Resin composition, prepreg and printed circuit board

Abstract

The invention belongs to the field of high polymer materials, and particularly relates to a resin composition, a prepreg and a printed circuit board. The resin composition provided by the invention is prepared from the following components: 40 to 80 parts of prepolymer, 10 to 50 parts of curing agent, 30 to 70 parts of epoxy resin, 1 to 10 parts of imidazole compound and 50 to 150 parts of filler, wherein the prepolymer is prepared from the following raw materials: maleimide resin and a fluorenyl compound containing amino groups; the maleimide resin comprises one or more of compounds with a structure as shown in a formula (I); the fluorenyl compound containing the amino group comprises one or more of compounds with a structure as shown in a formula (II). According to the resin composition provided by the invention, the maleimide resin modified prepolymer is selected and has good compatibility with epoxy resin, so that the addition of filler can be effectively reduced, and further the processability of the resin composition can be ensured; and the resin composition provided by the invention has excellent heat resistance.

Description

Technical Field

[0001] The present application belongs to the field of polymer materials, and specifically relates to a resin composition, a prepreg, and a printed circuit board. Background Art

[0002] In recent years, the diversification, multi-functionality, portability, and thinness of electronic products have become the goals pursued by electronic products. Printed Circuit Board (PCB) is the core component of electronic products. It completes the electrical connection of electronic products by printing or etching metal conductive paths on insulating substrates and soldering electronic components. Copper clad laminate, which is the substrate of printed circuit boards, also requires excellent thermal stability to meet the impedance design and thermal shock during the processing of printed circuit boards.

[0003] The resin composition plays a decisive role in the performance of copper clad laminates. The resin composition is mostly prepared by dielectric materials based on epoxy resin. However, the resin composition including epoxy resin has insufficient heat resistance and a high thermal expansion coefficient, and then there is a problem that the circuit board is prone to warping. At present, in order to reduce the thermal expansion system of the resin composition, a large amount of inorganic fillers with low thermal expansion coefficients are usually added. Although the thermal expansion coefficient of the composition can be significantly reduced in this way, the negative effects brought about cannot be ignored, such as excessive viscosity of the resin composition, which causes the processing performance to deteriorate significantly. Summary of the invention

[0004] Based on this, the present application provides a resin composition, a prepreg, and a printed circuit board. The resin composition provided in the present application uses a prepolymer modified by a maleimide resin, which has good compatibility with an epoxy resin, can achieve excellent heat resistance, can effectively reduce the addition of fillers, and thus can ensure its processing performance.

[0005] In a first aspect of the present application, a resin composition is provided, comprising the following components:

[0006] Prepolymer 40~80 parts,

[0007] 10~50 parts of curing agent,

[0008] Epoxy resin 30~70 parts,

[0009] 1 to 10 parts of an imidazole compound, and

[0010] Filler 50~120 parts;

[0011] Wherein, the raw materials for preparing the prepolymer include maleimide resin and amino-containing fluorene-based compound;

[0012] The maleimide resin includes one or more compounds having the structure shown in formula (I);

[0013] In formula (I), Ar1 and Ar2 are each independently absent, , unsubstituted or substituted with at least one R´ 20 Arylene, and at least one of Ar1 and Ar2 is , unsubstituted or substituted with at least one R´ 20 Arylene; L1 is absent, -O-, C1~C6 alkylene, C1~C6 haloalkylene, C6~C 20 Aromatic group, , , , or , L 11 , L 12 , L 13 , L 14 and L 15 Each is independently unsubstituted or substituted with at least one R'C6~C 20 Aromatic group, A is C1~C6 alkylene; R', when it appears each time, is independently halogen or C1~C3 alkylene; q is any integer from 1 to 6;

[0014] The amino-containing fluorenyl compound includes one or more compounds having the structure shown in formula (II);

[0015] In formula (II), each occurrence of Cy is independently C6~C 20 aromatic group; each occurrence of R1 is independently H, halogen, amino, C1~C6 alkyl, C1~C6 haloalkyl or C6~C 20 Aromatic group; n is any integer from 0 to 3.

[0016] In one embodiment, the raw materials for preparing the prepolymer further include unsaturated phenolic compounds; the unsaturated phenolic compounds have one or more of the following characteristics:

[0017] (1) The unsaturated phenolic compound includes one or more compounds having the structure represented by formula (III);

[0018] , in formula (III), X is selected from -CH2-, -C(CH3)2- or S(=O)2, and R2, when it appears each time, is independently C2~C6 alkenyl or C2~C6 alkynyl;

[0019] (2) The mass ratio of the unsaturated phenol compound to the maleimide resin is (0.5-1.5):4.

[0020] In one embodiment, the maleimide resin comprises , , , , and One or more of; R', when it appears each time, is independently halogen or C1~C3 alkylene; m is any integer from 0 to 4.

[0021] In one embodiment, the amino-containing fluorenyl compound comprises , and One or more of; R1, when it appears each time, is independently H, amino or C1~C3 alkyl; n is any integer from 0 to 3.

[0022] In one embodiment, the prepolymer has one or more of the following characteristics:

[0023] (1) The mass ratio of the maleimide resin to the amino-containing fluorenyl compound is (1-4):4;

[0024] (2) The preparation step of the prepolymer includes: heating the amino-containing fluorenyl compound to a molten state, then adding other preparation raw materials, and causing a polymerization reaction at a polymerization temperature to prepare the prepolymer; optionally, the polymerization temperature is 100°C to 180°C.

