Low dielectric resin, resin composition and application thereof

Abstract

The invention relates to the technical field of high polymer materials, in particular to low-dielectric resin, a resin composition and application thereof. The resin comprises a structure as shown in a formula (1): # imgabs0 # n is a repeating unit and is selected from a number from 1 to 10; and m is an integer of 1-2. The resin, the resin composition and the resin mixture have excellent characteristics of low dielectric property, heat and humidity resistance and toughness. Therefore, the resin, the resin composition and the resin mixture of the present application can be used in laminates of printed wiring boards of 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 develop towards miniaturization, high performance and high reliability, printed circuit boards (PCBs), as an indispensable component of electronic devices, have become increasingly stringent in terms of material selection and performance requirements. In order to increase signal transmission speed and adapt to different usage environments, the laminates of printed circuit boards used in 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 the present 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 purpose and other related purposes, the present application is obtained through the following technical solutions.

[0005] On the one hand, the present application provides a resin, wherein the resin comprises a structure shown in 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, wherein the resin composition 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 shown in the above formula (1) or the above resin composition and at least one other resin, wherein the other resin is selected from resins that react with the resin of the structure shown in 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 beneficial effects of this application are:

[0015] The resin, resin composition, and resin mixture of the present application have excellent properties of 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 of various electrical devices. DETAILED DESCRIPTION

[0016] 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.

[0017] 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.

[0018] 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.

[0019]

Term Explanation

[0020] If not otherwise specified, "resin" is generally a customary name for a synthetic polymer, but in the present invention, "resin" may include monomers, polymers thereof, combinations of monomers, combinations of polymers thereof, or combinations of monomers and polymers thereof, and is not limited thereto. For example, in the present invention, "maleimide resin" may include maleimide monomers, maleimide polymers, combinations of maleimide monomers, combinations of maleimide polymers, or combinations of maleimide monomers and maleimide polymers.

[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 (eg, 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 above resin further comprises a retarder. By adding the retarder, the reaction conditions can be controlled and the storage stability can be improved. The retarder can be added during the synthesis or after the synthesis. The amount of the retarder added is 0.01-1 part by weight per 100 parts by weight.

[0028] Examples of retarders include phenols, sulfurs, phosphors, amines, nitroso, nitroxyl free radicals, etc. In addition, the retarders may be used alone or in combination of multiple types. Among them, in the present invention, phenol type, amine type, nitroso type, nitroxyl free radical type are preferred. 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, Dekastab LA-81. Examples of nitroso retarders include ammonium salts of p-nitrosophenol, N-nitrosodiphenylamine, and N-nitrosophenylhydroxylamine. Examples of nitroxyl free 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 includes 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 ketone peroxides; diacyl peroxides such as benzoyl peroxide; dialkyl peroxides such as diisopropyl peroxide, α,α'-di(tert-butylperoxy)diisopropylbenzene, 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 perbenzoate; 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, isopropyl hydroperoxide, tert-butyl peroxyethyloctanoate, and lauroyl peroxide.

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

[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, based on 100 parts by mass of the curable resin composition.

[0033] The resin also 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 phosphine compounds such as primary phosphines such as alkylphosphines and phenylphosphine, secondary phosphines such as dialkylphosphines and diphenylphosphine, and 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 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.

[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. As specific examples of phosphorus-containing compounds, 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. 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 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 and 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 the spherical silica.

[0041] [Resin composition]

[0042] The present application also provides a resin composition, wherein the resin composition has 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 (eg, 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. By adding the retarder, the reaction conditions can be controlled and the storage stability can be improved. The retarder can be added during the synthesis or after the 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, phosphors, amines, nitroso, nitroxyl free radicals, etc. In addition, the retarders may be used alone or in combination of multiple types. Among them, in the present invention, phenol type, amine type, nitroso type, nitroxyl free radical type are preferred. 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, 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 ketone peroxides; diacyl peroxides such as benzoyl peroxide; dialkyl peroxides such as diisopropyl peroxide, α,α'-di(tert-butylperoxy)diisopropylbenzene, 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 perbenzoate; 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, isopropyl hydroperoxide, tert-butyl peroxyethyloctanoate, and lauroyl peroxide.

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

[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, based on 100 parts by mass of the curable resin composition.

[0057] The resin composition also includes 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 phosphine compounds such as primary phosphines such as alkylphosphines and phenylphosphine, secondary phosphines such as dialkylphosphines and diphenylphosphine, and 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 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.

