Modified maleimide prepolymer, resin composition, prepreg and application thereof

Abstract

The present application relates to the field of polymer materials, and specifically to a modified maleimide prepolymer, a resin composition, a prepreg and its application. The modified maleimide prepolymer of the present application is obtained by polymerizing a maleimide resin and an unsaturated fluorene-based compound; the unsaturated fluorene-based compound includes one or more of the compounds having the structure shown in formula (I); this makes the modified maleimide prepolymer provided by the present application have both excellent heat resistance and low dielectric loss.

Description

Technical Field

[0001] The present application belongs to the field of polymer materials, and specifically relates to a modified maleimide prepolymer, a resin composition, a prepreg and applications thereof. Background Art

[0002] With the rapid development of the information industry, electronic products are developing towards lightweight, miniaturization, high reliability, low cost, multi-function and digitalization. Printed Circuit Board (PCB) is an important electronic component. It forms conductive lines and patterns on an insulating substrate through printing, etching and other processes to provide a carrier for electrical connection for electronic components. Copper clad laminates, which are the base materials of printed circuit boards, require lower thermal expansion coefficients and higher heat resistance to meet the needs of modern production.

[0003] The main resin plays a decisive role in the performance of copper clad laminates. Maleimide resins with maleimide groups as end groups are widely used because of their excellent dielectric properties. However, maleimide resins have shortcomings such as high melting temperature, poor solubility, and high brittleness of cured products, which are manifested in poor impact resistance, low elongation at break, and low fracture toughness. These defects limit their application to a certain extent, making it difficult to meet the requirements of manufacturing thin and multifunctional copper clad laminates.

[0004] In order to broaden the application scope of maleimide resin, the main method at present is to modify maleimide resin. There is a method to polymerize and modify bismaleimide resin and cyanate resin. Although the polymer has a high glass transition temperature and a low thermal expansion coefficient, its dielectric properties (Dk / Df 4.3 / 0.008) are poor. In addition, there is a method to add fluoroketone compounds and xylene to phenol compounds to obtain monomers; then the monomers and allyl bisphenol A are heated to melt, and then diphenylmethane bismaleimide monomer is added to prepare a modified bismaleimide resin prepolymer. Although the modification of maleimide resin by this method effectively reduces its curing temperature and dielectric constant, it limits the crosslinking density and sacrifices the heat resistance of maleimide resin. Therefore, it is difficult for technicians in this field to overcome the problem of obtaining maleimide resin with both excellent heat resistance and low dielectric properties. Summary of the invention

[0005] Based on this, the present application provides a modified maleimide prepolymer, a resin composition, a prepreg and applications thereof. The modified maleimide prepolymer provided in the present application has both excellent heat resistance and low dielectric loss.

[0006] In a first aspect of the present application, a modified maleimide prepolymer is provided, wherein the modified maleimide prepolymer is obtained by polymerizing a maleimide resin and an unsaturated fluorene compound;

[0007] The unsaturated fluorene-based compound includes one or more compounds having the structure shown in formula (I);

[0008] ;

[0009] In formula (I), A 1 and A 2 are independently halogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl or a group represented by formula (II); and A 1 , A 2 At least one of them is a group represented by formula (II); R 11 , R 12 are independently halogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl or C 6 ~C 20 Aromatic group;

[0010] ;

[0011] In formula (II), Cy is C 6 ~C 20 Aromatic group; R 21 Single bond, O, S, C 1 ~C 6 Alkylene or C 1 ~C 6 Haloalkylene; R 22 is absent, halogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl or C 6 ~C 20 Aromatic group; R23 , R 24 Each independently is a single bond, S or C 1 ~C 6 Alkylene; R 25 C 2 ~C 6 Alkenyl or C 2 ~C 6 Alkynyl; n is any integer from 0 to 6.

[0012] In one embodiment, A 1 and A 2 Each is independently a group represented by formula (II); in formula (II), Cy is C 6 ~C 20 Aromatic group, R 21 is a single bond, R 22 is absent, halogen or C 1 ~C 6 Alkyl, R 23 is a single bond or C 1 ~C 3 Alkylene, R 24 is a single bond or C 1 ~C 3 Alkylene, R 25 C 2 ~C 6 Alkenyl or C 2 ~C 6 Alkynyl; n is any integer from 0 to 6.

[0013] In one embodiment, A 1 and A 2 Each independently represents one or more of formula (III-1) to formula (III-10): , , , , , , , , , ; Among them, R 22 is absent, halogen or C 1 ~C 6 Alkyl, R 23 is a single bond or C 1 ~C 3 Alkylene, R 24 is a single bond or C 1 ~C 3 Alkylene, n is any integer from 0 to 4.