[0025] In one embodiment, the imidazole compound includes one or more compounds having the structure shown in formula (IV); , in formula (IV), R3 is a C1~C6 alkyl group.

[0026] In one embodiment, the resin composition has one or more of the following characteristics:

[0027] (1) The curing agent includes one or more of a cyanate resin and a benzoxazine resin;

[0028] (2) The epoxy resin includes one or more of naphthalene epoxy resin, bisphenol A epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber-modified epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, anthracene epoxy resin and silicone-modified epoxy resin;

[0029] (3) In the resin composition, the mass percentage of the filler is 30% to 42%.

[0030] In one embodiment, the resin composition further comprises a functional additive;

[0031] Optionally, the functional additive is 1 to 5 parts by weight; the functional additive includes one or more of a dispersant, a leveling agent, a defoaming agent and a coupling agent.

[0032] A second aspect of the present application provides a prepreg, comprising a reinforcing material and a resin layer supported on the surface of the reinforcing material, wherein the resin layer is formed by drying the resin composition described in any one of the embodiments of the first aspect of the present application.

[0033] A third aspect of the present application provides a printed circuit board, wherein the printed circuit board comprises the prepreg described in the second aspect of the present application.

[0034] The resin composition provided in this application has at least the following beneficial effects:

[0035] In the resin composition provided by the present application, the raw materials for preparing the prepolymer include maleimide resin and fluorenyl compounds containing amino groups, and the maleimide ring in the maleimide resin has high bond energy and stability, and it can produce a steric hindrance effect at the same time, hindering the excessive proximity and interaction of the molecular chain, so as to limit the free movement of the molecular chain and reduce the problem of decreased heat resistance caused by the movement of the molecular chain. In the fluorenyl compound containing amino groups, the fluorenyl group has a rigid planar structure of a larger conjugated system, which can effectively prevent the movement of the molecular chain at high temperatures. Furthermore, the amino group can react with the maleimide group in the maleimide resin to form a cross-linked structure, and the tight cross-linked network can effectively resist the thermal motion of the molecular chain, thereby reducing the thermal expansion coefficient.

[0036] Furthermore, under the coordinated action of the curing agent, epoxy resin and imidazole compound, the resin composition of the present application can form a highly cross-linked network structure during the curing process, which is beneficial to improving the thermal stability of the material, and also helps to maintain a low thermal expansion coefficient, so that the resin composition can have excellent heat resistance by adding a lower content of filler. DETAILED DESCRIPTION

[0037] The resin combination, prepreg and printed circuit board of the present application are further described in detail below in conjunction with specific embodiments. The application can be realized in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the application more thorough and comprehensive. Of course, they are merely examples, and the purpose is not to limit the application.

[0038] When a numerical range is disclosed herein, the above range is considered to be continuous and includes the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0039] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application. Unless otherwise specified or there is a contradiction, the terms or phrases used herein have the following meanings:

[0040] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0041] In the present application, the percentage content, unless otherwise specified, refers to mass percentage for solid-liquid mixing and solid-solid mixing, and volume percentage for liquid-liquid mixing.

[0042] In this application, when it comes to percentage concentration, unless otherwise specified, it refers to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of the component.

[0043] In the present application, "*" indicates a connection site.

[0044] In the present application, when a linking site is not specified in a group, it means that an optional linking site in the group can be used as a linking site.

[0045] In the present application, the single bond to which the substituent is connected runs through the corresponding ring, indicating that the substituent can be connected to any position of the ring, for example R is connected to any substitutable position of the benzene ring.

[0046] In the present application, "absence" means that the group is not contained and other adjacent groups are directly bonded. For example, When Ar1 is absent, formula (I) is .

[0047] In the present application, "aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom. It can be a monocyclic aromatic group, a condensed aromatic group, or a polycyclic aromatic group. For polycyclic rings, at least one is an aromatic ring system. Phrases containing this term, for example, "C6~C 20"Aryl" refers to an aromatic group containing 6 to 20 carbon atoms, each occurrence of which can be independently C6 aromatic, C 10 Aryl, C 14 Aryl, C 18 Aryl, C 20 Suitable examples include, but are not limited to, benzene, biphenyl, naphthalene, anthracene, phenanthrene, perylene, triphenylene, and derivatives thereof.

[0048] In the present application, "aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic group by removing a hydrogen atom.

[0049] In the present application, "alkyl" refers to a saturated hydrocarbon group containing a primary (normal) carbon atom, or a secondary carbon atom, or a tertiary carbon atom, or a quaternary carbon atom, or a combination thereof. Phrases containing this term, for example, "C1~C6 alkyl" refers to an alkyl group containing 1 to 6 carbon atoms, and each time it appears, it can be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl. Suitable examples include, but are not limited to: methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-propyl, n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-butyl, n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(C H3)CH2CH3), tert-butyl (1,1-dimethylethyl, 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl, n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2).

