAILED DESCRIPTION

[0016] The following describes the implementation of the present application through specific embodiments. People familiar with this technology can easily understand other advantages and effects of the present application from the contents disclosed in this specification.

[0017] Before further describing the specific embodiments of this application, it should be understood that the scope of protection of this application is not limited to the specific embodiments described below; it should also be understood that the terms used in the examples of this application are intended to describe specific embodiments and are not intended to limit the scope of protection of this application. The experimental methods in the following examples where specific conditions are not specified are generally based on conventional conditions or the conditions recommended by the respective manufacturers.

[0018] When the embodiments provide numerical ranges, it should be understood that, unless otherwise specified herein, both endpoints of each numerical range and any numerical value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in this 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 this 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 this application.

[0019]

Term Explanation

[0020] Unless otherwise specified, "resin" is generally a customary name for a synthetic polymer. However, in the present invention, "resin" may be interpreted to include, but is not limited to, a monomer, a polymer thereof, a combination of monomers, a combination of polymers thereof, or a combination of a monomer and a polymer thereof. For example, in the present invention, "maleimide resin" may be interpreted to include, but is not limited to, a maleimide monomer, a maleimide polymer, a combination of maleimide monomers, a combination of maleimide polymers, or a combination of a maleimide monomer and a maleimide polymer.

[0021] Resin

[0022] The present application provides a resin having a structure shown in formula (1):

[0023]

[0024] n is a repeating unit, and is selected from a number of 1 to 10. Preferably, n is selected from a number of 1.1 to 10 (e.g., 1.1, 1.2, 1.3, 2, 3, 5, 10, etc.), and more preferably a number of 1.1 to 5.

[0025] m is an integer of 1-2.

[0026] In the resin provided by the present invention, optionally, the resin further comprises one or more of a retarder, an initiator, a curing accelerator, a flame retardant, and an inorganic additive. Specifically:

[0027] The resin further comprises a retarder. The addition of a retarder can control reaction conditions and improve storage stability. The retarder can be added during or after synthesis. The retarder is added in an amount of 0.01 to 1 part by weight per 100 parts by weight.

[0028] Examples of retarders include phenols, sulfurs, phosphorus, amines, nitroso groups, and nitroxyl radicals. A single retarder may be used alone, or a combination of multiple retarders may be used. Among these, phenols, amines, nitroso groups, and nitroxyl radicals are preferred in the present invention. The above-mentioned phenolic retardants include, but are not limited to, the following monophenols: 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-butyl-p-cresol, tert-butyl-p-ethylphenol, stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, isooctyl-3-(3,5-di-tert-butyl)-4-hydroxyphenyl) propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, 2,4-bis[(octylthio))methyl]-o-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol). Sulfur retardants include, but are not limited to, dilauryl 3,3'-thiodipropionate and dimyristyl 3,3'-thiodipropionate. Amine retarders include, but are not limited to, Adekastab LA-40MP, Adekastab LA-40Si, Adekastab LA-402AF, Adekastab LA-87, Adekastab LA-82, and Dekastab LA-81. Examples of nitroso retarders include ammonium salts of p-nitrosophenol, N-nitrosodiphenylamine, and N-nitrosophenylhydroxylamine. Examples of nitroxyl radical retarders include di-tert-butylnitroxide, 2,2,6,6-tetramethylpiperidin-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidin-1-oxyl, and 4-methoxy-2,2,6,6-tetramethylpiperidin-1-oxyl.

[0029] The resin further comprises an initiator, such as a free radical polymerization initiator or a cationic initiator, and the free radical polymerization initiator is such as a peroxide initiator or an azo initiator.

[0030] Peroxide initiators such as methyl ethyl ketone peroxide, acetylacetone peroxide and other peroxide ketones; diacyl peroxides such as benzoyl peroxide; dialkyl peroxides such as diisopropyl peroxide, α,α'-di(tert-butylperoxy)diisopropyl benzene, 1,3-bis(tert-butylperoxyisopropyl)benzene; peroxyketals such as tert-butyl perbenzoate, 1,1-di-tert-butylperoxycyclohexane; isopropyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, peroxy Alkyl peresters such as tert-amyl 2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, and tert-amyl peroxybenzoate; percarbonates such as di(2-ethylhexyl) peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl peroxyisopropyl carbonate, and 1,6-bis(tert-butylperoxycarbonyloxy)hexane; organic peroxides such as tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxyethyloctanoate, and lauroyl peroxide.