[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. As specific examples of phosphorus-containing compounds, trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylyl phosphate, 1,3-phenylene bis (phosphoric acid esters such as dixylyl phosphate) 1, 4-phenylene bis (xylyl 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. 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 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 and 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 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 formula (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 ethylenic unsaturated bonds. Optionally, the resin containing ethylenic unsaturated bonds 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, selected from a number of 1 to 10, preferably a number of 1 to 5. The Mn measured by gel permeation chromatography is 400-5000, and the 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, selected from a number of 1 to 10, preferably a number of 1 to 5. The Mn measured by gel permeation chromatography is 1400-8000, and the 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] The Mn measured by gel permeation chromatography is 700-5000, and the Mw is 750-8000. The Mn is preferably 700-2000, and the Mw is preferably 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 ethylenic unsaturated bonds is 100:0.1-100:500. Optionally, the mass ratio of the resin of formula (1) to the resin containing ethylenic 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 ethylenic unsaturated bonds is 100:0.1-100:500. Optionally, the mass ratio of the total mass of the resins of formula (1-1) and formula (1-2) to the resin containing ethylenic 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 the use of the resin as described above in the present invention, the resin composition as described above in the present invention and / or the resin mixture as described above in the present invention in prepreg, circuit substrate and laminated film.

[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 to obtain the obtained substrate.

[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; 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.

[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 mentioned 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, resin mixture and organic solvent as described above in the present application, and coating the obtained material on a substrate film and drying it.

[0094] In one embodiment, the resin represented by formula (1) and the ethylenically unsaturated bond-containing resin composition are added with an organic solvent, 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] Wherein, 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 obtain the product by dehydrohalogenation under alkaline conditions, such as sodium hydroxide, potassium hydroxide, triethylamine, pyridine, etc.

[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, non-protonic 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 solvent 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, a condenser and a 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 added and reacted at 130°C for 8 hours. After natural cooling, the mixture was neutralized with an aqueous sodium hydroxide solution, extracted with 1200 parts by mass of toluene, and the organic layer was washed 5 times with 100 parts by mass of water. The solvent and excess 2-bromoethylbenzene were distilled off under heating and reduced pressure, thereby obtaining resin A1 (Mn: 980, Mw: 1640) with a repeating unit n of 2.1.

[0107] Step 2

[0108] 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 to a flask equipped with a thermometer, a condenser and a stirrer, and reacted at 40° C. for 5 hours. After natural cooling, 100 parts by mass of toluene was added, and the organic layer was washed 5 times with 100 parts by mass of water, and the organic solvent was distilled off under reduced pressure to obtain a resin B1 (Mn: 805, Mw: 1480) with a solid content of 60%, and the repeating unit n was 2.1.

[0109] Synthesis Example 2

[0110]

[0111] first step

[0112] 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 to a flask equipped with a thermometer, a condenser and a stirrer, and reacted at 130°C for 8 hours. After natural cooling, the mixture was neutralized with an aqueous sodium hydroxide solution, extracted with 1200 parts by mass of toluene, and the organic layer was washed 5 times with 100 parts by mass of water. The solvent and excess 2-bromoethylbenzene were distilled off under heating and reduced pressure, thereby obtaining resin A2 (Mn: 945, Mw: 1565) with a repeating unit n of 2.0.

[0113] Step 2

[0114] 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 to a flask equipped with a thermometer, a condenser and a stirrer, and reacted at 40° C. for 5 hours. After natural cooling, 100 parts by mass of toluene were added, and the organic layer was washed 5 times with 100 parts by mass of water, and the organic solvent was distilled off under reduced pressure to obtain a resin B2 (Mn: 850, Mw: 1420) with a solid content of 60%, and the repeating unit n was 2.0.

[0115] Synthesis Example 3

[0116]

[0117] In a flask equipped with a thermometer, a condenser, and a 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 natural cooling, the mixture was neutralized with an aqueous sodium hydroxide solution, extracted with 1200 parts by mass of toluene, and the organic layer was washed 5 times with 100 parts by mass of water. The solvent and excess 2-bromoethylbenzene were distilled off under heating and reduced pressure to obtain resin A3 (Mn: 1150, Mw: 2020), with a repeating unit n of 2.1.

[0118] Step 2

[0119] 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 to a flask equipped with a thermometer, a condenser and a stirrer, and reacted at 40° C. for 5 hours. After natural cooling, 100 parts by mass of toluene were added, and the organic layer was washed 5 times with 100 parts by mass of water, and the organic solvent was distilled off under reduced pressure to obtain a resin B3 (Mn: 1015, Mw: 1890) with a solid content of 60%, and the repeating unit n was 2.1.