[0050] "Alkylene" refers to a hydrocarbon group with two monovalent radical centers derived from an alkyl group by removing a hydrogen atom, which can be a saturated branched alkyl group or a saturated straight-chain alkyl group. For example, "C1-C6 alkylene" means that the alkyl part contains 1 to 6 carbon atoms, and each time it appears, it can be independently C1 alkylene, C4 alkylene, C5 alkylene, C6 alkylene. Suitable examples include, but are not limited to: methylene (-CH2-), 1,1-ethyl (-CH(CH3)-), 1,2-ethyl (-CH2CH2-), 1,1-propyl (-CH(CH2CH3)-), 1,2-propyl (-CH2CH(CH3)-), 1,3-propyl (-CH2CH2CH2-) and 1,4-butyl (-CH2CH2CH2CH2-).

[0051] In the present application, "halogen" refers to F, Cl, Br or I.

[0052] In the present application, "haloalkyl" refers to a group formed by replacing hydrogen atoms with halogen atoms on the basis of an alkyl group. For example, "C1-C6 haloalkyl" includes but is not limited to CH2F, -CF2CF3 or -CF2CF2CF3.

[0053] In the present application, "haloalkylene" refers to a group formed by replacing hydrogen atoms with halogen atoms on the basis of haloalkyl. For example, "C1-C6 haloalkylene" includes but is not limited to -CHF, -CF2CF2- or -CF2CF2CF2-.

[0054] In the present application, "alkenyl" refers to a group containing at least one unsaturated site, i.e., a carbon-carbon sp 2 A hydrocarbon of a positive carbon atom, a secondary carbon atom, a tertiary carbon atom or a ring carbon atom of a double bond. A phrase comprising the term, for example, "C2~C6 alkenyl" refers to an alkenyl group comprising 2 to 6 carbon atoms, and each occurrence may be independently of each other C2 alkenyl, C3 alkenyl, C4 alkenyl, C5 alkenyl, C6 alkenyl. Suitable examples include, but are not limited to, vinyl (-CH=CH2), allyl (-CH2CH=CH2), cyclopentenyl (-C5H7) and 5-hexenyl (-CH2CH2CH2CH2CH=CH2).

[0055] In the present application, "alkynyl" refers to a hydrocarbon containing a positive carbon atom, a secondary carbon atom, a tertiary carbon atom or a ring carbon atom having at least one unsaturated site, i.e., a carbon-carbon sp triple bond. Phrases containing this term, for example, "C2~C6 alkynyl" refers to an alkynyl containing 2 to 6 carbon atoms, and each occurrence may be independently C2 alkynyl, C3 alkynyl, C4 alkynyl, C5 alkynyl, C6 alkynyl. Suitable examples include, but are not limited to, ethynyl (-C≡CH) and propargyl (-CH2C≡CH).

[0056] In a first aspect of the present application, a resin composition is provided, comprising the following components:

[0057] Prepolymer 40~80 parts,

[0058] 10~50 parts of curing agent,

[0059] Epoxy resin 30~70 parts,

[0060] 1 to 10 parts of an imidazole compound; and

[0061] 50~120 parts of filler.

[0062] Wherein, the raw materials for preparing the prepolymer include maleimide resin and fluorenyl compounds containing amino groups. The maleimide ring in the maleimide resin has a high bond energy and stability, and it can produce a steric hindrance effect at the same time, hindering the molecular chain from being too close and interacting, so as to limit the free movement of the molecular chain and reduce the problem of reduced heat resistance caused by the movement of the molecular chain. In the fluorenyl compound containing amino groups, the fluorenyl group has a rigid planar structure of a larger conjugated system, and the amino group can participate in the formation of intramolecular or intermolecular hydrogen bonds to enhance the intermolecular interaction and improve the heat resistance of the resin composition. In addition, the amino group, as a reactive site, can also react chemically with functional groups in other resins such as maleimide groups, and adjust the crosslinking density and curing reaction rate. It is understandable that the weight proportion of the prepolymer can be selected from any value between 40 parts and 80 parts. For example, the weight proportions of the prepolymer include but are not limited to 40 parts, 43 parts, 45 parts, 48 ​​parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 75 parts, 78 parts or 80 parts, or in a range consisting of any two of the above point values ​​as endpoint values.

[0063] Curing agent can form a highly cross-linked network structure during curing to further enhance the heat resistance of resin combination.It is understandable that the weight parts of curing agent can be selected from any numerical value between 10 parts to 50 parts.Illustratively, the weight parts of curing agent include but are not limited to 10 parts, 13 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 ​​parts or 50 parts, or any two of the above-mentioned points are used as the scope of the endpoint value.

[0064] The epoxy resin and other components cooperate with each other. During the curing process, the molecular chains of the epoxy resin cross-link with other resin molecules to form a stable three-dimensional network structure to improve the overall heat resistance of the resin composition. For example, the weight percentage of the epoxy resin includes but is not limited to 30 parts, 33 parts, 35 parts, 38 parts, 40 parts, 43 parts, 45 parts, 48 ​​parts, 50 parts, 53 parts, 55 parts, 58 parts, 60 parts, 63 parts, 65 parts, 68 parts or 70 parts, or any two of the above points are used as endpoint values.

[0065] Imidazole compounds can catalyze the cross-linking reaction between resin molecules, making the curing process more complete and uniform, and ensuring that the resin composition forms a more complete cross-linked structure after curing. In this application, the weight parts of imidazole compounds include but are not limited to 1 part, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, or any two of the above points are used as the range of endpoint values.