[0031] Examples of the azo initiator include, but are not particularly limited to, known curing accelerators such as azobisisobutyronitrile, 4,4′-azobis(4-cyanovaleric acid), and 2,2′-azobis(2,4-dimethylvaleronitrile).

[0032] The amount of the radical polymerization initiator added is preferably 0.01 to 5 parts by mass, particularly preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the curable resin composition.

[0033] The resin further includes a curing accelerator, including pyridines, phosphorus compounds, amine compounds, imidazole compounds, organic acid metal salts, Lewis acids, and amine complex salts.

[0034] Examples of the phosphorus compound include primary phosphines such as alkylphosphines and phenylphosphine, secondary phosphines such as dialkylphosphines and diphenylphosphine, tertiary phosphines such as trialkylphosphines and triphenylphosphine, and phosphonium salt compounds.

[0035] Examples of the amine compound include 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.

[0036] Imidazole compounds include 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-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.

[0037] The curing accelerators may be used alone or in combination of two or more.

[0038] The resin further includes a flame retardant. Examples of flame retardants include phosphorus-containing compounds, and the phosphorus-containing compounds may be reactive or additive. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-diphenyl phosphate, 1,3-phenylene bis(diphenyl phosphate and other phosphates) 1,4-phenylene bis(diphenyl phosphate), 10(2,5-dihydroxyphenyl)- and other 9,10-dihydro-9-oxaphosphine 10H-9-oxa-10-phosphaphenanthrene-10-oxide; the active hydrogen of the epoxy resin and the above-mentioned phosphane is preferably a phosphate, a phosphane or a phosphorus-containing epoxy compound, such as a phosphorus-containing epoxy compound obtained by reaction with 1,3-diphenyl phosphate. Particularly preferred are 1,4-phenylene bis(xylylene phosphate), 4,4′-biphenyl(xylylene phosphate), or phosphorus-containing epoxy compounds.

[0039] The resin further includes an inorganic additive.

[0040] Examples of the inorganic additive include fused silica, crystalline silica, aluminum oxide, 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, fused silica can be used in a crushed or spherical form, but in order to increase the amount of fused silica and suppress the rise 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 spherical silica, it is preferred to appropriately adjust the particle size distribution of the spherical silica.

[0041] [Resin composition]

[0042] The present application also provides a resin composition having a structure shown in formula (1-1) and a structure shown in formula (1-2):

[0043]

[0044] n is a repeating unit, and is selected from a number of 1 to 10. Preferably, n is selected from a number of 1.1 to 10 (e.g., 1.1, 1.2, 1.3, 2, 3, 5, 10, etc.), and more preferably a number of 1.1 to 5.

[0045] Optionally, formula (1-1) is selected from any of the following structures:

[0046]

[0047] Optionally, formula (1-2) is selected from any of the following structures:

[0048]

[0049] Optionally, the mass ratio of the structure represented by formula (1-1) to the structure represented by formula (1-2) is (50-70):(30-50).

[0050] In the resin composition provided by the present invention, optionally, the resin composition further comprises one or more of a retarder, an initiator, a curing accelerator, a flame retardant, and an inorganic additive.

[0051] The resin composition further comprises a retarder. The addition of a retarder can control reaction conditions and improve storage stability. The retarder can be added during or after synthesis. The amount of the retarder added is 0.01-1 parts by weight per 100 parts by weight.