[0014] In one embodiment, the modified maleimide prepolymer has one or more of the following characteristics:

[0015] (1) The maleimide resin includes one or more of 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, bis(3,5-diethyl-4-maleimidophenyl)methane, polyphenylmethane bismaleimide, bismaleimide containing a biphenyl structure, bismaleimide containing a phosphorus structure, bismaleimide containing a naphthalene ring structure, bismaleimide containing an anthracene ring structure, and hyperbranched bismaleimide;

[0016] (2) The mass ratio of the maleimide resin to the unsaturated fluorene compound is 1:(0.5-1.2);

[0017] (3) The process parameters of the polymerization include: the polymerization temperature is 100°C~180°C.

[0018] In a second aspect of the present application, a resin composition is provided, comprising the following components in parts by weight:

[0019] 30 to 70 parts of the modified maleimide prepolymer described in any embodiment of the first aspect of the present application, 10 to 40 parts of a functional resin, 20 to 50 parts of a polyphenylene ether resin, 100 to 250 parts of a filler, and 1 to 5 parts of a curing accelerator.

[0020] In one embodiment, the polyphenylene ether resin includes one or more compounds having the structure shown in formula (IV);

[0021]

[0022] R 31 and R 33 are independently halogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 2 ~C 6 Alkenyl or C 2 ~C 6 Alkynyl; q1 is any integer from 0 to 4, q2 is any integer from 0 to 4;

[0023] R 32 Each independently does not exist, or ;

[0024] Y is a single bond or C 1 ~C 6 Alkylene; m1 and m2 are positive integers.

[0025] In one embodiment, the resin composition has one or more of the following characteristics:

[0026] (1) The curing accelerator includes one or more of a tertiary amine accelerator, an imidazole accelerator, a peroxide accelerator, an organic phosphorus accelerator and a transition metal carboxylate accelerator;

[0027] (2) The functional resin includes one or more of cyanate resin, benzoxazine resin, epoxy resin and hydrocarbon resin.

[0028] In one embodiment, the resin composition further comprises 1 to 5 parts of an auxiliary agent by weight, wherein the auxiliary agent comprises one or more of a dispersant, a leveling agent, a defoaming agent and a coupling agent.

[0029] According to a third aspect of the present application, a prepreg is provided, comprising a substrate and a resin composition loaded on the substrate; the resin composition is the resin composition described in any one of the embodiments of the second aspect of the present application.

[0030] The fourth aspect of the present application provides a use of the prepreg described in the third aspect of the present application in the preparation of a laminate, a copper clad laminate or a wiring board.

[0031] The modified maleimide prepolymer provided in the present application has at least the following beneficial effects:

[0032] The modified maleimide prepolymer provided by the present application is obtained by polymerization of maleimide resin and unsaturated fluorenyl compound, wherein the rigid structures such as benzene ring and imide heterocycle in maleimide can provide a stable skeleton structure for the modified maleimide prepolymer after polymerization; the higher chemical bond energy of benzene ring and imide heterocycle in the skeleton structure makes it difficult to break or deform when heated, thereby giving the modified maleimide prepolymer good heat resistance. In the unsaturated fluorenyl compound of specific structure, the aromatic ring in the fluorenyl has a conjugated system, and its electron cloud distribution is relatively uniform, and its polarization degree is low under the action of electric field; in addition, under the synergistic effect of the substituent of the specific structure of the unsaturated fluorenyl compound, it can adjust the dipole moment of the unsaturated fluorenyl compound molecule, reduce the orientation polarization and relaxation polarization of the molecule in the electric field, thereby reducing dielectric loss.

[0033] Therefore, the modified maleimide prepolymer provided in the present application has both excellent heat resistance and low dielectric loss. DETAILED DESCRIPTION

[0034] The modified maleimide prepolymer, resin combination, prepreg and application thereof 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 purpose is not intended to limit the application.

[0035] 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.

[0036] 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:

[0037] 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.

[0038] 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.

[0039] 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.

[0040] In the present application, "*" indicates a connection site.

[0041] 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.

[0042] 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.

[0043] In the present application, "halogen" refers to F, Cl, Br or I.