[0120] Comparative Example 1

[0121]

[0122] first step

[0123] 300 parts by mass of 2-bromoethylbenzene, 70 parts by mass of α,α'-dichloro-m-xylene and 20 parts by mass of concentrated sulfuric acid were added to a flask equipped with a thermometer, a condenser and a stirrer, and reacted at 130°C for 8 hours. After natural cooling, the mixture was neutralized with an aqueous sodium hydroxide solution, extracted with toluene, and the organic layer was washed 5 times with water. The solvent and excess 2-bromoethylbenzene were distilled off under heating and reduced pressure to obtain compound X-1 (Mn: 906, Mw: 1550), with a repeating unit n of 2.0.

[0124] Step 2

[0125] 25 parts of 50 parts of toluene, 150 parts of DMF, 15 parts of water and 5 parts of sodium hydroxide were added to a flask equipped with a thermometer, a condenser and a stirrer, and the mixture was reacted at 40°C for 5 hours. After natural cooling, 100 parts of toluene were added, and the organic layer was washed 5 times with 100 parts of water, and the organic solvent was removed by distillation under reduced pressure until the solid content of (Y-1) (Mn: 745, Mw: 1390) was 60%, and the repeating unit n was 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 method of dielectric constant and dielectric loss tangent: GB / T 40564-2021

[0130] 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.

[0131] Bending Strength IPC-TM-650 2.4.4

[0132] Glass transition temperature Tg: Determined 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) are prepared in the proportions shown in Tables 1 and 2, wherein the maleimide resin or polyphenylene ether resin is dissolved in toluene with a solid content of 60%, and heated, melted and mixed in a metal container, the solvent is removed, and the mixture is cured at 160°C for 1 hour and then at 200°C for 2 hours.

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

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

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

[0137] Table 1

[0138]

[0139] Table 2

[0140]

[0141]

[0142] According to 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 has lower dielectric properties, reduced moisture absorption, better toughness, etc. after curing with bismaleimide resin or polyphenylene ether resin than the comparative example. Specifically, in Table 2, compared with comparative example 4, the resin of Example 5 of the present invention has better toughness, lower dielectric, and higher glass transition temperature; compared with comparative example 5, the resin of Example 6 of the present invention has lower dielectric, lower moisture absorption, better thermal performance and bending performance; the toughness of Examples 9 and 10 is significantly improved compared with that of 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 application 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 technical personnel in this field, and they will be deemed to be included in the spirit, scope and content of this application.

Claims

1. A resin, characterized in that The resin comprises a structure represented by formula (1), n is a repeating unit, a number selected from 1-10; m is an integer of 1-2.

2. The resin according to claim 1, characterized in that Also includes any one or more of the following features: A1) n is selected from a number of 1.1-10, preferably a number of 1.1-5; A2) The resin further comprises one or more of a retarder, an initiator, a curing accelerator, a flame retardant, and an inorganic additive.

3. A resin composition, characterized in that The resin composition comprises a structure represented by formula (1-1) and a structure represented by formula (1-2), n is a repeating unit, and is a number selected from 1-10.

4. The resin composition according to claim 3, characterized in that Also includes any one or more of the following features: B1) the resin composition further comprises one or more of a retarder, an initiator, a curing accelerator, a flame retardant, and an inorganic additive; B2) The mass ratio of the structure represented by formula (1-1) to the structure represented by formula (1-2) is (50 to 70):(30 to 50).

5. A resin mixture, characterized in that: The resin mixture comprises a resin having a structure represented by formula (1) as described in any one of claims 1 to 2 or a resin composition as described in any one of claims 3 to 4 and at least one other resin, wherein the other resin is selected from resins that react with the resin having a structure represented by formula (1) or the resin composition.

6. The resin mixture according to claim 5, characterized in that The other resin is an ethylenically unsaturated bond-containing resin.

7. The resin mixture according to claim 6, characterized in that 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 having the structure represented by the formula (1) to the resin containing ethylenically unsaturated bonds is 100:0.1-100:500; C3) The mass ratio of the resin composition to the resin containing ethylenically unsaturated bonds is 100:0.1-100:

500.

8. The resin mixture according to claim 7, characterized in that 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.

9. The resin mixture according to claim 8, characterized in that 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.

10. Use of the resin according to any one of claims 1 to 2, the resin composition according to any one of claims 3 to 4 and / or the resin mixture according to any one of claims 5 to 9 in prepregs, circuit boards and laminated films.

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