[0066] It is understandable that the weight percentage of the filler can be selected from any value between 50 and 120. For example, the weight percentage of the filler includes but is not limited to 50, 60, 70, 80, 90, 100, 110 or 120 parts, or a range formed by any two of the above points as endpoints.

[0067] In one example, the filler includes one or more of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, eucryptite, silica, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay and kaolin.

[0068] The resin composition provided in the present application, under the coordinated action of the prepolymer, curing agent, epoxy resin and imidazole compound, enables the resin composition of the present application to form a highly cross-linked network structure during the curing process, which is beneficial to improving the thermal stability of the material and reducing the thermal stability of the resin composition.

[0069] In one example, the maleimide resin includes one or more compounds having the structure shown in formula (I);

[0070] .

[0071] In formula (I), Ar1 and Ar2 are each independently absent, , unsubstituted or substituted with at least one R´ 20 Arylene, and at least one of Ar1 and Ar2 is , unsubstituted or substituted with at least one R´20 R' is independently halogen or C1-C3 alkylene. q is any integer from 1 to 6. q is 1, 2, 3, 4, 5 or 6.

[0072] For example, Ar1 and Ar2 are each independently , , , , , , , or Each occurrence of R' is independently halogen, methyl or ethyl.

[0073] L1 is absent, -O-, C1~C6 alkylene, C1~C6 haloalkylene, C6~C 20 Aromatic group, , , , or .L 11 , L 12 , L 13 , L 14 and L 15 Each is independently unsubstituted or substituted with at least one R'C6~C 20 A is an aromatic group, A is a C1~C6 alkylene group. R', when it appears each time, is independently a halogen or a C1~C3 alkylene group.

[0074] Furthermore, L1 is absent, -O-, methyl, ethyl, propyl, C6~C 20 Aromatic group, or .L 14 and L 15 Each is independently unsubstituted or substituted with at least one R'C6~C 20 A is an aromatic group, A is a C1~C3 alkylene group. R', when it appears each time, is independently a halogen or a C1~C3 alkylene group.

[0075] Furthermore, L1 is absent, -O-, methyl, ethyl, propyl or , , , , , , , , or A is C1~C3 alkylene. R', when it appears each time, is independently halogen or C1~C3 alkylene.

[0076] In one example, the maleimide resin includes , , , , and One or more of; R', when it appears each time, is independently halogen or C1~C3 alkylene; m is any integer from 0 to 4.

[0077] Furthermore, the maleimide resin includes N,N'-m-phenylene bismaleimide , bis(4-maleimidophenyl)methane , 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane , bis(3,5-dimethyl-4-maleimidophenyl)methane , bis(3-ethyl-5-methyl-4-maleimidophenyl)methane , Di(3,5-diethyl-4-maleimidophenyl)methane and phosphorus-containing bismaleimide One or more of .

[0078] The maleimide has multiple maleimide groups, which can provide more reaction sites during the curing process to chemically react with epoxy resin, curing agent, etc. to form more cross-linking points to improve the heat resistance of the resin composition.

[0079] In one example, the amino-containing fluorenyl compound includes one or more compounds having a structure represented by formula (II);

[0080] In formula (II), each occurrence of Cy is independently C6~C 20 Aromatic group.

[0081] Furthermore, each time Cy appears, it is independently , , or .

[0082] Each occurrence of R1 is independently H, halogen, amino, C1~C6 alkyl, C1~C6 haloalkyl or C6~C 20 Aromatic group. n is any integer from 0 to 3. n is 0, 1, 2 or 3.

[0083] In one example, the amino-containing fluorenyl compound includes , and One or more of. Each time R1 appears, it is independently H, amino or C1-C3 alkyl; n is any integer from 0 to 3. Further, each time R1 appears, it is independently H, methyl or ethyl.

[0084] Furthermore, the amino-containing fluorenyl compound includes , , and One or more of .

[0085] In the above-mentioned amino-containing fluorenyl compound, the π electrons are delocalized and distributed throughout the fluorenyl structure, which forms a relatively stable electron cloud structure. When it is affected by high temperature, higher energy is required to destroy this stable electron cloud structure and chemical bonds, so that the amino-containing fluorenyl compound exhibits good thermal stability. Furthermore, the presence of the amino group can not only cross-link with active groups such as maleimide to increase the cross-linking density, but also enable the amino group to form intermolecular hydrogen bonds between the compounds, which helps to enhance the intermolecular interaction force and make the molecular chains more tightly bound. Furthermore, in a high temperature environment, it can prevent the softening or decomposition of the material caused by excessive movement of the molecular chains, further improving the heat resistance of the resin composition.

[0086] In one example, the raw materials for preparing the prepolymer also include unsaturated phenolic compounds.

[0087] Unsaturated phenol compounds can participate in cross-linking reactions during polymerization to form a more complex and stable network structure, which prevents the sliding and breaking of molecular chains at high temperatures and further enhances the heat resistance of the material. At the same time, the benzene ring structure in the phenol compounds also has a certain thermal stability, which can maintain the physical and chemical properties of the material under high temperature conditions. Further, functional groups such as phenolic hydroxyl groups can adjust the charge distribution within the molecule, reduce the energy loss of the material under the action of an electric field, improve the electrical insulation performance of the material, and meet the needs of electronic devices with higher dielectric properties.