[0044] In this application, "alkyl" refers to a saturated hydrocarbon group containing primary (normal) carbon atoms, secondary carbon atoms, tertiary carbon atoms, quaternary carbon atoms, or a combination thereof. Phrases containing this term, such as "C 1 ~C 6 "Alkyl" refers to an alkyl group containing 1 to 6 carbon atoms, each occurrence of which can be independently C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Suitable examples include, but are not limited to, methyl (Me, -CH 3 ), ethyl (Et, -CH 2 CH 3 ), 1-propyl (n-propyl, n-Pr, n-propyl, -CH 2 CH 2 CH 3 ), 2-propyl (i-Pr, i-propyl, -CH (CH 3 ) 2 ), 1-butyl (n-butyl, n-Bu, n-butyl, -CH 2 CH 2 CH 2 CH 3 ), 2-methyl-1-propyl (i-Bu, i-butyl, -CH 2 CH(CH 3 ) 2 ), 2-butyl (s-Bu, s-butyl, -CH (CH 3 )CH 2 CH 3 ), tert-butyl (1,1-dimethylethyl, 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH 3 ) 3 ), 1-pentyl (n-pentyl, n-pentyl, -CH 2 CH 2 CH 2 CH 2 CH 3 ), 2-pentyl (-CH(CH 3 )CH 2 CH 2 CH 3 ), 3-pentyl (-CH(CH 2 CH 3 ) 2 ), 2-methyl-2-butyl (-C(CH 3 ) 2 CH 2 CH 3), 3-methyl-2-butyl (-CH(CH 3 )CH(CH 3 ) 2 ).

[0045] In the present application, "haloalkyl" refers to a group formed by replacing hydrogen atoms with halogen atoms on the basis of an alkyl group. 1 ~C 6 "Haloalkyl" includes but is not limited to CH 2 F, -CF 2 CF 3 or -CF 2 CF 2 CF 3 .

[0046] In the present application, "alkenyl" refers to a group containing at least one unsaturated site, i.e., a carbon-carbon sp 2 A hydrocarbon containing a positive, secondary, tertiary, or cyclic carbon atom with a double bond. Phrases containing this term, such as "C 2 ~C 6 "Alkenyl" refers to an alkenyl group containing 2 to 6 carbon atoms, each occurrence of which can be independently C 2 Alkenyl, C 3 Alkenyl, C 4 Alkenyl, C 5 Alkenyl, C 6 Suitable examples include, but are not limited to, vinyl (-CH=CH 2 ), allyl (-CH 2 CH=CH 2 ), cyclopentenyl (-C 5 H 7 ) and 5-hexenyl (-CH 2 CH 2 CH 2 CH 2 CH=CH 2 ).

[0047] 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, such as "C 2 ~C 6 "Alkynyl" refers to an alkynyl group containing 2 to 6 carbon atoms, each occurrence of which can be independently C 2 Alkynyl, C 3 Alkynyl, C 4 Alkynyl, C 5 Alkynyl, C 6 Suitable examples include, but are not limited to, ethynyl (-C≡CH) and propargyl (-CH2 C≡CH).

[0048] In the present application, "aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom, which 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, such as "C 6 ~C 20 "Aryl" refers to an aromatic group containing 6 to 20 carbon atoms, each occurrence of which can be independently C 6 Aryl, 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.

[0049] "Alkylene" refers to a hydrocarbon group having two monovalent radical centers derived from an alkyl group by removing a hydrogen atom, which may be a saturated branched alkyl group or a saturated straight chain alkyl group. For example, "C 1 ~C 6 "Alkylene" means that the alkyl portion contains 1 to 6 carbon atoms, each occurrence can be independently C 1 Alkylene, C 4 Alkylene, C 5 Alkylene, C 6 Suitable examples include, but are not limited to, methylene (-CH 2 -), 1,1-ethyl (-CH(CH 3 )-), 1,2-ethyl (-CH 2 CH 2 -), 1,1-propyl (-CH(CH 2 CH 3 )-), 1,2-propyl (-CH 2 CH(CH 3 )-), 1,3-propyl (-CH 2 CH 2 CH 2 -) and 1,4-butyl (-CH 2 CH 2 CH 2 CH 2 -).

[0050] In a first aspect of the present application, a modified maleimide prepolymer is provided. The modified maleimide prepolymer is obtained by polymerizing a maleimide resin and an unsaturated fluorene compound.

[0051] The unsaturated fluorene-based compound includes one or more compounds having the structure shown in formula (I);

[0052] .

[0053] In formula (I), A 1 and A 2 are independently halogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl or a group represented by formula (II). 1 , A 2 At least one of them is a group represented by formula (II). 11 , R 12 are independently halogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl or C 6 ~C 20 Aromatic group.