[0052] Examples of retarders include phenols, sulfurs, phosphorus, amines, nitroso groups, and nitroxyl radicals. A single retarder may be used alone, or a combination of multiple retarders may be used. Among these, phenols, amines, nitroso groups, and nitroxyl radicals are preferred in the present invention. The above-mentioned phenolic retardants include, but are not limited to, the following monophenols: 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-butyl-p-cresol, tert-butyl-p-ethylphenol, stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, isooctyl-3-(3,5-di-tert-butyl)-4-hydroxyphenyl) propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, 2,4-bis[(octylthio))methyl]-o-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol). Sulfur retardants include, but are not limited to, dilauryl 3,3'-thiodipropionate and dimyristyl 3,3'-thiodipropionate. Amine retarders include, but are not limited to, Adekastab LA-40MP, Adekastab LA-40Si, Adekastab LA-402AF, Adekastab LA-87, Adekastab LA-82, and Dekastab LA-81. Examples of nitroso retarders include ammonium salts of p-nitrosophenol, N-nitrosodiphenylamine, and N-nitrosophenylhydroxylamine. Examples of nitroxyl radical retarders include di-tert-butylnitroxide, 2,2,6,6-tetramethylpiperidin-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidin-1-oxyl, and 4-methoxy-2,2,6,6-tetramethylpiperidin-1-oxyl.

[0053] The resin composition further comprises an initiator, such as a free radical polymerization initiator or a cationic initiator, and the free radical polymerization initiator is such as a peroxide initiator or an azo initiator.

[0054] Peroxide initiators such as methyl ethyl ketone peroxide, acetylacetone peroxide and other peroxide ketones; diacyl peroxides such as benzoyl peroxide; dialkyl peroxides such as diisopropyl peroxide, α,α'-di(tert-butylperoxy)diisopropyl benzene, 1,3-bis(tert-butylperoxyisopropyl)benzene; peroxyketals such as tert-butyl perbenzoate, 1,1-di-tert-butylperoxycyclohexane; isopropyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, peroxy Alkyl peresters such as tert-amyl 2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, and tert-amyl peroxybenzoate; percarbonates such as di(2-ethylhexyl) peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl peroxyisopropyl carbonate, and 1,6-bis(tert-butylperoxycarbonyloxy)hexane; organic peroxides such as tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxyethyloctanoate, and lauroyl peroxide.

[0055] Examples of the azo initiator include, but are not particularly limited to, known curing accelerators such as azobisisobutyronitrile, 4,4′-azobis(4-cyanovaleric acid), and 2,2′-azobis(2,4-dimethylvaleronitrile).

[0056] The amount of the radical polymerization initiator added is preferably 0.01 to 5 parts by mass, particularly preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the curable resin composition.

[0057] The resin composition further comprises a curing accelerator, including pyridines, phosphorus compounds, amine compounds, imidazole compounds, organic acid metal salts, Lewis acids and amine complex salts.

[0058] Examples of the phosphorus compound include primary phosphines such as alkylphosphines and phenylphosphine, secondary phosphines such as dialkylphosphines and diphenylphosphine, tertiary phosphines such as trialkylphosphines and triphenylphosphine, and phosphonium salt compounds.

[0059] Examples of the amine compound include 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.

[0060] Imidazole compounds include 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-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.

[0061] The curing accelerators may be used alone or in combination of two or more.

[0062] The resin composition further includes a flame retardant. Examples of flame retardants include phosphorus-containing compounds, and the phosphorus-containing compounds may be reactive or additive. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-diphenyl phosphate, 1,3-phenylene bis(diphenyl phosphate and other phosphates) 1, 4-phenylene bis(diphenyl phosphate), 10(2,5-dihydroxyphenyl)- and other 9,10-dihydro-9-oxaphosphine 10H-9-oxa-10-phosphaphenanthrene-10-oxide; the active hydrogen of the epoxy resin and the above-mentioned phosphane is preferably a phosphate, a phosphane or a phosphorus-containing epoxy compound, such as a phosphorus-containing epoxy compound obtained by reaction with 1,3-diphenyl phosphate. Particularly preferred are 1,4-phenylene bis(xylylene phosphate), 4,4′-biphenyl(xylylene phosphate), or phosphorus-containing epoxy compounds.

[0063] The resin composition further includes an inorganic additive.

[0064] Examples of the inorganic additive include fused silica, crystalline silica, aluminum oxide, 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, fused silica can be used in a crushed or spherical form, but in order to increase the amount of fused silica and suppress the rise 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 spherical silica, it is preferred to appropriately adjust the particle size distribution of the spherical silica.