[0088] In one example, the unsaturated phenolic compound includes one or more compounds having a structure represented by formula (III);

[0089] In formula (III), X is selected from -CH2-, -C(CH3)2- or S(=O)2, and each occurrence of R2 is independently C2~C6 alkenyl or C2~C6 alkynyl.

[0090] Furthermore, the unsaturated phenol compound includes one or more of diallyl bisphenol A, diallyl bisphenol S, diallyl bisphenol F and bisphenol A bisallyl ether.

[0091] For example, the unsaturated phenolic compound includes , , and One or more of .

[0092] The cyclic structure of the maleimide resin itself provides a good basis for thermal stability, and the unsaturated bonds in the unsaturated phenolic compound can undergo a cross-linking reaction with the maleimide resin. This cross-linking structure can limit the movement of the molecular chain under high temperature conditions, preventing the material from softening, deforming or decomposing due to the thermal movement of the molecular chain, thereby significantly improving the heat resistance of the material. In one example, the mass ratio of the unsaturated phenolic compound to the maleimide resin is (0.5~1.5):4. For example, the mass ratio of the unsaturated phenolic compound to the maleimide resin includes but is not limited to 0.5:4, 0.8:4, 0.9:4, 1:4, 1.1:4, 1.3:4 or 1.5:4, or within the range consisting of any two of the above point values ​​as endpoint values.

[0093] In one example, the mass ratio of the maleimide resin to the amino-containing fluorenyl compound is (1-4):4. The mass ratio of the maleimide resin to the amino-containing fluorenyl compound is limited, and the cooperation between the two can effectively resist the molecular chain movement and decomposition caused by high temperature; at the same time, it helps to optimize the cohesive energy and stress distribution and improve the heat resistance. For example, the mass ratio of the maleimide resin to the amino-containing fluorenyl compound includes but is not limited to 0.5:4, 0.8:4, 0.9:4, 1:4, 1.1:4, 1.3:4 or 1.5:4, or within the range formed by any two of the above point values ​​as endpoint values.

[0094] In one example, the step of preparing the prepolymer includes: subjecting the raw materials to a polymerization reaction at a polymerization temperature to prepare the prepolymer.

[0095] In one example, the polymerization temperature is 100°C to 180°C. The polymerization reaction temperature is between 100°C and 180°C, which effectively improves production efficiency, helps control the molecular weight and distribution of the prepolymer to balance material properties, and reduces side reactions. For example, the polymerization temperature includes but is not limited to 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C or 180°C, or any two of the above point values ​​as endpoint values.

[0096] In one example, the process parameters of the polymerization further include: a polymerization time of 60 min to 200 min. For example, the polymerization time includes but is not limited to 60 min, 70 min, 80 min, 90 min, 100 min, 120 min, 140 min, 160 min, 180 min or 200 min, or a range formed by any two of the above point values ​​as endpoint values.

[0097] Furthermore, the preparation step of the prepolymer includes: heating the amino-containing fluorenyl compound to a molten state, adding maleimide resin according to a mass ratio, polymerizing at 100°C to 180°C for 60min to 200min, and cooling to room temperature to prepare the prepolymer.

[0098] Furthermore, the preparation step of the prepolymer includes: heating the amino-containing fluorenyl compound and the unsaturated phenol compound to a molten state, adding maleimide resin according to a mass ratio, polymerizing at 100°C to 180°C for 60min to 200min, and cooling to room temperature to prepare the prepolymer.

[0099] The present application adopts a melting method to prepare a prepolymer, and the method does not need to add an additional organic solvent, avoids the addition of a solvent in a solvent method and a subsequent complicated removal process, and the operation is simpler and more efficient. At the same time, since the method does not need to consider the recovery of the solvent, it has a good process preparation advantage. In addition, since there is no interference from the solvent in the melting method, bismaleimide and the amino-containing fluorenyl compound can be better chemically bonded, thereby optimizing the chemical structure of the prepolymer, making the chemical bonds inside the resin composition more stable, and in a high temperature environment, the possibility of chemical bond fracture is reduced, so that the resin composition exhibits a more excellent heat resistance.

[0100] In one example, the imidazole compound includes one or more compounds having the structure shown in formula (IV); In formula (IV), R3 is a C1~C6 alkyl group.

[0101] In one example, the imidazole compound includes , , and One or more of .

[0102] In one example, the curing agent includes one or more of a cyanate resin and a benzoxazine resin.

[0103] In one example, the cyanate resin includes one or more of bisphenol A type cyanate resin, phenol formaldehyde type cyanate resin, bisphenol F type cyanate resin, bisphenol M type cyanate resin, bisphenol E type cyanate resin, naphthalene type cyanate resin, biphenyl type cyanate resin, phosphorus-containing structure cyanate resin, bisphenol S type cyanate resin and dicyclopentadiene bisphenol type cyanate resin.

[0104] In one example, the benzoxazine resin includes one or more of an allyl benzoxazine resin, a bisphenol A benzoxazine resin, a bisphenol F benzoxazine resin, a main chain benzoxazine resin, a phosphorus-containing benzoxazine resin, a bisphenol S benzoxazine resin, a dicyclopentadiene benzoxazine resin, a biphenyl benzoxazine resin, a tetraphenol ethane benzoxazine resin and a naphthalene benzoxazine resin.