[0054] ;

[0055] In formula (II), Cy is C 6 ~C 20 Aromatic group. 21 Single bond, O, S, C 1 ~C 6 Alkylene or C 1 ~C 6 Haloalkylene. 22 is absent, halogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl or C 6 ~C 20 Aromatic group. 23 , R 24 Each independently is a single bond, S or C 1 ~C 6 Alkylene. 25C 2 ~C 6 Alkenyl or C 2 ~C 6 Alkynyl; n is any integer from 0 to 6.

[0056] The modified maleimide prepolymer provided by the present application is obtained by polymerization of maleimide resin and unsaturated fluorenyl compound, wherein the rigid structures such as benzene ring and imide heterocycle in maleimide can provide a stable skeleton structure for the modified maleimide prepolymer after polymerization; the higher chemical bond energy of benzene ring and imide heterocycle in the skeleton structure makes it difficult to break or deform when heated, thereby giving the modified maleimide prepolymer good heat resistance. In the unsaturated fluorenyl compound of specific structure, the aromatic ring in the fluorenyl has a conjugated system, and its electron cloud distribution is relatively uniform, and its polarization degree is low under the action of electric field; in addition, under the synergistic effect of the substituent of the specific structure of the unsaturated fluorenyl compound, it can adjust the dipole moment of the unsaturated fluorenyl compound molecule, reduce the orientation polarization and relaxation polarization of the molecule in the electric field, thereby reducing dielectric loss.

[0057] Therefore, the modified maleimide prepolymer provided in the present application has both excellent heat resistance and low dielectric loss.

[0058] Furthermore, A 1 and A 2 Each is independently a group represented by formula (II). In formula (II), Cy is C 6 ~C 20 Aromatic group. 21 is a single bond. 22 is absent, halogen or C 1 ~C 6 Alkyl. 23 is a single bond or C 1 ~C 3 Alkylene. 24 is a single bond or C 1 ~C 3 Alkylene. 25 C 2 ~C 6 Alkenyl or C 2 ~C 6 Alkynyl. n is any integer from 0 to 6. For example, n is 0, 1, 2, 3, 4, 5 or 6. It is understood that the value of n is ≤ the value of the substitutable sites on the Cy ring. For example, if the Cy ring is a six-membered ring, then n is any value from 0 to 4.

[0059] Furthermore, A 1 and A 2 Each independently represents one or more of formula (III-1) to formula (III-10): , , , , , , , , , Among them, R 22 is absent, halogen or C 1 ~C 6 Alkyl. 23 is a single bond or C 1 ~C 3 Alkylene, R 24 is a single bond or C 1 ~C 3 Alkylene, n is any integer from 0 to 4.

[0060] Illustratively, the unsaturated fluorenyl compounds include , , , , and One or more of .

[0061] Further illustratively, the unsaturated fluorenyl compound includes , , and One or more of .

[0062] The unsaturated fluorenyl compound of the above structure contains multiple benzene rings in addition to the fluorenyl group. The rigid benzene ring structure is not easily deformed or the chemical bonds are broken, which helps to improve the heat resistance of the compound. In addition, the uniform electron cloud distribution of the conjugated system can further reduce the dielectric loss of the modified maleimide prepolymer.

[0063] In one example, the maleimide resin includes one or more of 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, bis(3,5-diethyl-4-maleimidophenyl)methane, polyphenylmethane bismaleimide, bismaleimide containing a biphenyl structure, bismaleimide containing a phosphorus structure, bismaleimide containing a naphthalene ring structure, bismaleimide containing an anthracene ring structure, and hyperbranched bismaleimide.

[0064] In one example, the mass ratio of the maleimide resin to the unsaturated fluorene-based compound is 1:(0.5~1.2). Within this mass ratio range, the maleimide resin can provide sufficient heat-resistant structural units to be incorporated into the modified maleimide prepolymer to ensure the stability of the modified maleimide prepolymer at high temperatures. At the same time, an appropriate amount of unsaturated fluorene-based compounds can give full play to their role in regulating dielectric properties and cooperate with the structural units of the maleimide resin; the modified maleimide prepolymer formed by the polymerization of the two at this mass ratio can not only rely on the maleimide resin to maintain high heat resistance, but also achieve lower dielectric loss with the help of unsaturated fluorene-based compounds. For example, the mass ratio of the maleimide resin to the unsaturated fluorene-based compound includes but is not limited to 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1 or 1:1.2, or within the range formed by any two of the above point values ​​as endpoint values.