[0065] Resin mixture

[0066] The present application also provides a resin mixture, which comprises the resin of the structure represented by formula (1) or the resin composition of the present invention and at least one other resin, wherein the other resin is selected from resins that react with the resin of the structure represented by formula (1) or the resin composition.

[0067] Right now:

[0068] In one embodiment, the resin mixture comprises the resin represented by formula (1) and at least one other resin reactive therewith.

[0069] In another embodiment, the resin mixture comprises the structure represented by formula (1-1) and the structure represented by formula (1-2), and other resins that react with formulas (1-1) and (1-2).

[0070] In the resin mixture provided by the present invention, the other resin reacting with formula (1), formula (1-1), and formula (1-2) is a resin containing an ethylenically unsaturated bond. Optionally, the resin containing an ethylenically unsaturated bond includes one of maleimide resin and polyphenylene ether, or a combination thereof.

[0071] Maleimide resin is Ar is selected from an aromatic group, an aliphatic group, or a group composed of an aliphatic group and an aromatic group. Further optionally, the maleimide resin containing an ethylenically unsaturated bond is one or more of formulas (2), (3), (4), and (5):

[0072] q is a repeating unit, and is selected from a number of 1 to 10, preferably a number of 1 to 5. Gel permeation chromatography test shows that Mn is 400-5000, and Mw is 420-8000.

[0073] s is a repeating unit, selected from a number of 0.5-10, preferably a number of 0.5-5. Gel permeation chromatography test Mn is 700-7000, Mw is 750-10000. Optionally, formula (3) is selected from

[0074]

[0075] t is a repeating unit, and is selected from a number of 1 to 10, preferably a number of 1 to 5. Gel permeation chromatography test shows that Mn is 1400-8000, and Mw is 1450-12000.

[0076] The polyphenylene ether containing ethylenically unsaturated bonds is preferably a polyphenylene ether containing a styrene group, such as a polyphenylene ether resin as shown in the following formula (6), wherein r is a repeating unit selected from 1-20, and k is a repeating unit selected from 1-20, preferably, r+k=2-40, and more preferably, r+k=2-20.

[0077]

[0078] Gel permeation chromatography (GPC) analysis shows that the Mn is 700-5000 and the Mw is 750-8000, preferably 700-2000 and 750-3000.

[0079] In the resin mixture provided by the present invention, the mass ratio of the resin of formula (1) to the resin containing ethylenically unsaturated bonds is 100:0.1-100:500. Alternatively, the mass ratio of the resin of formula (1) to the resin containing ethylenically unsaturated bonds can be, for example, 100:1-100:500, 100:0.1-50:500, 100:50-100:500, 100:0.1-10:500, 100:10-30:500, 100:30-50:500, 100:50-80:500, 100:80-100:500, etc.

[0080] In the resin mixture provided by the present invention, the mass ratio of the total mass of the resins of the resin composition formula (1-1) and formula (1-2) to the resin containing ethylenically unsaturated bonds is 100:0.1-100:500. Alternatively, the mass ratio of the total mass of the resins of formula (1-1) and formula (1-2) to the resin containing ethylenically unsaturated bonds can be, for example, 100:1-100:500, 100:0.1-50:500, 100:50-100:500, 100:0.1-10:500, 100:10-30:500, 100:30-50:500, 100:50-80:500, 100:80-100:500, etc. Preferably, it is 100:1-100:300.

[0081]

application

[0082] The present invention also provides use of the aforementioned resin, the aforementioned resin composition, and / or the aforementioned resin mixture in prepregs, circuit boards, and build-up films.

[0083]

Prepreg

[0084] The present application also provides a prepreg, which is obtained by impregnating a reinforcing substrate with the resin, resin composition, or resin mixture as described above in the present application, and semi-curing the obtained reinforcing substrate.

[0085] In one embodiment, the resin represented by formula (1) and the ethylenically unsaturated bond-containing resin composition are impregnated into a reinforcing substrate, and the obtained reinforcing substrate is semi-cured.

[0086] In another embodiment, the resins represented by formula (1-1) and formula (1-2) and the ethylenically unsaturated bond-containing resin composition are impregnated into a reinforcing substrate, and the obtained reinforcing substrate is semi-cured.