[0105] In one example, the epoxy resin includes one or more of naphthalene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol S-type epoxy resin, bisphenol F-type epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, o-cresol-formaldehyde epoxy resin, bisphenol A novolac epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber-modified epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, anthracene-type epoxy resin and silicone-modified epoxy resin.

[0106] Furthermore, the filler is silicon dioxide. Furthermore, the filler is spherical silicon dioxide.

[0107] When silicon dioxide is used as a filler, it can make the resin composition conducive to heat dissipation and can inhibit thermal expansion to ensure chemical stability. At the same time, silicon dioxide can also enhance the mechanical properties and thermal stability of the resin composition. Spherical silicon dioxide has more excellent fluidity and dispersibility, and it has good compatibility with resin matrices such as polyphenylene ether resins, prepolymers, and functional resins, and can effectively avoid the reunion of the resin matrix.

[0108] In one example, in the resin composition, the mass percentage of the filler is 30% to 42%. For example, the mass percentage of the filler includes but is not limited to 30%, 31%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35%, 35.5%, 36%, 37%, 38%, 39%, 40%, 41% or 42%, or any two of the above points as endpoint values.

[0109] In one example, the resin composition further includes a functional additive.

[0110] In one example, the resin composition further comprises 1 to 5 parts of an auxiliary agent by weight. For example, the weight of the auxiliary agent includes but is not limited to 1 part, 2 parts, 3 parts, 4 parts or 5 parts.

[0111] For example, the auxiliary agent includes one or more of a dispersant, a leveling agent, a defoaming agent and a coupling agent.

[0112] In a second aspect of the present application, a semi-cured sheet is provided, comprising a reinforcing material and a resin layer supported on the surface of the reinforcing material, wherein the resin layer is formed by drying the resin composition described in any example of the first aspect of the present application.

[0113] The present application also provides a method for preparing a prepreg, comprising the following steps:

[0114] Mixing the components of the resin composition in a solvent to prepare a coating liquid;

[0115] The coating liquid is applied to the surface of the substrate and a first heating treatment is performed to prepare the prepreg.

[0116] It is understandable that the present application does not limit the method of mixing the components in the solvent, as long as the method can be used to mix the components. For example, the components that can be dissolved in the organic solvent can be first put into the organic solvent to completely dissolve, and heating can be performed as needed; then the components that are insoluble in the organic solvent, such as flame retardants and inorganic fillers, are added and stirred and mixed using a ball mill, a bead mill, a planetary mixer, a roller mill, etc.

[0117] The present application does not limit the manner in which the coating liquid is loaded on the substrate. Examples include impregnation, coating, and spraying. In addition, as a method for manufacturing a prepreg, the method includes drying and heating the resin composition after loading it on the substrate. In addition, the impregnation, coating, and spraying steps in the present application may be repeated multiple times as needed. In addition, multiple thermosetting resin compositions with different compositions and solid contents may be used for repeated impregnation to adjust the final composition and glue content.

[0118] In one example, the process parameters of the first heating treatment include: a heating temperature of 100° C. to 200° C. For example, the heating temperature includes but is not limited to 100° C., 120° C., 150° C., 180° C. or 200° C., or a range formed by any two of the above point values ​​as endpoint values.

[0119] In one example, the process parameters of the first heating treatment further include: a heating time of 2 min to 20 min. For example, the heating time includes but is not limited to 2 min, 5 min, 10 min, 15 min, 18 min or 20 min, or a range formed by any two of the above point values ​​as endpoint values.

[0120] In one example, the substrate includes one or more of an inorganic fiber material and an organic fiber material. For example, the inorganic fiber material includes one or more of glass fiber, carbon fiber, silicon carbide fiber and asbestos fiber. The organic fiber material includes one or more of nylon, ultra-high molecular weight polyethylene fiber, aramid fiber, polyimide fiber, polyester fiber and cotton fiber.

[0121] The present application also provides an application of a prepreg in the preparation of a laminate, a copper-clad laminate or a wiring board.

[0122] The present application also provides a laminate, which includes the prepreg described in the above embodiment.

[0123] The present application also provides a method for preparing a laminate, comprising the following steps:

[0124] One or more prepregs are selected and laminated to prepare the laminate.

[0125] In one example, the lamination process parameters include: the temperature is set to 150℃~300℃, the pressure is set to 10 kgf / cm 2 ~40kgf / cm 2 , vacuum degree <2kPa, hot pressing forming 200min~400min.

[0126] The present application also provides a copper clad laminate, which includes the prepreg described in the above embodiment and a metal foil covering one side or both sides of the laminated prepreg.

[0127] In one example, the thickness of the metal foil is 3 μm to 105 μm.

[0128] A third aspect of the present application provides a printed circuit board, wherein the printed circuit board comprises the prepreg described in the second aspect of the present application.

[0129] In order to make the purpose and advantages of the present invention clearer, the present application is further described in detail below in conjunction with specific examples. It should be understood that the specific examples described herein are only used to explain the present invention and shall not be used to limit the present invention. The following examples do not include other components except inevitable impurities unless otherwise specified. The drugs and instruments used in the examples are conventionally selected in the art unless otherwise specified. The experimental methods for which specific conditions are not specified in the examples are implemented according to conventional conditions, such as the conditions described in the literature, books, or the methods recommended by the manufacturer.