[0065] The polymerization temperature plays an important role in ensuring the reactivity of the maleimide resin and the unsaturated fluorene compound and forming a stable polymer structure. In one example, the process parameters of the polymerization include: the polymerization temperature is 100°C~180°C. During the polymerization process, the appropriate temperature can connect the molecular chains of the maleimide resin and the unsaturated fluorene compound in a more orderly manner to form a modified maleimide prepolymer having a heat-resistant structure and low dielectric loss characteristics. 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 the range of endpoint values.

[0066] 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.

[0067] Furthermore, the preparation step of the modified maleimide prepolymer includes: heating the unsaturated fluorenyl compound to a molten state, adding a maleimide resin according to a mass ratio, polymerizing at 100° C. to 180° C. for 60 min to 200 min, and cooling to room temperature to prepare the modified maleimide prepolymer.

[0068] In a second aspect of the present application, a resin composition is provided, comprising the following components in parts by weight:

[0069] 30 to 70 parts of the modified maleimide prepolymer described in any one of the examples of the first aspect of the present application, 10 to 40 parts of a functional resin, 20 to 50 parts of a polyphenylene ether resin, 100 to 250 parts of a filler, and 1 to 5 parts of a curing accelerator.

[0070] It is understandable that the weight percentage of the modified maleimide prepolymer can be selected from any value between 30 and 70. For example, the weight percentage of the modified maleimide prepolymer includes but is not limited to 30, 35, 40, 45, 50, 55, 60, 65 or 70 parts, or within the range formed by any two of the above points as endpoints.

[0071] It is understandable that the weight percentage of the functional resin can be selected from any value between 10 and 40. For example, the weight percentage of the functional resin includes but is not limited to 10, 13, 15, 18, 20, 22, 25, 28, 30, 32, 35, 38 or 40 parts, or any two of the above points as the endpoint values.

[0072] It is understandable that the weight percentage of the polyphenylene ether resin can be selected from any value between 20 and 50. For example, the weight percentage of the polyphenylene ether resin includes but is not limited to 20, 25, 30, 35, 40, 45 or 50 parts, or a range consisting of any two of the above points as endpoints.

[0073] It is understandable that the weight percentage of the filler can be selected from any value between 100 and 250. For example, the weight percentage of the filler includes but is not limited to 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240 or 250 parts, or any two of the above points as the range of endpoint values.

[0074] It is understandable that the weight percentage of the curing accelerator can be selected from any value between 1 and 5. For example, the weight percentage of the curing accelerator includes, but is not limited to, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5 parts, or a range consisting of any two of the above points as endpoints.

[0075] In the resin combination provided by the present application, the modified maleimide prepolymer has excellent heat resistance and low dielectric loss. Functional resin can enhance the performance of the resin combination in specific aspects according to its own characteristics, such as flame retardant or chemical corrosion resistance, etc., to ensure the stable performance of the resin combination. The addition of polyphenylene ether resin can give the resin combination excellent electrical insulation, water resistance and mechanical properties, which can not only help to reduce dielectric loss but also improve overall strength, and then help to improve peel strength. In addition, the added filler can further reduce the thermal expansion of the resin combination, and increase the rigid structure of the resin combination, which is also conducive to the improvement of peel strength. Curing accelerator can further ensure that each component in the resin combination is fully cured, so that each component is closely combined, and it is ensured that the entire resin combination structure is stable, thereby collaboratively realizing the excellent comprehensive performance of lower thermal expansion coefficient, lower dielectric loss and higher peel strength.

[0076] In one example, the polyphenylene ether resin includes one or more of the compounds having the structure shown in formula (IV)

[0077] .

[0078] R 31 and R 33 are independently halogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 2 ~C 6 Alkenyl or C 2 ~C 6 Alkynyl.

[0079] Furthermore, R 31 and R 33 Each independently is C 1 ~C 3 Furthermore, R 31 and R 33 Each is independently -CH 3 or -CH 2 CH 3 .

[0080] R 32 Each independently does not exist, or .

[0081] Y is a single bond or C 1 ~C 6 Alkylene; m1 and m2 are positive integers. Further, the value of m1+m2 is 5 to 60. For example, the value of m1+m2 includes but is not limited to 5, 10, 20, 30, 40, 50 or 60.

[0082] q1 is any integer from 0 to 4. q1 is 0, 1, 2, 3 or 4.

[0083] q2 is any integer from 0 to 4. q2 is 0, 1, 2, 3 or 4. Further, the polyphenylene ether resin comprises , and One or more of .