[0087] 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; preferably, open fiber cloth or flat cloth is used among the glass fiber cloth; and preferably, the glass fiber cloth is E glass fiber cloth, S glass fiber cloth, or Q glass fiber cloth.

[0088]

Circuit board

[0089] The present application also provides a circuit substrate, which is obtained by mixing the resin, resin composition, resin mixture and organic solvent as described above in the present application to obtain a varnish, and the varnish and copper foil are formed into a plate under heating and pressure.

[0090] In one embodiment, the resin represented by formula (1) and the ethylenically unsaturated bond-containing resin composition are added with an organic solvent to obtain a varnish, and the varnish and copper foil are formed into a sheet under heating and pressure.

[0091] In another embodiment, the resins represented by formula (1-1) and formula (1-2) and the ethylenically unsaturated bond-containing resin composition are added with an organic solvent to obtain a varnish, and the varnish and copper foil are formed into a sheet under heating and pressure.

[0092]

Laminated Film

[0093] The present application also provides a laminated film, which is prepared by mixing the resin, resin composition, or resin mixture described above with an organic solvent, coating the obtained material on a substrate film, and drying the mixture.

[0094] In one embodiment, an organic solvent is added to the resin represented by formula (1) and the ethylenically unsaturated bond-containing resin composition, and the resulting product is coated on a substrate film and dried.

[0095] In another embodiment, the resins represented by formula (1-1) and formula (1-2) and the ethylenically unsaturated bond-containing resin composition are added with an organic solvent, and the resulting material is coated on a substrate film and dried.

[0096] The substrate film is selected from at least one of PET film, PP film, PE film and PVC film.

[0097] [Resin synthesis method]

[0098]

[0099] X is selected from halogen, such as bromine, chlorine, iodine.

[0100] The first step is acidic conditions. The acidic catalyst used can be sulfuric acid, hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid, activated clay, ion exchange resin and the like. These can be used alone or in combination of two or more.

[0101] The second step is to remove the hydrogen halogenide under alkaline conditions. Examples of alkaline conditions include sodium hydroxide, potassium hydroxide, triethylamine, pyridine, and the like.

[0102] Examples of the solvent used include aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ester solvents such as ethyl acetate and butyl acetate, and methyl isobutyl. In addition to water-insoluble solvents, aprotic polar solvents can also be used, examples of which include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone and N-methylpyrrolidone. The solvents can be used alone or in combination of two or more.

[0103] Synthesis Example 1

[0104]

[0105] first step

[0106] In a flask equipped with a thermometer, condenser, and stirrer, 300 parts by mass of 1,3-diisopropenylbenzene, 80 parts by mass of 2-bromoethylbenzene, and 20 parts by mass of concentrated sulfuric acid were placed and reacted at 130°C for 8 hours. After cooling naturally, the mixture was neutralized with aqueous sodium hydroxide solution, extracted with 1200 parts by mass of toluene, and the organic layer was washed five times with 100 parts by mass of water. The solvent and excess 2-bromoethylbenzene were distilled off under reduced pressure with heating to obtain resin A1 (Mn: 980, Mw: 1640) with a repeating unit n of 2.1.

[0107] Step 2

[0108] In a flask equipped with a thermometer, condenser, and stirrer, 25 parts by mass of A1 obtained in the first step, 50 parts by mass of toluene, 150 parts by mass of DMF, 15 parts by mass of water, and 5 parts by mass of sodium hydroxide were added and reacted at 40°C for 5 hours. After cooling naturally, 100 parts by mass of toluene was added, and the organic layer was washed five times with 100 parts by mass of water. The organic solvent was then distilled off under reduced pressure to obtain resin B1 (Mn: 805, Mw: 1480) with a solid content of 60% and a repeating unit n of 2.1.

[0109] Synthesis Example 2

[0110]

[0111] first step

[0112] In a flask equipped with a thermometer, condenser, and stirrer, 300 parts by mass of 1,4-diisopropenylbenzene, 80 parts by mass of 2-bromoethylbenzene, and 20 parts by mass of concentrated sulfuric acid were added and reacted at 130°C for 8 hours. After cooling naturally, the mixture was neutralized with aqueous sodium hydroxide solution, extracted with 1200 parts by mass of toluene, and the organic layer was washed five times with 100 parts by mass of water. The solvent and excess 2-bromoethylbenzene were distilled off under reduced pressure with heating to obtain resin A2 (Mn: 945, Mw: 1565) with a repeating unit n of 2.0.