[0130] The raw materials used in the following examples and comparative examples are as follows:

[0131] [Amino group-containing fluorenyl compounds]

[0132] Amino-containing fluorenyl compound A, structure ;CAS: 15499-84-0; Purchased from: Tianjin Zotye.

[0133] [Maleimide resin]

[0134] Bismaleimide resin, structure , purchased from: Yamato Chemical Industry, model: BMI-2300.

[0135] [Unsaturated phenolic compounds]

[0136] Diallyl bisphenol A was purchased from Honghu Shuangma Resin Factory.

[0137] [Epoxy resin]

[0138] Naphthalene epoxy resin, purchased from Nippon Kayaku, model NC-7000H.

[0139] [Curing agent]

[0140] Bisphenol A cyanate was purchased from Lonza Group, model BA-3000S.

[0141] [Functional resin]

[0142] Polyphenylene ether resin: purchased from Sabic, model number SA-9000.

[0143] [filler]

[0144] Spherical silica, purchased from Yaduma, model number is SO-C4.

[0145] [Imidazole compounds]

[0146] 2-Methylimidazole, purchased from Shikoku Chemical Co., Ltd.

[0147] [Additives]

[0148] Dispersant, purchased from BYK Chemicals, model defoamer BYK-1650.

[0149] Preparation Example 1

[0150] 50 parts of amino-containing fluorenyl compound A were heated to a molten state, and then 100 parts of bismaleimide resin were added, and the mixture was prepolymerized at 150° C. for 90 minutes and then cooled to room temperature to prepare a modified maleimide prepolymer A.

[0151] Preparation Example 2

[0152] 75 parts of the amino-containing fluorenyl compound A were heated to a molten state, and then 100 parts of the bismaleimide resin were added, and the mixture was prepolymerized at 150° C. for 120 minutes and then cooled to room temperature to prepare a modified maleimide prepolymer B.

[0153] Preparation Example 3

[0154] 100 parts of the amino-containing fluorenyl compound A were heated to a molten state, and then 100 parts of the bismaleimide resin were added, and the mixture was prepolymerized at 160° C. for 100 minutes and then cooled to room temperature to prepare a modified maleimide prepolymer C.

[0155] Preparation Example 4

[0156] First, 50 parts of amino-containing fluorenyl compound A and 25 parts of allyl bisphenol A were heated to a molten state, and then 100 parts of bismaleimide resin were added, and the mixture was prepolymerized at 160° C. for 120 minutes and then cooled to room temperature to prepare a modified maleimide prepolymer D.

[0157] Preparation Example 5

[0158] 75 parts of allyl bisphenol A were heated to a molten state, and then 100 parts of bismaleimide resin were added, and the mixture was prepolymerized at 150° C. for 130 minutes and then cooled to room temperature to prepare a modified maleimide prepolymer E.

[0159] The compositions of the resin compositions provided in the examples and comparative examples are shown in Tables 1 and 2 below:

[0160] Table 1

[0161]

[0162] Table 2

[0163]

[0164] The preparation process of the resin composition of the embodiment and the comparative example is as follows:

[0165] The modified maleimide prepolymer or maleimide resin and other resins are mixed in a solvent, wherein the solvent includes butanone, cyclohexanone and propylene glycol methyl ether in a mass ratio of 3:2:1; fillers, imidazole compounds and additives are added under stirring conditions, and stirring is continued to prepare a resin composition.

[0166] The preparation process of the prepregs of the embodiments and comparative examples is as follows:

[0167] After impregnating the 2116 type glass fiber cloth with the resin composition prepared in the above examples and comparative examples, the cloth was placed in a hot air circulation oven, the temperature was set to 165° C., and heated for 6 minutes to prepare a prepreg.

[0168] The preparation process of the copper clad laminate of the embodiment and the comparative example is as follows:

[0169] Eight prepregs prepared in each embodiment and comparative example were stacked, and a 18 μm electrolytic copper foil was placed on each side. Then, the prepregs were placed in a programmable temperature and pressure controlled vacuum press. Under vacuum, the pressure was 20 kgf / cm 2 The process was heated and pressed at 180°C for 1 hour, and then heated and pressed at 220°C for 2 hours to obtain a copper-clad laminate with a thickness of about 0.85 mm.

[0170] Performance Tests of Copper-Clad Laminates of Examples and Comparative Examples

[0171] 1. Compatibility of resin composition: After the resin composition is left to stand for 24 hours, visually observe whether there is stratification. If there is no stratification, mark it as "OK", if there is stratification, mark it as "precipitation".

[0172] 2. Peel strength: Tested using a universal tensile testing machine in accordance with IPC-TM-650 2.4.8.

[0173] 3. Glass transition temperature (Tg): The glass transition temperature (Tg) was measured using a dynamic mechanical analyzer (DMA850 manufactured by TA Instruments); its test specification used the IPC-TM650 2.4.25D test method.

[0174] 4. Thermal expansion coefficient test and expansion rate in X / Y / Z axis direction: tested according to IPC-TM650 2.4.24.

[0175] 5. Flame retardant performance measurement: Tested according to IPC-TM650 2.3.10.