[0084] The polyphenylene ether resin of the above structure contains terminal vinyl groups or acrylate groups, etc., and has good compatibility with prepolymers and functional resins. For example, the polyphenylene ether of the above structure includes but is not limited to SABIC SA9000 and Mitsubishi Chemical OPE-1200.

[0085] In one example, the curing accelerator includes one or more of a tertiary amine accelerator, an imidazole accelerator, a peroxide accelerator, an organic phosphorus accelerator, and a transition metal carboxylate accelerator.

[0086] For example, the peroxide-based accelerator includes, but is not limited to, dicumyl peroxide.

[0087] In one example, the functional resin includes one or more of a cyanate resin, a benzoxazine resin, an epoxy resin, and a hydrocarbon resin.

[0088] It is understandable that in the present application, there is no particular restriction on the type of cyanate resin. For example, cyanate includes, but is not limited to, one or more of bisphenol A cyanate resin, phenolic cyanate resin, bisphenol F cyanate resin, bisphenol M cyanate resin, bisphenol E cyanate resin, naphthalene cyanate resin, biphenyl cyanate resin, phosphorus-containing structure cyanate resin, bisphenol S cyanate resin, and dicyclopentadiene bisphenol cyanate resin.

[0089] It is understandable that in the present application, the type of benzoxazine resin is not particularly limited. For example, the benzoxazine resin includes, but is not limited to, one or more of an allyl-type benzoxazine resin, a bisphenol A-type benzoxazine resin, a bisphenol F-type benzoxazine resin, a main-chain benzoxazine resin, a phosphorus-containing benzoxazine resin, a bisphenol S-type benzoxazine resin, a dicyclopentadiene benzoxazine resin, a biphenyl-type benzoxazine resin, a tetraphenol-based ethane benzoxazine resin, and a naphthalene-type benzoxazine resin.

[0090] It is understandable that in the present application, the type of epoxy resin is not particularly limited. For example, epoxy resin includes but is not limited to 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 type 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 one or more.

[0091] Furthermore, the functional resin is a hydrocarbon resin. Furthermore, the hydrocarbon resin is one or more of polybutadiene and butadiene-styrene copolymer.

[0092] 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.

[0093] Furthermore, the filler is silicon dioxide. Furthermore, the filler is spherical silicon dioxide.

[0094] 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.

[0095] 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.

[0096] For example, the auxiliary agent includes one or more of a dispersant, a leveling agent, a defoaming agent and a coupling agent.

[0097] According to a third aspect of the present application, a prepreg is provided, comprising a substrate and a resin composition loaded on the substrate; the resin composition is the resin composition described in any one of the examples of the second aspect of the present application.

[0098] The present application also provides a method for preparing a prepreg, comprising the following steps:

[0099] Mixing the components of the resin composition in a solvent to prepare a coating liquid;

[0100] The coating liquid is applied to the surface of the substrate and a first heating treatment is performed to prepare the prepreg.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] The fourth aspect of the present application provides a use of the prepreg described in the third aspect of the present application in the preparation of a laminate, a copper clad laminate or a wiring board.

[0107] The present application also provides a laminate, which includes the prepreg described in the above embodiment.

[0108] The present application also provides a method for preparing a laminate, comprising the following steps:

[0109] One or more prepregs are selected and laminated to prepare the laminate.

[0110] 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.

[0111] 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.

[0112] In one example, the thickness of the metal foil is 3 μm to 105 μm.

[0113] 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.

[0114] The raw materials used in the following examples and comparative examples are as follows:

[0115] [Unsaturated fluorenyl compounds]

[0116] Fluorenyl compound A, structure ;CAS: 142494-81-3; Purchased from: Kungang New Materials;

[0117] Fluorenyl compound B, structure ; Prepared with reference to CN1882632A.

[0118] [Maleimide resin]

[0119] Bismaleimide resin: purchased from Yamato Chemical Industry Co., Ltd., model number is BMI-5100.

[0120] [Functional resin]

[0121] Hydrocarbon resin: polybutadiene, purchased from Japan Soda, model B-1000;

[0122] Hydrocarbon resin: butadiene and styrene copolymer, purchased from Cray Valley Company, model R100.

[0123] [Polyphenylene ether resin]

[0124] Modified polyphenylene ether: purchased from Sabic, model SA-9000;

[0125] Modified polyphenylene ether: purchased from Mitsubishi Chemical, model OPE-1200.

[0126] [filler]

[0127] Spherical silica: purchased from Yaduma, model number is SO-C1.