[0113] Step 2

[0114] In a flask equipped with a thermometer, condenser, and stirrer, 25 parts by mass of A2 obtained in the first step, 50 parts by mass of toluene, 150 parts by mass of DMF, 15 parts by mass of water, and 5 parts by mass of sodium hydroxide were added and reacted at 40°C for 5 hours. After cooling naturally, 100 parts by mass of toluene was added, and the organic layer was washed five times with 100 parts by mass of water. The organic solvent was then distilled off under reduced pressure to obtain resin B2 (Mn: 850, Mw: 1420) with a solid content of 60% and a repeating unit n of 2.0.

[0115] Synthesis Example 3

[0116]

[0117] In a flask equipped with a thermometer, condenser, and stirrer, 300 parts by mass of 4,4'-diisopropenyl-1,1'-biphenyl, 80 parts by mass of 2-bromoethylbenzene, and 20 parts by mass of concentrated sulfuric acid were added and reacted at 130°C for 8 hours. After cooling, the mixture was neutralized with aqueous sodium hydroxide solution, extracted with 1200 parts by mass of toluene, and the organic layer was washed five times with 100 parts by mass of water. The solvent and excess 2-bromoethylbenzene were distilled off under reduced pressure with heating to obtain resin A3 (Mn: 1150, Mw: 2020) with a repeating unit n of 2.1.

[0118] Step 2

[0119] In a flask equipped with a thermometer, condenser, and stirrer, 25 parts by mass of A3 obtained in the first step, 50 parts by mass of toluene, 150 parts by mass of DMF, 15 parts by mass of water, and 5 parts by mass of sodium hydroxide were added and reacted at 40°C for 5 hours. After cooling naturally, 100 parts by mass of toluene was added, and the organic layer was washed five times with 100 parts by mass of water. The organic solvent was then distilled off under reduced pressure to obtain resin B3 (Mn: 1015, Mw: 1890) with a solid content of 60% and a repeating unit n of 2.1.

[0120] Comparative Example 1

[0121]

[0122] first step

[0123] In a flask equipped with a thermometer, condenser, and stirrer, 300 parts by mass of 2-bromoethylbenzene, 70 parts by mass of α,α'-dichlorom-xylene, and 20 parts by mass of concentrated sulfuric acid were added and reacted at 130°C for 8 hours. After cooling naturally, the mixture was neutralized with aqueous sodium hydroxide solution, extracted with toluene, and the organic layer washed five times with water. The solvent and excess 2-bromoethylbenzene were distilled off under reduced pressure with heating to obtain compound X-1 (Mn: 906, Mw: 1550), with a repeating unit n of 2.0.

[0124] Step 2

[0125] In a flask equipped with a thermometer, condenser, and stirrer, 25 parts of 50 parts of toluene, 150 parts by mass of DMF, 15 parts by mass of water, and 5 parts by mass of sodium hydroxide were added, and the mixture was reacted at 40°C for 5 hours. After natural cooling, 100 parts by mass of toluene was added, and the organic layer was washed five times with 100 parts by mass of water. The organic solvent was then distilled off under reduced pressure until a solid content of 60% was obtained, yielding (Y-1) (Mn: 745, Mw: 1390), with a repeating unit n of 2.0.

[0126] Test Case

[0127] Test instruments and methods:

[0128] GPC instrument: Agilent 1260 Infinity II; conditions: THF flow rate 1 mL / min, 35° C. Monodisperse polystyrene with known molecular weight was used.

[0129] Determination of dielectric constant and dielectric loss tangent: GB / T 40564-2021

[0130] Moisture absorption: The laminate obtained above was cut into pieces of 25 mm in width and 75 mm in length to prepare test pieces. The test pieces were placed in an atmosphere of 85°C / 85% RH for 168 hours, and the weight change before and after the test pieces was measured.