[0176] The test results of the copper-clad laminates of the above embodiments and comparative examples are shown in Tables 3 and 4 below:

[0177] Table 3

[0178]

[0179] Table 4

[0180]

[0181] As shown in Tables 3 and 4, Comparative Example 1 only uses bismaleimide resin modified with allyl bisphenol A, which has a high thermal expansion coefficient, poor flame retardant properties, and poor heat resistance. Unmodified bismaleimide resin is used in Comparative Example 2, and the content of prepolymer in Comparative Example 3 is high, both of which lead to an increase in the thermal expansion coefficient and poor heat resistance. Comparative Example 4 is basically the same as Example 1, with the main difference being that Comparative Example 4 only uses polyphenylene ether resin, and its heat resistance and flame retardant properties are both poorer than those of Example 1. Comparative Example 5 only includes epoxy resin and does not include cyanate resin, resulting in a high thermal expansion coefficient and poor heat resistance in Comparative Example 5.

[0182] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0183] The above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solution of the present application in detail, but it cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several variations and improvements can be made, which all belong to the protection scope of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the protection scope of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the content of the attached claims, and the description can be used to interpret the content of the claims.

Claims

1. A resin composition, characterized in that Includes the following components: Prepolymer 40~80 parts, 10~50 parts of curing agent, Epoxy resin 30~70 parts, 1 to 10 parts of an imidazole compound, and Filler 50~120 parts; Wherein, the raw materials for preparing the prepolymer include maleimide resin and amino-containing fluorene-based compound; The maleimide resin includes one or more compounds having the structure shown in formula (I); In formula (I), Ar1 and Ar2 are each independently absent, , unsubstituted or substituted with at least one R´ 20 Arylene, and at least one of Ar1 and Ar2 is , unsubstituted or substituted with at least one R´ 20 Arylene; L1 is absent, -O-, C1~C6 alkylene, C1~C6 haloalkylene, C6~C 20 Aromatic group, , , , or , L 11 , L 12 , L 13 , L 14 and L 15 Each is independently unsubstituted or substituted with at least one R'C6~C 20 Aromatic group, A is C1~C6 alkylene; R', when it appears each time, is independently halogen or C1~C3 alkylene; q is any integer from 1 to 6; The amino-containing fluorenyl compound includes one or more compounds having the structure shown in formula (II); In formula (II), each occurrence of Cy is independently C6~C 20 aromatic group; each occurrence of R1 is independently H, halogen, amino, C1~C6 alkyl, C1~C6 haloalkyl or C6~C 20 Aromatic group; n is any integer from 0 to 3.

2. The resin composition according to claim 1, characterized in that The raw materials for preparing the prepolymer further include unsaturated phenolic compounds; the unsaturated phenolic compounds have one or more of the following characteristics: (1) The unsaturated phenolic compound includes one or more compounds having the structure represented by formula (III); , in formula (III), X is selected from -CH2-, -C(CH3)2- or S(=O)2, and R2, when it appears each time, is independently C2~C6 alkenyl or C2~C6 alkynyl; (2) The mass ratio of the unsaturated phenol compound to the maleimide resin is (0.5-1.5):

4.

3. The resin composition according to claim 1 or 2, characterized in that The maleimide resin comprises , , , , and One or more of; R', when it appears each time, is independently halogen or C1~C3 alkylene; m is any integer from 0 to 4.

4. The resin composition according to claim 1 or 2, characterized in that The amino-containing fluorenyl compound includes , and One or more of; R1, when it appears each time, is independently H, amino or C1~C3 alkyl; n is any integer from 0 to 3.

5. The resin composition according to claim 1 or 2, characterized in that The prepolymer has one or more of the following characteristics: (1) The mass ratio of the maleimide resin to the amino-containing fluorenyl compound is (1-4):4; (2) The step of preparing the prepolymer comprises: heating the amino-containing fluorenyl compound to a molten state, then adding other raw materials, and causing a polymerization reaction at a polymerization temperature to prepare the prepolymer; Optionally, the polymerization temperature is 100°C to 180°C.

6. The resin composition according to claim 1 or 2, characterized in that The imidazole compound includes one or more compounds having the structure shown in formula (IV); , in formula (IV), R3 is a C1~C6 alkyl group.

7. The resin composition according to claim 1 or 2, characterized in that The resin composition has one or more of the following characteristics: (1) The curing agent includes one or more of a cyanate resin and a benzoxazine resin; (2) The epoxy resin includes one or more of naphthalene epoxy resin, bisphenol A epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, unsaturated epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin, resorcinol epoxy resin, rubber-modified epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, anthracene epoxy resin and silicone-modified epoxy resin; (3) In the resin composition, the mass percentage of the filler is 30% to 42%.

8. The resin composition according to claim 1 or 2, characterized in that The resin composition further comprises a functional additive; Optionally, the functional additive is 1 to 5 parts by weight; the functional additive includes one or more of a dispersant, a leveling agent, a defoaming agent and a coupling agent.

9. A prepreg, characterized in that: The invention comprises a reinforcing material and a resin layer supported on the surface of the reinforcing material, wherein the resin layer is formed by drying the resin composition according to any one of claims 1 to 8.

10. A printed circuit board, characterized in that: The printed circuit board comprises the prepreg according to claim 9.

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