[0128] [Curing accelerator]

[0129] Dicumyl peroxide (DCP): purchased from Aksu.

[0130] [Additives]

[0131] Dispersant: purchased from BYK Chemical, model ANTI-TERRA-210.

[0132] Preparation Example 1

[0133] 50 parts of fluorenyl compound 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 100 minutes and then cooled to room temperature to prepare a modified maleimide prepolymer A.

[0134] Preparation Example 2

[0135] 75 parts of fluorenyl compound A were heated to a molten state, and then 100 parts of bismaleimide resin were added, and the mixture was prepolymerized at 165° C. for 120 minutes and then cooled to room temperature to prepare a modified maleimide prepolymer B.

[0136] Preparation Example 3

[0137] 100 parts of fluorenyl compound A were heated to a molten state, and then 100 parts of bismaleimide resin were added, and the mixture was prepolymerized at 170° C. for 120 minutes and then cooled to room temperature to prepare a modified maleimide prepolymer C.

[0138] Preparation Example 4

[0139] 50 parts of the fluorenyl compound B 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 D.

[0140] The compositions of the resin compositions provided in the examples and comparative examples are shown in Tables 1 and 2 below:

[0141] Table 1

[0142]

[0143] Table 2

[0144]

[0145] The preparation process of the resin composition of the embodiment and the comparative example is as follows:

[0146] The modified maleimide prepolymer or maleimide resin, functional resin and polyphenylene ether resin are mixed in a solvent, wherein the solvent comprises butanone, cyclohexanone and toluene in a mass ratio of 1:1:1; fillers, fixing accelerators and auxiliary agents are added under stirring conditions, and stirring is continued to prepare a resin composition.

[0147] The preparation process of the prepregs of the embodiments and comparative examples is as follows:

[0148] 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 160° C., and heated for 5 minutes to prepare a prepreg.

[0149] The preparation process of the copper clad laminate of the embodiment and the comparative example is as follows:

[0150] 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 35 kgf / cm 2 The temperature was 220° C. and the pressurization was performed for 3 hours to prepare a copper-clad laminate with a thickness of about 0.85 mm.

[0151] Performance Tests of Copper Clad Laminates of Examples and Comparative Examples

[0152] 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".

[0153] 2. Peel strength: Tested using a universal tensile testing machine in accordance with IPC-TM-650 2.4.8.

[0154] 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.

[0155] 4. Thermal expansion coefficient test and expansion rate in the X / Y / Z axis direction: Measured by TA instrument company's TA Q800 thermal expansion analyzer, the measuring temperature is 50℃~260℃, the heating rate is 10℃ / min, and the thermal expansion coefficient and expansion rate of the sample in the Y / Z axis direction are tested.

[0156] 5. Dielectric constant and dielectric loss measurement: Agilent E5071C network analyzer was used to measure the dielectric constant (Dk) and dielectric loss (Df) at an operating frequency of 10 GHz according to IPC-TM650 2.5.5.2.

[0157] The test results of the copper-clad laminates of the above embodiments and comparative examples are shown in Tables 3 and 4 below:

[0158] Table 3

[0159]

[0160] Table 4

[0161]

[0162] In Comparative Example 1, maleimide resin is selected instead of the modified maleimide prepolymer selected in Examples 1 to 6 of the present application, resulting in poor compatibility of the copper-clad laminate prepared in Comparative Example 1, and lower peel strength, glass transition temperature, etc. compared with Examples 1 to 6; and the thermal expansion performance and dielectric properties of Comparative Example 1 are higher than those of Examples 1 to 6, which indicates that the comprehensive performance of the copper-clad laminate prepared in Comparative Example 1 is lower than that of Examples 1 to 6. In Comparative Example 2, the prepolymer selected is fluorene-based compound B and bismaleimide resin, and the copper-clad laminate prepared therefrom has a higher thermal expansion coefficient, a larger dielectric coefficient and a larger dielectric loss, and its comprehensive performance is worse than that of the examples.

[0163] In Example 6, due to the high weight percentage of the modified maleimide prepolymer, its comprehensive performance is slightly worse than that of Examples 1 to 5. Example 7 is basically the same as Example 2, the main difference being that a butadiene styrene copolymer is selected in Example 7, and the thermal expansion performance and dielectric properties of Example 7 are slightly worse than those of Example 2. Example 8 is basically the same as Example 2, the main difference being that the polyphenylene ether resin selected in Example 8 is only vinyl terminated, and its dielectric constant is slightly lower than that of Example 2.

[0164] 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.