[0131] Flexural Strength IPC-TM-650 2.4.4

[0132] 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

[0133] The materials (parts by mass) were prepared according to the proportions shown in Tables 1 and 2, wherein the maleimide resin or polyphenylene ether resin was dissolved in toluene with a solid content of 60%, and then heated, melted, and mixed in a metal container. The solvent was removed and the mixture was cured at 160°C for 1 hour and then at 200°C for 2 hours.

[0134] (M1): The substance represented by formula (2) was prepared by the synthesis method of Example 1 of CN112334513B.

[0135] (MY1): The substance represented by formula (3) was prepared according to the method of Synthesis Example 1 of CN113748149B.

[0136] (OP1): In formula (6), OPE-2St (polyphenylene ether with a styrene structure manufactured by Mitsubishi Gas Chemical Co., Ltd.) is selected.

[0137] Table 1

[0138]

[0139] Table 2

[0140]

[0141]

[0142] As can be seen from Table 1, the resin represented by formula (1) of the present invention has lower dielectric properties and has significantly improved toughness when combined with the biphenyl structure resin (resin represented by formula 1-2).

[0143] The resin represented by formula (1) of the present invention, after curing with bismaleimide resin or polyphenylene ether resin, has lower dielectric properties, reduced moisture absorption, and better toughness than the comparative examples. Specifically, in Table 2, compared with comparative example 4, Example 5 shows better toughness, lower dielectric properties, and a higher glass transition temperature; compared with comparative example 5, Example 6 shows lower dielectric properties, lower moisture absorption, and better thermal and bending properties; and the toughness of Examples 9 and 10 is significantly improved compared with comparative example 6. The resin of the present application is more suitable for use as a low-dielectric printed circuit board material.

[0144] The low-dielectric resin, resin composition, and applications proposed in this application have been described through preferred embodiments. It is apparent to those skilled in the art that modifications, variations, and combinations of the process methods described herein can be made without departing from the content, spirit, and scope of this application to implement the technology of this application. It is particularly important to note that all similar substitutions and modifications that would be apparent to those skilled in the art are considered to be encompassed within the spirit, scope, and content of this application.

Claims

1. A resin composition, characterized in that The resin composition comprises a resin having a structure represented by formula (1-1) and a resin having a structure represented by formula (1-2). n is a repeating unit, a number selected from 1.1-10; The mass ratio of the resin having the structure represented by formula (1-1) to the resin having the structure represented by formula (1-2) is (50-70):(30-50).

2. The resin composition according to claim 1, wherein The resin composition further comprises one or more of a retarder, an initiator, a curing accelerator, a flame retardant, and an inorganic additive.

3. A resin mixture, characterized in that The resin mixture comprises the resin composition according to any one of claims 1 to 2 and at least one other resin, wherein the other resin is selected from resins that react with the resin composition.

4. The resin mixture according to claim 3, wherein The other resin is an ethylenically unsaturated bond-containing resin.

5. The resin mixture according to claim 4, wherein Also includes any one or more of the following features: C1) the resin containing ethylenically unsaturated bonds comprises one or a combination of maleimide resin and polyphenylene ether; C2) The mass ratio of the resin composition to the resin containing ethylenically unsaturated bonds is 100:0.1-100:

500.

6. The resin mixture according to claim 5, wherein Also includes any one or more of the following features: C11) the maleimide resin is Ar is selected from an aromatic group, an aliphatic group, or a combination of an aliphatic and an aromatic group; C12) The polyphenylene ether is a polyphenylene ether containing a styrene group.

7. The resin mixture according to claim 6, wherein Also includes any one or more of the following features: C111) The maleimide resin is selected from one or more of formula (2), formula (3), formula (4), and formula (5): q is a repeating unit, a number selected from 1-10; s is a repeating unit, selected from a number of 0.5-10; t is a repeating unit, a number selected from 1-10; C121) The polyphenylene ether is a polyphenylene ether resin represented by formula (6), r is a repeating unit selected from 1-20, and k is a repeating unit selected from 1-20.

8. Use of the resin composition according to any one of claims 1 to 2 and / or the resin mixture according to any one of claims 3 to 7 in prepregs, circuit boards, and build-up films.

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