[0165] 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 modified maleimide prepolymer, characterized in that: The modified maleimide prepolymer is obtained by polymerizing a maleimide resin and an unsaturated fluorene compound; The unsaturated fluorene-based compound includes one or more compounds having the structure shown in formula (I); ； In formula (I), A1 and A2 are each independently halogen, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 alkynyl or a group represented by formula (II); and at least one of A1 and A2 is a group represented by formula (II); R 11 , R 12 Each of them is independently halogen, C1~C6 alkyl, C1~C6 haloalkyl, C2~C6 alkenyl, C2~C6 alkynyl or C6~C 20 Aromatic group; ； In formula (II), Cy is C6~C 20 Aromatic group; R 21 is a single bond, O, S, C1~C6 alkylene or C1~C6 halogenated alkylene; R 22 is absent, halogen, C1~C6 alkyl, C1~C6 haloalkyl, C2~C6 alkenyl, C2~C6 alkynyl or C6~C 20 Aromatic group; R 23 , R 24 Each independently represents a single bond, S or a C1~C6 alkylene group; R 25 is a C2~C6 alkenyl or C2~C6 alkynyl group; n is any integer from 0 to 6.

2. The modified maleimide prepolymer according to claim 1, characterized in that A1 and A2 are each independently a group represented by formula (II); wherein Cy is C6~C 20 Aromatic group, R 21 is a single bond, R 22 is absent, halogen or C1~C6 alkyl, R 23 is a single bond or a C1~C3 alkylene group, R 24 is a single bond or a C1~C3 alkylene group, R 25 is a C2~C6 alkenyl or C2~C6 alkynyl group; n is any integer from 0 to 6.

3. The modified maleimide prepolymer according to claim 1, characterized in that: A1 and A2 are each independently one or more of formula (III-1) to formula (III-10): , , , , , , , , , ; Among them, R 22 is absent, halogen or C1~C6 alkyl, R 23 is a single bond or a C1~C3 alkylene group, R 24 is a single bond or a C1~C3 alkylene group, and n is any integer from 0 to 4.

4. The modified maleimide prepolymer according to any one of claims 1 to 3, characterized in that: The modified maleimide prepolymer has one or more of the following characteristics: (1) The maleimide resin includes one or more of 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, bis(3,5-diethyl-4-maleimidophenyl)methane, polyphenylmethane bismaleimide, bismaleimide containing a biphenyl structure, bismaleimide containing a phosphorus structure, bismaleimide containing a naphthalene ring structure, bismaleimide containing an anthracene ring structure, and hyperbranched bismaleimide; (2) The mass ratio of the maleimide resin to the unsaturated fluorene compound is 1:(0.5-1.2); (3) The process parameters of the polymerization include: the polymerization temperature is 100°C~180°C.

5. A resin composition, characterized in that In parts by weight, it includes the following components: 30 to 70 parts of the modified maleimide prepolymer according to any one of claims 1 to 4, 10 to 40 parts of a functional resin, 20 to 50 parts of a polyphenylene ether resin, 100 to 250 parts of a filler, and 1 to 5 parts of a curing accelerator.

6. The resin composition according to claim 5, wherein the polyphenylene ether resin comprises one or more compounds having a structure represented by formula (IV); R 31 and R 33 Each is independently halogen, C1~C6 alkyl, C1~C6 haloalkyl, C2~C6 alkenyl or C2~C6 alkynyl; q1 is any integer from 0 to 4, q2 is any integer from 0 to 4; R 32 Each independently does not exist, or ; Y is a single bond or a C1~C6 alkylene group; m1 and m2 are positive integers.

7. The resin composition according to claim 5 or 6, characterized in that The resin composition has one or more of the following characteristics: (1) The curing accelerator includes one or more of a tertiary amine accelerator, an imidazole accelerator, a peroxide accelerator, an organic phosphorus accelerator and a transition metal carboxylate accelerator; (2) The functional resin includes one or more of cyanate resin, benzoxazine resin, epoxy resin and hydrocarbon resin.

8. The resin composition according to claim 5 or 6, characterized in that The resin composition further comprises 1 to 5 parts of an auxiliary agent by weight, wherein the auxiliary agent comprises one or more of a dispersant, a leveling agent, a defoaming agent and a coupling agent.

9. A prepreg, characterized in that: The prepreg comprises a substrate and a resin composition loaded on the substrate; the resin composition is the resin composition according to any one of claims 5 to 7.

10. Use of the prepreg according to claim 9 in preparing a laminate, a copper clad laminate or a wiring board.

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